CN115894535A - Polycyclic aromatic compound, multimer thereof, material for organic device, organic electroluminescent element, and application thereof - Google Patents

Polycyclic aromatic compound, multimer thereof, material for organic device, organic electroluminescent element, and application thereof Download PDF

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CN115894535A
CN115894535A CN202211168536.5A CN202211168536A CN115894535A CN 115894535 A CN115894535 A CN 115894535A CN 202211168536 A CN202211168536 A CN 202211168536A CN 115894535 A CN115894535 A CN 115894535A
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carbon atoms
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heteroaryl
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畠山琢次
前田健永
田中裕之
田端敬太
森绚子
东真人
马场大辅
南凌
小林孝弘
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Kwansei Gakuin Educational Foundation
SK Materials JNC Co Ltd
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SK Materials JNC Co Ltd
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    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
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    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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Abstract

The invention provides a novel polycyclic aromatic compound and a polymer thereof, a material for an organic device, an organic electroluminescent element and an application thereof. The polycyclic aromatic compound represented by the general formula (1) increases the options for materials for organic devices. In addition, by using the novel material, for example, an organic EL element is provided. The A ring, B ring, and C ring are optionally substituted aryl or heteroaryl rings, Y 1 B (boron), etc., X 1 And X 2 The compound of formula (1) has adamantyl group represented by formula (G), rg is hydrogen or a substituent, and not all Rg are hydrogen, for > N-R, etc. [ chemical 286 ]]
Figure DDA0003862503660000011

Description

Polycyclic aromatic compound, polymer thereof, material for organic device, organic electroluminescent element, and application thereof
Technical Field
The present invention relates to a polycyclic aromatic compound and a multimer thereof, and an organic device such as an organic electroluminescent element, an organic field effect transistor, an organic thin-film solar cell, and a wavelength conversion filter, a display device, and a lighting device using the same. In the present specification, the "polycyclic aromatic compound" and the "multimer" thereof may be collectively referred to as the "polycyclic aromatic compound", and the "organic electroluminescent element" may be referred to as the "organic EL element" or simply as the "element".
Background
Conventionally, various studies have been made on display devices using light emitting elements that emit light by an electric field, because they can achieve power saving and reduction in thickness, and further, organic electroluminescent elements including organic materials have been actively studied because they are easy to reduce the weight and increase the size. In particular, active studies have been made so far on the development of an organic material having light-emitting characteristics such as blue, which is one of the three primary colors of light, and on the development of an organic material having charge transport capability (having a possibility of becoming a semiconductor or a superconductor) including holes, electrons, and the like, both of high-molecular compounds and low-molecular compounds.
An organic Electroluminescence (EL) element has a structure including: a pair of electrodes including an anode and a cathode, and one or more layers which are disposed between the pair of electrodes and include an organic compound. The layer containing an organic compound includes a light-emitting layer, a charge transporting/injecting layer for transporting or injecting charges such as holes and electrons, and various organic materials suitable for the layers have been developed.
For example, as a material used for an organic EL device or an organic thin film solar cell, a material obtained by improving a triphenylamine derivative has been reported (international publication No. 2012/118164). The material is as follows: referring to N, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1'-biphenyl-4,4' -diamine (N, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1'-biphenyl-4,4' -diamine, TPD), which has been put into practical use, aromatic rings constituting triphenylamine are linked to each other, whereby nitrogen is disposed at the center of the ring structure and the planarity thereof is improved. In the above-mentioned document, for example, the charge transport properties of the NO-linked compound (compound 1 on page 63) were evaluated, but there is NO description of a method for producing a material other than the NO-linked compound, and the properties obtained by a material other than the NO-linked compound are unknown because the electron state of the whole compound differs depending on the elements to be linked.
The host material of an organic EL device is generally a molecule in which a plurality of conventional aromatic rings such as benzene and carbazole are connected by a single bond, a phosphorus atom, or a silicon atom. This is because a large Highest Occupied Molecular Orbital (HOMO) -Lowest Unoccupied Molecular Orbital (LUMO) gap (band gap Eg in the thin film) required for the host material is ensured by linking a large number of aromatic rings having a smaller conjugated system. Furthermore, high triplet excitation energy (E) is also required for the host material of an organic EL device using a phosphorescent material or a thermally active delayed fluorescence material T ) However, by linking an aromatic ring or a substituent group of an acceptor or an acceptor to the molecule, a Single Occupied Molecular Orbital (SOMO) 1 and SOMO2 in a triplet excited state (T1) are localized, and exchange interaction between the two orbitals is reduced, whereby triplet excitation energy (E) can be increased T ). However, the redox stability of the aromatic ring having a small conjugated system is insufficient, and the life of the device using a molecule connecting the conventional aromatic rings as a host material is insufficient. On the other hand, polycyclic aromatic compounds having extended pi-conjugated systems generally have excellent redox stability, but are attributed to HOMO-LUMO gaps (band gap Eg in thin films) or triplet excitation energy (E) T ) Low and therefore is considered unsuitable for the host material.
Under such circumstances, in recent years, a compound obtained by condensing a plurality of aromatic rings with boron or the like as a central atom has been reported (international publication No. 2015/102118). In the above document, evaluation of an organic EL element using the compound obtained by condensing a plurality of aromatic rings as a dopant material of a light-emitting layer was carried out. Further, there have been reported examples in which such a compound is further increased in amount (International publication No. 2018/212169) or examples in which a conjugated system is extended in the molecule via a linker (Korean patent laid-open Nos. 10-2020-0121228 and 2020/217229).
[ Prior art documents ]
[ patent document ]
[ patent document 1] International publication No. 2012/118164
[ patent document 2] International publication No. 2015/102118
[ patent document 3] International publication No. 2018/212169
[ patent document 4] Korean laid-open patent No. 10-2020-0121228
[ patent document 5] International publication No. 2020/217229
Disclosure of Invention
[ problems to be solved by the invention ]
As reported in patent documents 1 to 5, various materials have been developed as materials used for organic EL devices, but in order to increase the selection of materials for organic EL devices, it is desired to develop materials containing compounds different from those used in the past. In particular, it is useful to search for organic EL characteristics obtained from materials other than NO-linking compounds in which nitrogen is disposed at the center of a ring structure, and methods for producing the same.
Further, patent documents 2 to 5 report polycyclic aromatic compounds containing boron and organic EL devices using the same, but these documents disclose a very large number of compounds, and it is useful to search for materials for a light-emitting layer, particularly dopant materials, which can improve organic EL characteristics such as light emission efficiency and device lifetime, in order to further improve device characteristics.
Further, as a method for forming an organic layer constituting an organic EL element, a wet film formation method is currently used in addition to a vacuum deposition method, and therefore, development of an ink material for wet film formation for forming a hole injection layer, a hole transport layer, and a light emitting layer is actively carried out, and it is also advantageous to search for such an ink material.
[ means for solving the problems ]
As a result of diligent research directed toward solving the above problems, the present inventors have found that an excellent organic EL element can be obtained by disposing a layer containing a polycyclic aromatic compound having a novel structure between a pair of electrodes to form, for example, an organic EL element, and have completed the present invention. That is, the present invention provides the following polycyclic aromatic compound, and further provides a material for an organic device such as a material for an organic EL element containing the following polycyclic aromatic compound.
In the present specification, the chemical structure or the substituent is sometimes represented by a carbon number, but the carbon number in the case of substituting a substituent on the chemical structure or in the case of further substituting a substituent on the substituent means the carbon number of each of the chemical structure or the substituent, and does not mean the total carbon number of the chemical structure and the substituent or the total carbon number of the substituent and the substituent. For example, the "substituent B having a carbon number Y substituted with the substituent a having a carbon number X" means that the "substituent a having a carbon number X" is substituted with the "substituent B having a carbon number Y, and the carbon number Y is not the total carbon number of the substituent a and the substituent B. For example, the "substituent B having a carbon number Y substituted with the substituent a" means that the substituent a "(not limited to a carbon number) is substituted with the" substituent B having a carbon number Y "and the carbon number Y is not the total carbon number of the substituent a and the substituent B.
Item 1.
Disclosed is a polycyclic aromatic compound represented by the general formula (1) below or a polymer of the polycyclic aromatic compound having a plurality of unit structures represented by the general formula (1) below.
[ solution 15]
Figure BDA0003862503640000031
In the formula (1), the reaction mixture is,
ring A, ring B, and ring C are each independently an aryl or heteroaryl ring, at least one hydrogen in these rings may be substituted,
Y 1 Is > B-, > P (= O) -, > P (= S) -, > Al-, > Ga-, > As-, > Si (-R) -, or > Ge (-R) -, wherein R of "> Si (-R) -" and R of "> Ge (-R) -" are independently aryl which may be substituted, heteroaryl which may be substituted, alkyl which may be substituted, or cycloalkyl which may be substituted,
X 1 and X 2 Independently from each other > N-R, > O, > S, > C (-R) 2 、＞Si(-R) 2 Or > Se, said "> R of N-R" > C (-R) 2 "R, and" > Si (-R) 2 R of "are each independently hydrogen, aryl which may be substituted, heteroaryl which may be substituted, alkyl which may be substituted, or cycloalkyl which may be substituted,
in addition, as X 1 And X 2 Said "> C (-R) 2 "two R of each other and" > Si (-R) 2 "two R's may be independently bonded to each other via a linking group,
in addition, as X 1 And X 2 The "> R of N-R" > C (-R) 2 "R, and" > Si (-R) 2 R of "" may be independently bonded to at least one of the A ring, the B ring, and the C ring via a linking group, respectively,
at least one hydrogen in the compound or unit structure represented by the formula (1) is substituted with a group represented by the formula (G),
in the formula (G), the compound represented by the formula (G),
rg are each independently hydrogen or a substituent, wherein not all Rg are hydrogen,
* Is a bonding position with the compound or unit structure represented by the formula (1),
at least one of the A ring, B ring, C ring, aryl group, and heteroaryl group in the compound or unit structure represented by the formula (1) may be condensed with at least one cycloalkane, at least one hydrogen in the cycloalkane may be substituted, and at least one of the cycloalkanes — -CH 2 - "may be substituted by" -O- ", and,
at least one hydrogen in the compound or unit structure represented by the formula (1) may be substituted with deuterium, cyano, or halogen.
Item 2.
The polycyclic aromatic compound or the multimer thereof according to item 1, wherein in the formula (1),
the A ring, the B ring, and the C ring are each independently an aryl ring or a heteroaryl ring, at least one hydrogen in these rings may be substituted independently by an aryl group which may be substituted, a heteroaryl group which may be substituted, a diarylamino group which may be substituted, a diheteroarylamino group which may be substituted, a diarylboron group which may be substituted, an alkyl group which may be substituted, a cycloalkyl group which may be substituted, an alkenyl group which may be substituted, an alkoxy group which may be substituted, an aryloxy group which may be substituted, an arylthio group which may be substituted, or a substituted silyl group, two aryl groups of the diarylamino group may be bonded via a linking group, two heteroaryl groups of the diheteroarylamino group may be bonded via a linking group, an aryl group and a heteroaryl group of the arylheteroarylamino group may be bonded via a linking group, two aryl groups of the diarylboron group may be bonded via a linking group,
Y 1 R > B-, > P (= O) -, > P (= S) -, > Al-, > Ga-, > As-, > Si (-R) -, or > Ge (-R) -, said R > Si (-R) - "and R > Ge (-R) -" being independently aryl, heteroaryl, alkyl, or cycloalkyl, respectively, at least one of the hydrogens of the R being independently substituted with alkyl or cycloalkyl, respectively,
X 1 and X 2 Independently from each other > N-R, > O, > S, > C (-R) 2 、＞Si(-R) 2 Or > Se, said "> R of N-R" > C (-R) 2 "R, and" > Si (-R) 2 "each R of which is independently hydrogen, aryl, heteroaryl, alkyl, or cycloalkyl, at least one hydrogen of said R may be independently substituted with aryl, alkyl, or cycloalkyl which may be substituted with alkyl or cycloalkyl,
in addition, as X 1 And X 2 Said "> C (-R) 2 "two R of each other and" > Si (-R) 2 "two R' S may each independently of one another be bound via a single bond, -CH = CH-," C-CR = CR-, -C ≡ C-, -N (-R) -, -O-, -S-, -C (-R) 2 -、-Si(-R) 2 a-or-Se-bond, R of the "-CR = CR-", "-N (-R) -", and "-C (-R) 2 - "R, and" -Si (-R) 2 - "R's are each independently hydrogen, aryl, heteroaryl, alkyl, alkenyl, alkynyl, or cycloalkyl, at least one of which may be independently substituted with alkyl or cycloalkyl, and two adjacent R's may be bonded to each other to each independently form a cycloalkylene ring, an arylene ring, or a heteroarylene ring,
In addition, as X 1 And X 2 The "> R of N-R" > C (-R) 2 "R, and" > Si (-R) 2 R of "may each independently be via a single bond, -CH = CH-, -CR = CR-, -C.ident.C-, -N (-R) -, -O-, -S-, -C (-R) 2 -、-Si(-R) 2 -, or-Se-bonded to at least one of the A ring, the B ring, and the C ring, R of the "-CR = CR-", "-R of the" -N (-R) - "," -C (-R) 2 - "R, and" -Si (-R) 2 - "R's are each independently hydrogen, aryl, heteroaryl, alkyl, alkenyl, alkynyl, or cycloalkyl, at least one of which may be independently substituted with alkyl or cycloalkyl, and two adjacent R's may be bonded to each other to each independently form a cycloalkylene ring, an arylene ring, or a heteroarylene ring,
at least one hydrogen in the compound or unit structure represented by the formula (1) is substituted with a group represented by the formula (G),
in the formula (G), the compound represented by the formula (G),
rg is each independently hydrogen, an aryl group which may be substituted, a heteroaryl group which may be substituted, a diarylamino group which may be substituted, a diheteroarylamino group which may be substituted, an arylheteroarylamino group which may be substituted, a diarylboron group which may be substituted, an alkyl group which may be substituted, a cycloalkyl group which may be substituted, an alkenyl group which may be substituted, an alkoxy group which may be substituted, an aryloxy group which may be substituted, an arylthio group which may be substituted, a substituted silyl group, or halogen, two aryl groups of the diarylamino group may be bonded via a linking group, two heteroaryl groups of the diheteroarylamino group may be bonded via a linking group, an aryl group and a heteroaryl group of the arylheteroarylamino group may be bonded via a linking group, two aryl groups of the diarylboron group may be bonded via a linking group, wherein Rg is not all hydrogen,
* Is a bonding position with the compound or unit structure represented by the formula (1),
at least one of the A ring, B ring, C ring, aryl group and heteroaryl group in the compound or unit structure represented by the formula (1) may be condensed with at least one cycloalkane, at least one hydrogen in the cycloalkane may be independently substituted with an aryl group, a heteroaryl group, an alkyl group or a cycloalkyl group, respectively, and at least one-CH in the cycloalkane 2 - "may be substituted by" -O- ", and,
at least one hydrogen in the compound or unit structure represented by the formula (1) may be substituted with deuterium, cyano, or halogen.
Item 3.
The polycyclic aromatic compound or the multimer thereof according to item 1, wherein the general formula (1) is represented by the following general formula (2).
[ solution 16]
Figure BDA0003862503640000051
In the formula (2), the reaction mixture is,
R 1 ～R 11 each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboron, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, or alkylbicycloalkylsilyl, R 1 ～R 11 At least one hydrogen in the diarylamino group can be independently substituted with an aryl group, a heteroaryl group, an alkyl group, or a cycloalkyl group, two aryl groups of the diarylamino group can be bonded via a linking group, two heteroaryl groups of the diheteroarylamino group can be bonded via a linking group, an aryl group and a heteroaryl group of the arylheteroarylamino group can be bonded via a linking group, two aryl groups of the diarylboron group can be bonded via a linking group,
In addition, R 1 ～R 3 、R 4 ～R 7 And R 8 ～R 11 Wherein adjacent groups in (a) may be bonded to each other and form an aryl ring or a heteroaryl ring together with the a-ring, the b-ring, and the c-ring, respectively, at least one hydrogen in the formed ring may be independently substituted with an aryl group, a heteroaryl group, a diarylamino group, a diheteroarylamino group, a diarylboron group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group, an arylthio group, a triarylsilyl group, a trialkylsilyl group, a tricycloalkylsilyl group, a dialkylcycloalkylsilyl group, or an alkylbicycloalkylsilyl group, at least one of these substituents may be independently substituted with an aryl group, a heteroaryl group, an alkyl group, or a cycloalkyl group, two aryl groups of the diarylamino group may be bonded via a linking group, two heteroaryl groups of the diheteroarylamino group may be bonded via a linking group, an aryl group and a heteroaryl group of the arylheteroarylamino group may be bonded via a linking group, two aryl groups of the diarylboron group may be bonded via a linking group,
any of the rings a, b and C "-C (-R) =" (where R is R) 1 ～R 11 ) May be substituted with "-N =", optionally "-C (-R) = C (-R) -" (where R is R 1 ～R 11 ) May be substituted by "-N (-R) -", "-O-", "-S-", "-C (-R) 2 -”、“-Si(-R) 2 - ", or" -Se- ", the R of" -N (-R) - ", the" -C (-R) 2 - "R, and" -Si (-R) 2 - "R are each independently hydrogen, aryl, heteroaryl, alkyl, or cycloalkyl, at least one of said R hydrogens may each be independently substituted with alkyl or cycloalkyl, and said" -C (-R) 2 - "two R of each other and" -Si (-R) 2 Two R of-can each independently be via a single bond, -CH = CH-) -CR = CR-, -C ≡ C-, -N (-R) -, -O-, -S-, -C (-R) 2 -、-Si(-R) 2 -, or-Se-is bonded, R of the "-CR = CR-", "-N (-R) -", and "-C (-R) 2 R of- "and" -Si (-R) 2 R of-are each independently hydrogen, aryl, heteroaryl, alkyl, alkenyl, alkynyl, or cycloalkyl, and at least one of the hydrogens may each independently be taken through alkyl or cycloalkylSubstituted, two adjacent R groups may be bonded to each other to form a cycloalkylene ring, an arylene ring, or a heteroarylene ring, respectively and independently,
Y 1 is > B-, > P (= O) -, or > P (= S) -,
X 1 and X 2 Each independently > N-R, > O, > S, or > C (-R) 2 R of "> N-R" and "> C (-R) 2 "each R of which is independently hydrogen, aryl, heteroaryl, alkyl, or cycloalkyl, at least one hydrogen of said R may be independently substituted with aryl, alkyl, or cycloalkyl which may be substituted with alkyl or cycloalkyl,
In addition, as X 1 And X 2 Said "> C (-R) 2 "two R' S may be bonded to each other via a single bond, -CH = CH-, -CR = CR-) -C.ident.C-, -N (-R) -, -O-, -S-, -C (-R) 2 -、-Si(-R) 2 a-or-Se-bond, R of the "-CR = CR-", "-R of the" -N (-R) - "," -C (-R) 2 R of- "and" -Si (-R) 2 - "R's are each independently hydrogen, aryl, heteroaryl, alkyl, alkenyl, alkynyl, or cycloalkyl, at least one of which may be independently substituted with alkyl or cycloalkyl, and two adjacent R's may be bonded to each other to each independently form a cycloalkylene ring, an arylene ring, or a heteroarylene ring,
in addition, as X 1 And X 2 R of "> N-R" and "> C (-R) 2 R of "may be independently selected from the group consisting of a single bond, -CH = CH-, -CR = CR-," and-C.ident.C-, -N (-R) -, -O-, -S-, -C (-R) 2 -、-Si(-R) 2 -, or-Se-bonded to at least one of the a ring, the b ring, and the C ring, R of the "-CR = CR-", "-R of the" -N (-R) - "," -C (-R) 2 R of- "and" -Si (-R) 2 - "R's are each independently hydrogen, aryl, heteroaryl, alkyl, alkenyl, alkynyl, or cycloalkyl, at least one of which may be independently substituted with alkyl or cycloalkyl, and two adjacent R's may be bonded to each other to each independently form a cycloalkylene ring, an arylene ring, or a heteroarylene ring,
At least one hydrogen in the compound or unit structure represented by the formula (2) is substituted with a group represented by the formula (G),
in the formula (G), the reaction mixture is,
rg are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, alkylbicycloalkylsilyl, or halogen, at least one of Rg is each independently substituted with aryl, heteroaryl, alkyl, or cycloalkyl, two aryl groups of the diarylamino can be bonded via a linking group, two heteroaryl groups of the diheteroarylamino can be bonded via a linking group, aryl and heteroaryl groups of the arylheteroarylamino can be hydrogen bonded via a linking group, two aryl groups of the diarylboryl can be Rg bonded via a linking group, wherein not all are hydrogen,
* Is a bonding position with the compound or unit structure represented by the formula (2),
at least one of the a-ring, b-ring, c-ring, formed ring, aryl group, and heteroaryl group in the compound or unit structure represented by the formula (2) may be condensed with at least one cycloalkane, at least one of hydrogens in the cycloalkane may be independently substituted with an aryl group, a heteroaryl group, an alkyl group, or a cycloalkyl group, respectively, and at least one of the cycloalkanes "-CH 2 - "may be substituted by" -O- ", and,
at least one hydrogen in the compound or unit structure represented by the formula (2) may be substituted with deuterium, cyano, or halogen.
Item 4.
The polycyclic aromatic compound or the multimer thereof according to item 3, wherein in the formula (2),
R 1 ～R 11 independently represents hydrogen, aryl group having 6 to 30 carbon atoms, heteroaryl group having 2 to 30 carbon atoms, diarylamino group (wherein the aryl group is aryl group having 6 to 12 carbon atoms), diheteroarylamino group (wherein the heteroaryl group is heteroaryl group having 2 to 15 carbon atoms), arylheteroarylamino group (wherein the aryl group is aryl group having 6 to 12 carbon atoms, and the heteroaryl group is heteroaryl group having 6 to 12 carbon atoms)A heteroaryl group having 2 to 15 carbon atoms), a diarylboron group (wherein the aryl group is an aryl group having 6 to 12 carbon atoms), an alkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms, an alkenyl group having 1 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an arylthio group having 6 to 30 carbon atoms, a triarylsilyl group (wherein the aryl group is an aryl group having 6 to 12 carbon atoms), a trialkylsilyl group (wherein the alkyl group is an alkyl group having 1 to 12 carbon atoms), a tricycloalkylsilyl group (wherein the cycloalkyl group is a cycloalkyl group having 3 to 12 carbon atoms), a dialkylcycloalkylsilyl group (wherein the alkyl group is an alkyl group having 1 to 12 carbon atoms and the cycloalkyl group is a cycloalkyl group having 3 to 12 carbon atoms), or an alkylbicycloalkylsilyl group (wherein the alkyl group is an alkyl group having 1 to 12 carbon atoms and the cycloalkyl group is a cycloalkyl group having 3 to 12 carbon atoms), R 1 ～R 11 Wherein at least one hydrogen in the alkyl group is independently substituted with an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 14 carbon atoms,
in addition, R 1 ～R 3 、R 4 ～R 7 And R 8 ～R 11 Wherein adjacent groups in (a) may be bonded to each other and form an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms together with the a ring, the b ring, and the c ring, respectively, at least one hydrogen in the formed rings may independently be an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a diarylamino group (wherein the aryl group is an aryl group having 6 to 12 carbon atoms), a diheteroarylamino group (wherein the heteroaryl group is an aryl group having 2 to 15 carbon atoms, a heteroaryl group is a heteroaryl group having 2 to 15 carbon atoms), a diarylboron group (wherein the aryl group is an aryl group having 6 to 12 carbon atoms), an alkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms, an alkenyl group having 1 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an arylthio group having 6 to 30 carbon atoms, a triarylsilyl group (wherein the aryl group is an aryl group having 6 to 12 carbon atoms), a trialkylsilyl group (wherein the alkyl group has 1 to 12 carbon atoms), a cycloalkylalkyl group having 3 to 12 carbon atoms, or a cycloalkyl group (wherein the cycloalkyl group has 3 to 12 carbon atoms), a cycloalkyl group is an alkyl group having 3 to 12 carbon atoms, or a cycloalkyl group At least one hydrogen of these substituents may be independently substituted by an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 14 carbon atoms,
any of the rings a, b and C "-C (-R) =" (where R is R) 1 ～R 11 ) May be substituted with "-N =", optionally "-C (-R) = C (-R) -" (where R is R) 1 ～R 11 ) May be substituted with "-N (-R) -", "-O-", "-S-", "-C (-R) 2 -”、“-Si(-R) 2 - ", or" -Se- ", the R of" -N (-R) - ", the" -C (-R) 2 - "R, and" -Si (-R) 2 - "wherein R is each independently hydrogen, aryl having 6 to 12 carbon atoms, heteroaryl having 2 to 15 carbon atoms, alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms, at least one hydrogen in the R may be independently substituted by alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms," -C (-R) 2 - "two R of each other and" -Si (-R) 2 Two R of-can each independently be via a single bond, -CH = CH-) -CR = CR-, -C ≡ C-, -N (-R) -, -O-, -S-, -C (-R) 2 -、-Si(-R) 2 -, or-Se-is bonded, R of the "-CR = CR-", "-N (-R) -", and "-C (-R) 2 R of- "and" -Si (-R) 2 R in the formula- "is independently hydrogen, aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 10 carbon atoms, alkyl having 1 to 5 carbon atoms, alkenyl having 1 to 5 carbon atoms, alkynyl having 1 to 5 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, at least one of the hydrogens in the R may be independently substituted with alkyl having 1 to 5 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, and two adjacent Rs may be bonded to each other to independently form cycloalkylene ring having 3 to 14 carbon atoms, arylene ring having 6 to 12 carbon atoms or heteroarylene ring having 2 to 15 carbon atoms,
Y 1 Is > B-, > P (= O) -, or > P (= S) -,
X 1 and X 2 Each independently > N-R, > O, > S, or > C (-R) 2 R of "> N-R" and "> C (-R) 2 R's are each independently hydrogen, aryl having 6 to 18 carbon atoms, heteroaryl having 2 to 15 carbon atoms, alkyl having 1 to 6 carbon atoms, or alkyl having 3 to 14 carbon atomsA cycloalkyl group, wherein at least one hydrogen in R is independently substituted by an aryl group having 6 to 18 carbon atoms, an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 14 carbon atoms, which may be substituted by an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 14 carbon atoms,
in addition, as X 1 And X 2 Said "> C (-R) 2 "two R' S may be linked to each other via a single bond, -CH = CH-, -CR = CR-, -C.ident.C-, -N (-R) -, -O-, -S-, -C (-R) 2 -、-Si(-R) 2 -, or-Se-is bonded, R of the "-CR = CR-", "-N (-R) -", and "-C (-R) 2 R of- "and" -Si (-R) 2 R in the formula- "is independently hydrogen, aryl having 6 to 12 carbon atoms, heteroaryl having 2 to 15 carbon atoms, alkyl having 1 to 6 carbon atoms, alkenyl having 1 to 6 carbon atoms, alkynyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms, at least one of the hydrogens in the R may be independently substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms, and two adjacent Rs may be bonded to each other to independently form cycloalkylene having 3 to 14 carbon atoms, arylene having 6 to 12 carbon atoms or heteroarylene having 2 to 15 carbon atoms,
In addition, as X 1 And X 2 R of "> N-R" and "> C (-R) 2 R of "may each independently be via a single bond, -CH = CH-, -CR = CR-, -C.ident.C-, -N (-R) -, -O-, -S-, -C (-R) 2 -、-Si(-R) 2 -, or-Se-bonded to at least one of the rings a, b, and C, R of the "-CR = CR-", "-N (-R) -", and "-C (-R) 2 - "R, and" -Si (-R) 2 - "wherein R is each independently hydrogen, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, an alkynyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 14 carbon atoms, at least one hydrogen in the R may be each independently substituted by an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 14 carbon atoms, and two adjacent R's may be bonded to each other to form a cycloalkylene ring having 3 to 14 carbon atoms, an arylene ring having 6 to 12 carbon atoms, or a heteroarylene ring having 2 to 15 carbon atoms,
at least one hydrogen in the compound or unit structure represented by the formula (2) is substituted with a group represented by the formula (G),
in the formula (G), the compound represented by the formula (G),
rg is independently hydrogen, aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 12 carbon atoms), diheteroarylamino (wherein heteroaryl is heteroaryl having 2 to 15 carbon atoms), arylheteroarylamino (wherein aryl is aryl having 6 to 12 carbon atoms and heteroaryl is heteroaryl having 2 to 15 carbon atoms), diarylboryl (wherein aryl is aryl having 6 to 12 carbon atoms), alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, alkenyl having 1 to 24 carbon atoms, alkoxy having 1 to 24 carbon atoms, aryloxy having 6 to 30 carbon atoms, arylthio having 6 to 30 carbon atoms, triarylsilyl (wherein aryl is aryl having 6 to 12 carbon atoms), trialkylsilyl (wherein alkyl is alkyl having 1 to 12 carbon atoms), tricycloalkylsilyl (wherein cycloalkyl is cycloalkyl having 3 to 12 carbon atoms), dialkylcycloalkylsilyl (wherein alkyl has 1 to 12 carbon atoms and cycloalkyl has 3 to 12 carbon atoms), or alkylbicycloalkylsilyl (wherein alkyl has 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms is cycloalkyl having 3 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, aryl having 3 to 12 carbon atoms, halogen, aryl having 3 to 12 carbon atoms, aryl groups, wherein the alkyl group is substituted by at least one of hydrogen, halogen,
* Is a bonding position with the compound or unit structure represented by the formula (2),
at least one of the a-ring, b-ring, c-ring, ring formed, aryl group and heteroaryl group in the compound represented by the formula (2) or the unit structure may be condensed with at least one cycloalkane having 3 to 24 carbon atoms, at least one hydrogen in the cycloalkane may be independently substituted with an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 16 carbon atoms, and at least one ″ -CH in the cycloalkane may be substituted with an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 16 carbon atoms 2 - "may be substituted by" -O- ",
in the case of multimers, dimers or trimers having two or three unit structures represented by formula (2), and,
at least one hydrogen in the compound or unit structure represented by the formula (2) may be substituted with deuterium, cyano, or halogen.
Item 5.
The polycyclic aromatic compound or the multimer thereof according to item 3, wherein in the formula (2),
R 1 ～R 11 independently represents hydrogen, aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 12 carbon atoms), diheteroarylamino (wherein heteroaryl is heteroaryl having 2 to 15 carbon atoms), alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 24 carbon atoms (wherein adamantyl is excluded), alkoxy having 1 to 24 carbon atoms, aryloxy having 6 to 30 carbon atoms or arylthio having 6 to 30 carbon atoms, R 1 ～R 11 Wherein at least one hydrogen in the above-mentioned group (a) is independently substituted with an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 14 carbon atoms (excluding adamantyl groups),
in addition, R 1 ～R 3 、R 4 ～R 7 And R 8 ～R 11 Wherein adjacent groups in (a) may be bonded to each other and form an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms together with the a ring, the b ring and the c ring, respectively, at least one hydrogen in the formed rings may be independently substituted with an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a diarylamino group (wherein the aryl group is an aryl group having 6 to 12 carbon atoms), a diheteroarylamino group (wherein the heteroaryl group is a heteroaryl group having 2 to 15 carbon atoms), an alkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms (wherein adamantyl group is excluded), an alkoxy group having 1 to 24 carbon atoms, an aryloxy group having 6 to 30 carbon atoms or an arylthio group having 6 to 30 carbon atoms, and at least one hydrogen in these substituents may be independently substituted with an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 14 carbon atoms (wherein adamantyl group is excluded),
any of the rings a, b and C "-C (-R) =" (where R is R) 1 ～R 11 ) May be substituted with "-N =", optionally "-C (-R) = C (-R) -" (where R is R 1 ～R 11 ) Can be substituted into "-N (-R) -", "-O-", or "-S-", wherein R of the "-N (-R) -" is hydrogen, aryl with 6-12 carbon atoms, carbon atomA heteroaryl group having 2 to 15 carbon atoms, an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 14 carbon atoms (excluding adamantyl groups),
Y 1 is > B-, > P (= O) -, or > P (= S) -,
X 1 and X 2 Each independently represents > N-R, > O, or > S, wherein R of > N-R' is each independently hydrogen, aryl having 6 to 18 carbon atoms, heteroaryl having 2 to 15 carbon atoms, alkyl having 1 to 6 carbon atoms, or cycloalkyl having 3 to 14 carbon atoms (excluding adamantyl), and at least one of R is each independently substituted with aryl having 6 to 18 carbon atoms, alkyl having 1 to 6 carbon atoms, or cycloalkyl having 3 to 14 carbon atoms (excluding adamantyl), which may be substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms (excluding adamantyl),
in addition, as X 1 And X 2 R of said "> N-R" may each independently be via a single bond, -CH = CH-) -CR = CR-, -C ≡ C-, -N (-R) -, -O-, -S-, -C (-R) 2 -、-Si(-R) 2 -, or-Se-bonded to at least one of the rings a, b, and C, R of the "-CR = CR-", "-N (-R) -", and "-C (-R) 2 - "R, and" -Si (-R) 2 R of the formula- "is independently hydrogen, aryl group having 6 to 12 carbon atoms, heteroaryl group having 2 to 15 carbon atoms, alkyl group having 1 to 6 carbon atoms, alkenyl group having 1 to 6 carbon atoms, alkynyl group having 1 to 6 carbon atoms or cycloalkyl group having 3 to 14 carbon atoms (except adamantyl group),
at least one hydrogen in the compound or unit structure represented by the formula (2) is substituted with a group represented by the formula (G),
in the formula (G), the compound represented by the formula (G),
rg is independently hydrogen, aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 12 carbon atoms), diheteroarylamino (wherein heteroaryl is heteroaryl having 2 to 15 carbon atoms), alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 24 carbon atoms (wherein adamantyl is excluded), alkoxy having 1 to 24 carbon atoms, aryloxy having 6 to 30 carbon atoms, arylthio having 6 to 30 carbon atoms, or halogen, at least one hydrogen in Rg is independently substituted with aryl having 6 to 12 carbon atoms, heteroaryl having 2 to 15 carbon atoms, alkyl having 1 to 6 carbon atoms, or cycloalkyl having 3 to 14 carbon atoms (wherein adamantyl is excluded), wherein not all Rg are hydrogen,
* Is a bonding position with the compound or unit structure represented by the formula (2),
at least one of the a-ring, b-ring, c-ring, ring formed, aryl group and heteroaryl group in the compound or unit structure represented by the formula (2) may be condensed with at least one cycloalkane having 3 to 24 carbon atoms, wherein at least one hydrogen in the cycloalkane may be independently substituted with an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 16 carbon atoms,
In the case of multimers, dimers or trimers having two or three unit structures represented by formula (2), and,
at least one hydrogen in the compound or unit structure represented by the formula (2) may be substituted with deuterium, cyano, or halogen.
Item 6.
The polycyclic aromatic compound or the multimer thereof according to any one of items 1 to 5, wherein the X 1 And X 2 Is > N-R, X 1 And X 2 R or X of > N-R 1 And X 2 Two of R > N-R, i.e. "aryl" or "heteroaryl", are substituted with a group represented by the formula (G).
Item 7.
The polycyclic aromatic compound or the multimer thereof according to item 6, wherein said B-ring and C-ring, or said B-ring and C-ring, are condensed with cycloalkanes, at least one hydrogen in said cycloalkane being substituted, at least one of said cycloalkanes "-CH 2 - "may be substituted by" -O- ".
Item 8.
The polycyclic aromatic compound or the multimer thereof according to item 6 or item 7, wherein the X 1 And X 2 Wherein one R > N-R, that is, at least one hydrogen in the "aryl" or "heteroaryl" group is substituted with a group represented by the formula (G), and the other R > N-R is a group represented by the following formula (A) or formula (B).
[ solution 17]
Figure BDA0003862503640000101
In the formula (A) and the formula (B),
x is > N-R, > O, > S, > C (-R) 2 、＞Si(-R) 2 Or > Se, said "> R of N-R" > C (-R) 2 "R, and" > Si (-R) 2 R of "are each independently hydrogen, aryl which may be substituted, heteroaryl which may be substituted, alkyl which may be substituted, or cycloalkyl which may be substituted,
further, the "> C (-R) as X 2 "two R of each other and" > Si (-R) 2 "two R's may be independently bonded to each other via a linking group,
R a and R b Each independently is hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, or alkylbicycloalkylsilyl, R a And R b At least one hydrogen in the diarylamino group can be independently substituted with an aryl group, a heteroaryl group, an alkyl group, or a cycloalkyl group, two aryl groups of the diarylamino group can be bonded via a linking group, two heteroaryl groups of the diheteroarylamino group can be bonded via a linking group, an aryl group and a heteroaryl group of the arylheteroarylamino group can be bonded via a linking group, two aryl groups of the diarylboron group can be bonded via a linking group,
In addition, R a Or R b May be bonded to each other and form, together with the a1 ring and the b1 ring, an aryl ring or a heteroaryl ring, respectively, at least one hydrogen in the formed ring being independently aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboron, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, or heteroaryl, respectivelySilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, or alkylbicycloalkylsilyl, at least one of which may be independently substituted with aryl, heteroaryl, alkyl, or cycloalkyl, respectively, two aryl groups of the diarylamino group may be bonded via a linking group, two heteroaryl groups of the diheteroarylamino group may be bonded via a linking group, an aryl group and a heteroaryl group of the arylheteroarylamino group may be bonded via a linking group, two aryl groups of the diarylboron group may be bonded via a linking group,
any of the rings of a 1-C (-R) a ) = ", or any of the b1 rings" -C (-R) b ) = "may be substituted for" -N = ", and,
the group represented by the formula (A) is represented by R or any R > N-R as X a Is a position of (A) and is X 1 Or X 2 Is > N-R, the radical of formula (B) being any R b Is a position of (A) and is X 1 Or X 2 N-R.
Item 9.
The polycyclic aromatic compound or the multimer thereof according to claim 8, wherein at least one of the rings B and C, or at least one of the rings B and C is a heteroaryl ring.
Item 10.
The polycyclic aromatic compound according to claim 1, which is represented by any one of the following structural formulae.
[ formula 18]
Figure BDA0003862503640000111
[ solution 19]
Figure BDA0003862503640000121
[ solution 20]
Figure BDA0003862503640000131
[ solution 21]
Figure BDA0003862503640000141
[ solution 22]
Figure BDA0003862503640000151
[ solution 23]
Figure BDA0003862503640000161
[ formula 24]
Figure BDA0003862503640000171
[ solution 25]
Figure BDA0003862503640000172
[ chemical 26]
Figure BDA0003862503640000181
[ chemical No. 27]
Figure BDA0003862503640000191
[ solution 28]
Figure BDA0003862503640000201
Item 11.
A material for organic devices, comprising the polycyclic aromatic compound according to any one of items 1 to 10 or a multimer thereof.
Item 12.
The material for an organic device according to claim 11, which is a material for an organic electroluminescent element, a material for an organic field effect transistor, a material for an organic thin-film solar cell, or a material for a wavelength conversion filter.
Item 13.
The material for organic devices according to item 12, wherein the material for organic electroluminescent elements is a material for light-emitting layers.
Item 14.
An organic electroluminescent element comprising: a pair of electrodes including an anode and a cathode; and an organic layer disposed between the pair of electrodes, the organic layer containing the polycyclic aromatic compound according to any one of items 1 to 10 or a multimer thereof.
Item 15.
The organic electric field light-emitting element according to item 14, wherein the organic layer is a light-emitting layer.
Item 16.
A display device or a lighting device, comprising the organic electroluminescent element according to item 14 or item 15.
Item 17.
A wavelength conversion filter comprising the material for a wavelength conversion filter according to item 12.
[ Effect of the invention ]
According to a preferred embodiment of the present invention, there is provided a polycyclic aromatic compound having a novel structure which is useful as a material for an organic device such as a material for an organic EL element, and an excellent organic device such as an organic EL element can be provided by using the polycyclic aromatic compound.
Specifically, the present inventors have found that a polycyclic aromatic compound in which aromatic rings are connected by heterogeneous elements such as boron, nitrogen, oxygen, and sulfur has a large HOMO-LUMO gap (a band gap Eg in a thin film). The reason is considered to be that: the 6-membered ring containing a hetero element has low aromaticity, and the reduction of the HOMO-LUMO gap accompanying the expansion of the conjugated system is suppressed. Further, it was found that the HOMO-LUMO gap can be arbitrarily changed depending on the type of the hetero element and the connection method. This is considered to be because the energy of HOMO or LUMO varies arbitrarily according to the spatial expansion and energy of the free orbitals or lone electron pairs of the heterogeneous elements.
Since these polycyclic aromatic compounds locally exist in the atoms of the excited state of SOMO1 and SOMO2 due to perturbation of electrons of the heterogeneous elements, the half-value width of the fluorescence emission peak is narrow, and when used as a dopant of an organic EL element, light emission with high color purity can be obtained. For the same reason, singlet energy (S) 1 ) And triplet energy (T) 1 ) Energy difference (Δ S) of 1 T 1 ) Becomes small, exhibits thermally active delayed fluorescence, and can achieve high efficiency when used as an emitting dopant for an organic EL element.
Furthermore, since the energies of HOMO and LUMO can be arbitrarily varied by introducing a substituent, ionization potential (ionization potential) and electron affinity (electron affinity) can be optimized according to the surrounding material. The present invention is not particularly limited to these principles.
Drawings
Fig. 1 is a schematic sectional view showing an organic EL element according to the present embodiment.
[ description of symbols ]
100: organic electroluminescent element/organic EL element
101: substrate
102: anode
103: hole injection layer
104: hole transport layer
105: luminescent layer
106: electron transport layer
107: electron injection layer
108: cathode electrode
Detailed Description
1. Polycyclic aromatic compound
< description of the overall Structure of the Compound >
The present invention is a polycyclic aromatic compound represented by the following general formula (1) or a polymer thereof, preferably a polycyclic aromatic compound represented by the following general formula (2) or a polymer thereof, characterized by having a group represented by the following general formula (G). The symbols in the following structural formulae are defined as described above, and the symbols in all the structural formulae shown after the paragraph are also defined as described above.
[ solution 29]
Figure BDA0003862503640000221
The compound of formula (1) has a structure in which rings A, B, and C are condensed on a condensed bicyclic structure, and the compound of formula (2) has a structure in which rings a, B, and C are condensed on a condensed bicyclic structure. The condensed bicyclic structure is a structure in which two 6-membered saturated hydrocarbon rings are condensed with each other, and in the structural formula, Y is contained 1 And X 1 And X 2 Thereby forming a decahydronaphthalene structure.
The group represented by the formula (G) is an adamantyl group and has three Rg groups. The group represented by formula (G) is bonded to the structure of formula (1) or formula (2) in the interior. The details of the group represented by the formula (G) will be described later.
< description of the Ring Structure and substituents thereof in the Compound >
The a ring, the B ring, and the C ring in formula (1) are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings may be substituted with a substituent (except piperidinyl). The substituent is preferably an aryl group which may be substituted, a heteroaryl group which may be substituted, a diarylamino group which may be substituted, a diheteroarylamino group which may be substituted, an arylheteroarylamino group (an amino group having an aryl group and a heteroaryl group), a diarylboron group which may be substituted, an alkyl group which may be substituted, a cycloalkyl group which may be substituted, an alkenyl group which may be substituted, an alkoxy group which may be substituted, an aryloxy group which may be substituted, an arylthio group which may be substituted, or a substituted silyl group. In the case where these substituents further have a substituent, as the substituent, there may be mentioned: aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, or substituted silyl groups, and preferably, aryl, heteroaryl, alkyl, or cycloalkyl groups are listed. Further, details regarding the rings or substituents listed herein will be described together later.
In the description of formula (1), the two aryl groups of the diarylamino group may be bonded via a linking group, the two heteroaryl groups of the diheteroarylamino group may be bonded via a linking group, the aryl and heteroaryl groups of the arylheteroarylamino group may be bonded via a linking group, and the two aryl groups of the diarylboron group may be bonded via a linking group. Details regarding the manner of the linking group or linkage will be described later.
R in the formula (2) 1 ～R 11 Is hydrogen or a substituent, and specifically, is preferably hydrogen, a substitutable aryl group, a substitutable heteroaryl group, a substitutable diarylamino group, a substitutable diheteroarylamino group, a substitutable arylheteroarylamino group (an amino group having an aryl group and a heteroaryl group), a substitutable diarylboron group, a substitutable alkyl group, a substitutable cycloalkyl group, a substitutable alkenyl group, a substitutable alkoxy group, a substitutable aryloxy group, a substitutable arylthio group, or a substituted silyl group. In the case where these substituents further have a substituent, as the substituent, there may be mentioned: aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, or substituted silyl groups, and preferably, aryl, heteroaryl, alkyl, or cycloalkyl groups are listed. Further, details regarding the rings or substituents listed herein will be described together later.
In the description of formula (2), the two aryl groups of the diarylamino group may be bonded via a linking group, the two heteroaryl groups of the diheteroarylamino group may be bonded via a linking group, the aryl and heteroaryl groups of the arylheteroarylamino group may be bonded via a linking group, and the two aryl groups of the diarylboron group may be bonded via a linking group. Details regarding the manner of the linking group or linkage will be described later.
R in the formula (2) 1 ～R 11 Specific examples of (A) are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, or alkylbicycloalkylsilyl, and R is 1 ～R 11 At least one hydrogen in (a) may be substituted with an aryl, heteroaryl, alkyl, or cycloalkyl group. Further, details regarding the substituents listed herein will be described together later.
The aryl or heteroaryl ring as the a, B, and C rings in formula (1) is preferably a 5-or 6-membered ring having a bond in common with the condensed bicyclic structure.
Here, the "6-membered ring bonded in common to the condensed bicyclic structure" means, for example, a ring a, a ring b, and a ring c (benzene ring (6-membered ring)) condensed on the condensed bicyclic structure as shown in formula (2). The aryl or heteroaryl ring (as a ring a, B, and C) having the 6-membered ring "means that the 6-membered ring is formed as a ring a, B, and C alone, or another ring is further condensed with the 6-membered ring to form a ring a, B, and C so as to include the 6-membered ring. In other words, the phrase "aryl ring or heteroaryl ring having 6-membered rings (as A, B and C rings)" as used herein means that 6-membered rings constituting all or a part of the A, B and C rings are condensed to a condensed bicyclic structure. The same explanation applies to "5-membered ring".
The A ring, B ring, and C ring in formula (1) correspond to the a ring in formula (2) and the substituent R thereof 1 Substituent R 3 B ring and substituents R thereof 4 Substituent R 7 And ring c and substituents R thereof 8 Substituent R 11 . That is, the formula (2) corresponds to a structure in which "ring a, ring B, and ring C having 6-membered rings (as benzene rings)" are selected as ring a, ring B, and ring C of the formula (1). In this sense, each ring in formula (2) is represented by the lower case letters "a", "b", and "c".
< description of the Change in Ring Structure caused by the bond of substituents to each other >
In the formula (2), the substituent R of the ring a 1 Substituent R 3 Wherein adjacent groups are adjacent to each other, and a substituent R of ring b 4 ～R 7 And a substituent R of the c ring 8 ～R 11 May be bonded to each other and together with the a-ring, b-ring, or c-ring, respectively, form an aryl or heteroaryl ring, at least one hydrogen in the formed ring may be substituted with an aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboron, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, or alkylbicycloalkylsilyl group, and at least one of these substituents may be substituted with an aryl, heteroaryl, alkyl, or cycloalkyl group. Further, details regarding the rings or substituents listed herein will be described together later.
In the description of formula (2), the two aryl groups of the diarylamino group may be bonded via a linking group, the two heteroaryl groups of the diheteroarylamino group may be bonded via a linking group, the aryl and heteroaryl groups of the arylheteroarylamino group may be bonded via a linking group, and the two aryl groups of the diarylboron group may be bonded via a linking group. Details regarding the manner of the linking group or linkage will be described later.
Therefore, the polycyclic aromatic compound of formula (2) has a structure of a ring which constitutes the compound changed as shown in the following formulae (2-fr 1) to (2-fr 3) depending on the bonding form among the substituents in the a-ring, the b-ring, and the c-ring. The A 'ring and the B' ring in each formula correspond to the A ring and the B ring in formula (1), respectively. In addition, although not shown in the following formula, the ring structure of the C-ring may be changed similarly to the C' -ring, corresponding to the C-ring in formula (1).
[ solution 30]
Figure BDA0003862503640000241
When the formula (2) is used for illustration, the A 'ring and the B' ring in the formulae (2-fr 1) to (2-fr 3) represent the substituent R of the a ring 1 Substituent R 3 Or a substituent R of the b ring 4 Substituent R 7 The adjacent groups in (1) are bonded to each other and form an aryl ring or a heteroaryl ring together with the a-ring and the b-ring, respectively (may also be referred to as a condensed ring in which other ring structures are condensed onto the a-ring or the b-ring). Substituent R of c ring 8 Substituent R 11 The adjacent groups in (1) may be bonded to each other in the same manner, and form an aryl ring or heteroaryl ring together with the C ring, and the formed ring becomes a C' ring (may be referred to as a condensed ring in which another ring structure is condensed to the C ring). Further, according to the above formula, for example, the substituent R of the a ring 3 With substituents R of ring b 4 B ring substituent R 7 With substituents R of ring c 8 And a substituent R of ring c 11 With substituents R of ring a 1 It does not correspond to "adjacent radicals to each other", these are not bonded. That is, the term "adjacent groups" refers to groups adjacent to each other on the same ring.
Specific examples of the formulae (2-fr 1) to (2-fr 3) include a structure having an a 'ring or a B' ring formed by condensation of, for example, a benzene ring, an indole ring, a pyrrole ring, a benzofuran ring, a benzothiophene ring or the like with respect to a benzene ring as the a ring or the B ring, and the formed condensed ring a 'or condensed ring B' is a naphthalene ring, a carbazole ring, an indole ring, a dibenzofuran ring, a dibenzothiophene ring or the like, respectively. The same explanation can be given for the benzene ring as the c ring.
For example, the following more specific examples of formulae (2-fr 1) to (2-fr 3) are shown.
[ solution 31]
Figure BDA0003862503640000242
The formula (2-fr 1-ex) is a specific example of the formula (2-fr 1), and is adjacent R in the a-ring of the formula (2) 1 And R 2 And bonded to form an aryl ring (naphthalene ring) represented by A' together with the a ring (benzene ring). The aryl ring formed hasThe condensed bicyclic structure has a bonded 6-membered ring (benzene ring a) in common. Further, any substituent on aryl ring A' (ring A of formula (1)) except for R 3 In addition to the above, n is also represented by R, and the upper limit of n is the maximum number that can be substituted.
The formula (2-fr 2-ex) is a specific example of the formula (2-fr 2), and is R adjacent to each other in the b-ring of the formula (2) 5 And R 6 And bonded to form a heteroaryl ring (carbazole ring) represented by B' together with the B ring (benzene ring). The heteroaryl ring formed has a 6-membered ring (phenyl ring b) that shares a bond with the condensed bicyclic structure. Further, any substituent on the aryl ring B' (ring B of formula (1)) other than R 4 And R 7 In addition to the above, n is also represented by R, and the upper limit of n is the maximum number that can be substituted.
The formula (2-fr 3-ex) is a specific example of the formula (2-fr 3), and is R adjacent to each other in the a-ring of the formula (2) 1 And R 2 Bonded to and taken together with the a ring (benzene ring) to form a heteroaryl ring (dibenzofuran ring) represented by A', adjacent R in the b ring 5 And R 6 And bonded to form an aryl ring (naphthalene ring) represented by B' together with the B ring (benzene ring). The heteroaryl and aryl rings formed have 6-membered rings (benzene ring a and benzene ring b) that are bonded in common with the condensed bicyclic structure. Further, any substituent on heteroaryl ring A '(ring A of formula (1)) and aryl ring B' (ring B of formula (1)) is divided by R 3 、R 4 And R 7 In addition to the above, n is also represented by R, and the upper limit of n is the maximum number that can be substituted.
The above remarks also apply to the substituent R of the c ring 8 Substituent R 11 The adjacent groups in (1) are bonded to each other in the same manner, and the ring structure is changed to a C' ring, and the same can be applied to all the embodiments other than the specific examples.
< central element Y in Compound 1 Description of (1) >
Y in the formulae (1) and (2) 1 Is > B-, > P (= O) -, > P (= S) -, > Al-, > Ga-, > As-, > C (-R) -, > Si (-R) -, or > Ge (-R) -. The R of "> C (-R) -", R of "> Si (-R) -", and R of "> Ge (-R) -", are each independently an aryl group which may be substituted, an aryl group which may be substitutedSubstituted heteroaryl, alkyl which may be substituted, or cycloalkyl which may be substituted, as a substituent, is preferably alkyl or cycloalkyl. In the case of > P (= O) -, > P (= S) -, > C (-R) -, > Si (-R) -, or > Ge (-R) -, the atoms bonded to the A ring (a ring), the B ring (B ring), and the C ring are P, C, si, or Ge. Y is 1 Preferably > B-, > P (= O) -, > P (= S) -, > C (-R) -, or > Si (-R) -, more preferably > B-, > P (= O) -, or > P (= S) -, particularly preferably > B-. Further, details regarding the substituents listed herein will be described together later.
< connecting element X in Compound 1 And a connecting element X 2 Description of (1) >
X in the formulae (1) and (2) 1 And X 2 Independently from each other > N-R, > O, > S, > C (-R) 2 、＞Si(-R) 2 Or > Se. R of the "> N-R" "," > C (-R) 2 "R, and" > Si (-R) 2 Each R of "is independently hydrogen, an aryl group which may be substituted, a heteroaryl group which may be substituted, an alkyl group which may be substituted, or a cycloalkyl group which may be substituted, and as a substituent, an aryl group which may be substituted by an alkyl group or a cycloalkyl group, an alkyl group, or a cycloalkyl group is preferable.
As X 1 And X 2 From the viewpoint of stability, > N-R, > O, > S, or > C (-R) is preferred 2 More preferably > N-R, > O, or > C (-R) 2 More preferably, > N-R or > O, and particularly preferably, > N-R. In addition, from the viewpoint of short-wavelength light emission, > N-R, > O, or > C (-R) is preferable 2 More preferably > O or > C (-R) 2 。
Further, details regarding the substituents listed herein will be described together later.
In addition, as X 1 And X 2 "> C (-R) 2 "two R of each other and" > Si (-R) 2 "two R's may be independently bonded to each other via a linking group. Examples of the linking group include: single bond, -CH 2 -CH 2 -、-CHR-CHR-、-CR 2 -CR 2 -、-CH＝CH-、-CR＝CR-、-C≡C-、-N(-R)-、-O-、-S-、-C(-R) 2 -、-Si(-R) 2 Examples of-Se-or-Se-include the following structures. Furthermore, the R, "-CR of the" -CHR- " 2 -CR 2 R of- "," -CR = CR- "," -R of N (-R) - "," -C (-R) 2 - "R, and" -Si (-R) 2 Each R of- "is independently hydrogen, aryl, heteroaryl, alkyl, alkenyl, alkynyl, or cycloalkyl, at least one of which may be substituted with alkyl or cycloalkyl. Further, "-CHR-CHR-", "-CR 2 -CR 2 -”、“-CR＝CR-”、“-C(-R) 2 - ", and" -Si (-R) 2 Two adjacent R in the "may bond to each other to form a cycloalkylene ring, an arylene ring, and a heteroarylene ring (refer to the rightmost structural formula in the following structural formulae). Further, details regarding the substituents listed herein will be described together later.
[ solution 32]
Figure BDA0003862503640000261
As a linking group, a group having a hydroxyl group, preferably a single bond, -CR = CR-, -N (-R) -) -O-, -S-, -C (-R) 2 -、-Si(-R) 2 -, and-Se-, more preferably a single bond, -CR = CR-, -N (-R) -) -O-, -S-, and-C (-R) 2 <xnotran> -, , -CR = CR-, -N (-R) -, -O-, -S-, -CR = CR-. </xnotran>
The position at which two R are bonded via a linking group is not particularly limited as long as it is a position at which they can be bonded, and it is preferable that they are bonded at the most adjacent positions, and for example, in the case where two R are phenyl groups, they are bonded at the positions adjacent to each other (2-position) with reference to the bonding position (1-position) of "C" or "Si" in the phenyl group (see the structural formula).
< by X 1 And X 2 Description of the Change in Ring Structure caused by bond to Ring
X in the formulae (1) and (2) 1 The "> R of N-R" > C (-R) 2 "R, and" > Si (-R) 2 R of "" may be independently bonded to at least one of the ring A (ring a) and the ring B (ring B) as X 2 The "> R of N-R" > C (-R) 2 "R, and" > Si (-R) 2 R of "" may be independently bonded to at least one of the A ring (a ring) and the C ring (C ring), respectively, via a linking group.
As X which can participate in a bond 1 And X 2 Preferably > N-R and > C (-R) 2 More preferably > N-R.
As a ring bonded to X 1 Preferably B ring (B ring), for X 2 Preferably a C-ring (C-ring).
Examples of the linking group for bonding R to the ring include: single bond, -CH 2 -CH 2 -、-CHR-CHR-、-CR 2 -CR 2 -、-CH＝CH-、-CR＝CR-、-C≡C-、-N(-R)-、-O-、-S-、-C(-R) 2 -、-Si(-R) 2 -, and-Se-, preferably a single bond, -CH = CH-, -CR = CR-,; -N (-R) -, -O-, -S-, and-C (-R) 2 <xnotran> -, , -CH = CH-, -CR = CR-, -N (-R) -, -O-, -S-, , -CR = CR-, -N (-R) -, -O-, -S-, -CR = CR-. </xnotran> Furthermore, the R, "-CR of the" -CHR- " 2 -CR 2 R of- "," -CR = CR- "," -R of N (-R) - ", and" -C (-R) 2 - "R, and" -Si (-R) 2 Each R of- "is independently hydrogen, aryl, heteroaryl, alkyl, alkenyl, alkynyl, or cycloalkyl, at least one of which may be substituted with alkyl or cycloalkyl, and two adjacent R's may be bonded to each other to form a cycloalkylene ring, an arylene ring, and a heteroarylene ring. In addition, at least one hydrogen in these rings may also be substituted by alkyl or cycloalkyl groups.
Further, details regarding the substituents listed herein will be described together later.
"as X in the formula (1) 1 And X 2 The "> R of N-R" > C (-R) 2 "R, and" > Si (-R) 2 The definition of "R of each independently bonded to at least one ring of the A ring, the B ring, and the C ring via a linking group" corresponds to the formula(2) In as X 1 And X 2 The "> R of N-R" > C (-R) 2 "R, and" > Si (-R) 2 R of "are each independently via a single bond, -CH 2 -CH 2 -、-CHR-CHR-、-CR 2 -CR 2 -、-CH＝CH-、-CR＝CR-、-C≡C-、-N(-R)-、-O-、-S-、-C(-R) 2 -、-Si(-R) 2 -, and-Se-bonded to at least one ring of the a ring, the b ring, and the c ring ".
The above-mentioned regulation can be represented by the following structural formula, for example. The substituents in the a-ring and the b-ring which change the ring structure are not shown, but actually form R in the c-ring 8 ～R 11 As such. The ring structure of the c-ring is also changed in the same manner.
[ chemical formula 33]
Figure BDA0003862503640000271
The structural formula on the left represents the following compound:
X 1 (iii) a selection of (2) (> N-R, > C (-R) 2 And > Si (-R) 2 ) R in (1) is bonded to the b ring (benzene ring) through a linking group, thereby introducing X 1 While the other ring is condensed with respect to the B ring (benzene ring) to form a B' ring,
X 2 (iii) a selection of (2) (> N-R, > C (-R) 2 And > Si (-R) 2 ) R in (A) is bonded to the a ring (benzene ring) via a linking group, thereby introducing X 2 While the other rings are condensed with respect to the a ring (benzene ring) to form an A' ring.
The condensed rings B 'and A' thus formed are, for example, rings having an azepine structure, phenoxazine rings, phenothiazine rings, carbazole rings, acridine rings, or the like. In addition, although not included in the structural formula, there are also examples in which the c-ring is bonded.
The structural formula on the right represents a more specific example of the structural formula on the left and represents the following compounds:
as X 1 R (phenyl) of > N-R is represented by "-CR = CR-" (ortho-CR = CR- "as a linking groupTwo R bonded to each other to form an aryl ring as a phenylene ring) and a B ring (benzene ring) to form a ring B' having an azepine structure surrounded by a dotted line,
as X 2 R (phenyl) of > N-R is bonded to the a ring (benzene ring) through an "O-" as a linking group to form a phenoxazine ring A' surrounded by a dotted line.
The above description is applicable to the case where the ring structure of the c-ring is changed similarly, and is applicable to all the embodiments other than the specific examples.
< description of structural changes of ring a, ring b and ring c >
In the description so far, the a-ring, b-ring, and c-ring in formula (1) have been basically described as benzene rings, but examples of aryl rings or heteroaryl rings in which these ring structures are changed to 5-or 6-membered rings other than benzene rings are described below. The description so far is understood similarly to the case where these rings are subjected to the following structural changes.
< structural changes of a Ring, b Ring, and c Ring (1) >)
any of the rings a, b and C "-C (-R) =" (where R is R) 1 ～R 11 ) May be substituted with "-N =". The following structural formula is a formula in which only a part of the a-ring, b-ring, or c-ring and its peripheral structure is extracted.
[ chemical 34]
Figure BDA0003862503640000281
As shown above, the a-ring, b-ring, or c-ring represented by the benzene ring in formula (2) may be changed to a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, or another nitrogen-containing heteroaryl ring. Further, as described above, when an adjacent group is present on the a-ring, the b-ring, or the c-ring (R on the a-ring in the structural formula) 2 And R 3 R on ring b 5 And R 6 R on ring c 9 And R 10 ) These may be bonded and form a heteroaryl ring (quinoline ring in the formula) together with the a-ring, b-ring, or c-ring,and the ring formed may be further substituted (represented by n R).
The same applies to the case where the other site is substituted with "=" N ", or the case where adjacent substituents are bonded to each other to form another heteroaryl ring.
Structural change of < a Ring (2) >
any of "-C (-R) = C (-R) -" (where R is R) in the a ring 1 ～R 3 ) May be substituted with "-N (-R) -", "-O-", "-S-", "-C (-R) 2 -”、“-Si(-R) 2 - ", or" -Se- ", the R of" -N (-R) - ", the" -C (-R) 2 R of- "and" -Si (-R) 2 R of the-is hydrogen, aryl, heteroaryl, alkyl, or cycloalkyl, at least one of which may be substituted with alkyl or cycloalkyl. Further, details regarding the substituents listed herein will be described together later.
[ solution 35]
Figure BDA0003862503640000282
The above structural formula is a formula in which only a part of the a-ring and its peripheral structure is extracted, and the wavy line showing the partial structure is omitted in order to avoid complication.
As shown above, the a ring represented as a benzene ring in formula (2) may be changed to an R-substituted pyrrole ring, furan ring, thiophene ring, other nitrogen/oxygen/sulfur/silicon/selenium-containing heteroaryl ring (5-membered ring) or aryl ring (5-membered ring).
Other sites are substituted with "-N (-R) -", "-O-", "-S-", "-C (-R) 2 -”、“-Si(-R) 2 The same applies to the cases of- ", or" -Se- ".
“-C(-R) 2 - "two R of each other and" -Si (-R) 2 Two R of- "may be each independently bonded via a linking group. Examples of the linking group include: single bond, -CH 2 -CH 2 -、-CHR-CHR-、-CR 2 -CR 2 -、-CH＝CH-、-CR＝CR-、-C≡C-、-N(-R)-、-O-、-S-、-C(-R) 2 -、-Si(-R) 2 -、or-Se-, for example, the following structures can be mentioned. Furthermore, the R, "-CR of the" -CHR- " 2 -CR 2 R of- "," -CR = CR- "," -R of N (-R) - "," -C (-R) 2 - "R, and" -Si (-R) 2 Each R of- "is independently hydrogen, aryl, heteroaryl, alkyl, alkenyl, alkynyl, or cycloalkyl, at least one of which may be substituted with alkyl or cycloalkyl. Further, "-CHR-CHR-", "-CR 2 -CR 2 -”、“-CR＝CR-”、“-C(-R) 2 - ", and" -Si (-R) 2 Two adjacent R's in the above-mentioned formula may be bonded to each other to form a cycloalkylene ring, an arylene ring, and a heteroarylene ring (see the rightmost structural formula in the following structural formulae). Further, details regarding the substituents listed herein will be described together later.
[ solution 36]
Figure BDA0003862503640000291
As the linking group, a group having a hydroxyl group, preferably a single bond, -CR = CR-, -N (-R) -) -O-, -S-, -C (-R) 2 -、-Si(-R) 2 -, and-Se-, more preferably a single bond, -CR = CR-, -N (-R) -) -O-, -S-, and-C (-R) 2 <xnotran> -, , -CR = CR-, -N (-R) -, -O-, -S-, -CR = CR-. </xnotran>
The position at which two R are bonded via a linking group is not particularly limited as long as it is a position at which they can be bonded, and it is preferable that they are bonded at the most adjacent positions, and for example, in the case where two R are phenyl groups, they are bonded at the positions adjacent to each other (2-position) with reference to the bonding position (1-position) of "C" or "Si" in the phenyl group (see the structural formula).
Structural changes of < b-Ring and c-Ring (2) >
Any of the rings b and C-C (-R) b )＝C(-R b ) - "may be substituted by" -N (-R) - "," -O- "," -S- "," -C (-R) 2 -”、“-Si(-R) 2 - ", or" -Se- ", the R of" -N (-R) - ", the" -C (-R) 2 R of- ", and" -Si-R) 2 R of-is hydrogen, aryl, heteroaryl, alkyl, or cycloalkyl, at least one of which may be substituted with alkyl or cycloalkyl. Further, details regarding the substituents listed herein will be described together later.
[ solution 37]
Figure BDA0003862503640000301
The above structural formula is a formula in which only a part of the b-ring and its peripheral structure is extracted. Structural variations can be similarly described for the c-ring.
As shown above, the b-ring and c-ring represented by the benzene ring in formula (2) may be changed to an R-substituted pyrrole ring, furan ring, thiophene ring, other nitrogen/oxygen/sulfur/silicon/selenium-containing heteroaryl ring (5-membered ring) or aryl ring (5-membered ring). In addition, as mentioned above, in the b ring and c ring on the adjacent base cases (in the formula, the remaining two adjacent R 4 And R 5 ) These may be bonded and form a heteroaryl ring (a ring such as an R-substituted indole ring, benzofuran ring or benzothiophene ring in the formula) or an aryl ring (a ring such as an indene ring) together with the b ring and c ring, and the formed ring may be further substituted (represented by n R).
Further, there are also variations as described below. Structural variations can be similarly described for the c-ring.
[ solution 38]
Figure BDA0003862503640000302
Other sites are substituted with "-N (-R) -", "-O-", "-S-", "-C (-R) 2 -”、“-Si(-R) 2 The same applies to the case of- ", or" -Se- ".
As described above, the aryl ring or heteroaryl ring in which the b-ring and c-ring represented by the benzene ring are modified in formula (2) is preferably an indene ring, indole ring, benzofuran ring, or benzothiophene ring, more preferably a benzofuran ring or benzothiophene ring, and still more preferably a benzothiophene ring.
“-C(-R) 2 Two R of- "are each other and" -Si (-R) 2 Two R of- "may be each independently bonded via a linking group. Examples of the linking group include: single bond, -CH 2 -CH 2 -、-CHR-CHR-、-CR 2 -CR 2 -、-CH＝CH-、-CR＝CR-、-C≡C-、-N(-R)-、-O-、-S-、-C(-R) 2 -、-Si(-R) 2 Examples of-Se-or-Se-include the following structures. Furthermore, the R, "-CR, of said" -CHR-CHR- " 2 -CR 2 R of- "," -CR = CR- "," -R of N (-R) - "," -C (-R) 2 - "R, and" -Si (-R) 2 Each R of-is independently hydrogen, aryl, heteroaryl, alkyl, alkenyl, alkynyl, or cycloalkyl, at least one of which may be substituted with alkyl or cycloalkyl. Further, "-CHR-CHR-", "-CR 2 -CR 2 -”、“-CR＝CR-”、“-C(-R) 2 - ", and" -Si (-R) 2 Two adjacent R in the "may bond to each other to form a cycloalkylene ring, an arylene ring, and a heteroarylene ring (refer to the rightmost structural formula in the following structural formulae). Further, details regarding the substituents listed herein will be described together later.
[ chemical 39]
Figure BDA0003862503640000311
As a linking group, a group having a hydroxyl group, preferably a single bond, -CR = CR-, -N (-R) -, or-O-, -S-, -C (-R) 2 -、-Si(-R) 2 -, and-Se-, more preferably a single bond, -CR = CR-, -N (-R) -) -O-, -S-, and-C (-R) 2 <xnotran> -, , -CR = CR-, -N (-R) -, -O-, -S-, -CR = CR-. </xnotran>
The position at which two R are bonded via a linking group is not particularly limited as long as it is a position capable of bonding, and it is preferable to bond at the most adjacent position, and for example, when two R are phenyl groups, it is preferable to bond at the positions adjacent to each other (2-position) based on the bonding position (1-position) of "C" or "Si" in the phenyl group (see the structural formula).
Description of the group represented by the formula (G) >
The group represented by the formula (G) is an adamantyl group having three Rg groups. Each Rg is independently hydrogen or a substituent, wherein not all Rg are hydrogen. Preferably, one to two of the three Rg groups are substituents and the remainder is hydrogen, and more preferably, two of the three Rg groups are substituents and the remainder is hydrogen.
As the substituent, preferred is an aryl group which may be substituted, a heteroaryl group which may be substituted, a diarylamino group which may be substituted, a diheteroarylamino group which may be substituted, an arylheteroarylamino group which may be substituted, a diarylboron group which may be substituted, an alkyl group which may be substituted, a cycloalkyl group which may be substituted, an alkenyl group which may be substituted, an alkoxy group which may be substituted, an aryloxy group which may be substituted, an arylthio group which may be substituted, a substituted silane group, or a halogen, two aryl groups of the diarylamino group may be bonded via a linking group, two heteroaryl groups of the diarylamino group may be bonded via a linking group, an aryl group and a heteroaryl group of the arylheteroarylamino group may be bonded via a linking group, and two aryl groups of the diarylboron group may be bonded via a linking group. Further, details regarding the substituents listed herein will be described together later.
More specifically, the substituent is an aryl group, a heteroaryl group, a diarylamino group, a diheteroarylamino group, an arylheteroarylamino group, a diarylboryl group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group, an arylthio group, a triarylsilyl group, a trialkylsilyl group, a tricycloalkylsilyl group, a dialkylcycloalkylsilyl group, an alkylbicycloalkylsilyl group, or a halogen, at least one of the substituents may be independently substituted with an aryl group, a heteroaryl group, an alkyl group, or a cycloalkyl group, two aryl groups of the diarylamino group may be bonded via a linking group, two heteroaryl groups of the diheteroarylamino group may be bonded via a linking group, an aryl group and a heteroaryl group of the arylheteroarylamino group may be bonded via a linking group, and two aryl groups of the diarylboryl group may be bonded via a linking group.
The substituent is more specifically an alkyl group or a halogen, preferably, for example, a methyl group or fluorine, and more preferably, a methyl group.
Further, details regarding the substituents listed herein will be described together later.
The group represented by formula (G) is bonded to an arbitrary position of the structure of formula (1) or formula (2) at x. In the polycyclic aromatic compound of formula (1) or formula (2), the number of the groups represented by formula (G) is 1 to the maximum number capable of bonding, preferably one to five, more preferably one to three, further preferably one to two, and particularly preferably one.
One embodiment of the bonding position of the group represented by formula (G) includes the following: x 1 And X 2 Is > N-R, at least one hydrogen of said > N-R (one or two > N-R) R, i.e. "aryl" or "heteroaryl", is substituted with a group represented by formula (G). In particular, there may be mentioned a mode in which at least one hydrogen of the "aryl group" is substituted by a group represented by the formula (G). The "aryl" or "heteroaryl" may be substituted, for example, with aryl, alkyl, or cycloalkyl groups which may be substituted with alkyl or cycloalkyl groups. Further, details regarding the substituents listed herein will be described together later.
R > N-R to which the group represented by the formula (G) is bonded includes "aryl groups" such as phenyl, fluorenyl, biphenyl, terphenyl, or quaterphenyl groups, and "heteroaryl groups" such as carbazolyl, dibenzothienyl, or dibenzofuranyl groups.
Specific examples of R > N-R to which the group represented by formula (G) is bonded include those represented by any one of the following formulae (RG-1) to (RG-12).
[ solution 40]
Figure BDA0003862503640000331
In the formulae (RG-1) to (RG-12), a bond site to a nitrogen atom is represented. The definition of Rg and its preferred ranges can be referred to the description in the present specification. Further, at least one hydrogen of the groups represented by the formulae (RG-1) to (RG-12) may be substituted with an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a t-butyl group). Among formulae (RG-1) to (RG-12), formulae (RG-1) to (RG-9) are preferable, formulae (RG-1) to (RG-4), formulae (RG-7), and formulae (RG-8) are more preferable, and formulae (RG-1) to (RG-4) are most preferable.
In addition, as an embodiment of the bonding position of the group represented by the formula (G), there can be mentioned a mode in which the group represented by the formula (G) is directly bonded to the a ring (a ring), the B ring (B ring), or the C ring (C ring).
< description of the Ring Or substituent >
Next, details of the ring or the substituent (including not only the first substituent but also a second substituent further substituted on the first substituent) listed in the description so far will be collectively described.
The "aryl ring" is, for example, an aryl ring having 6 to 30 carbon atoms, and is preferably an aryl ring having 6 to 20 carbon atoms, an aryl ring having 6 to 16 carbon atoms, an aryl ring having 6 to 12 carbon atoms, an aryl ring having 6 to 10 carbon atoms or the like.
The "aryl ring" as the ring A, ring B and ring C in the formula (1) corresponds to the "R" defined in the formula (2) 1 ～R 3 、R 4 ～R 7 And R 8 ～R 11 The "formed aryl ring" is an aryl ring formed by bonding adjacent groups in (a) to each other and forming a ring (a), a ring (b), and a ring (c), respectively, and the ring (a), (b), or (c) already contains a benzene ring having 6 carbon atoms, so that the total carbon number 9 of the condensed rings formed by condensing the smallest 5-membered ring on the benzene ring is the lower limit of carbon numbers.
Specific "aryl rings" are for example: a benzene ring as a monocyclic system, a naphthalene ring as a condensed bicyclic system, or an indene ring, an acenaphthene ring, a fluorene ring, a phenalene ring, a phenanthrene ring, an anthracene ring, or a 9, 10-dihydroanthracene ring as a condensed tricyclic system, a triphenylene ring, a pyrene ring, or a quaterphenyl ring as a condensed tetracyclic system, or a perylene ring or a quaterphenyl ring as a condensed pentacyclic system, and the like.
In addition, the following structures are also included in the "aryl ring": at least one hydrogen in the aryl ring is substituted with an aryl group such as a phenyl group (specifically, a group described later), an alkyl group such as a methyl group (specifically, a group described later), or a cycloalkyl group such as a cyclohexyl group or an adamantyl group (specifically, a group described later).
For example, a dimethylfluorene ring, a dimethylbenzene ring, and a dimethylindene ring in which two hydrogens of a methylene group in the fluorene ring, the benzofluorene ring, and the indene ring are substituted with methyl groups are also included in the aryl ring. In addition, a 9, 10-tetramethyl-9, 10-dihydroanthracene ring in which four hydrogens of two methylene groups in the 9, 10-dihydroanthracene ring are substituted with methyl groups is also included in the aryl ring.
The "heteroaryl ring" is, for example, a heteroaryl ring having 2 to 30 carbon atoms, preferably a heteroaryl ring having 2 to 25 carbon atoms, a heteroaryl ring having 2 to 20 carbon atoms, a heteroaryl ring having 2 to 15 carbon atoms, a heteroaryl ring having 2 to 10 carbon atoms, or the like. The "heteroaryl ring" is, for example, a heterocyclic ring containing one to five heteroatoms selected from oxygen, sulfur and nitrogen as ring-constituting atoms in addition to carbon.
Furthermore, the "heteroaryl ring" as the A ring, B ring, and C ring in formula (1) corresponds to the "R" specified in formula (2) 1 ～R 3 、R 4 ～R 7 And R 8 ～R 11 The heteroaryl ring (b) is a heteroaryl ring in which adjacent groups in (a) are bonded to each other and each of which is formed together with the a-ring, the b-ring, and the c-ring, and the "heteroaryl ring formed" is a heteroaryl ring in which the a-ring, the b-ring, or the c-ring already contains a benzene ring having 6 carbon atoms, and therefore the total carbon number of the condensed rings formed by condensing the smallest 5-membered ring on the benzene ring is 6, which is the lower limit carbon number. In the above-mentioned cases, the benzene rings, i.e., the a-ring, the b-ring, and the c-ring, may be changed to a nitrogen-containing heteroaryl ring (6-or 5-membered ring), an oxygen/sulfur-containing heteroaryl ring (5-membered ring), or the like, and therefore the number of carbons in the lower limit is changed accordingly.
Specific "heteroaryl ring" is, for example, a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an oxadiazole ring, a thiadiazole ring, a triazole ring, a tetrazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring, an indole ring, an isoindole ring, a 1H-indazole ring, a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, a 1H-benzotriazole ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinazoline ring, a quinoxaline ring, a phenanthroline ring, a phthalazine ring, a naphthyridine ring, a purine ring, a pteridine ring, a carbazole ring, an acridine ring, a phenoxathiin ring, a phenoxazine ring, a phenothiazine ring, a a phenazine ring, a phenazasillene (phenazasidine) ring, an indolizine ring, a furan ring, a benzofuran ring, an isobenzofuran ring, a dibenzofuran ring, a naphthobenzofuran ring, a xanthene ring, a thiophene ring, a benzothiophene ring, an isobenzothiophene ring, a dibenzothiophene ring, a naphthobenzothiophene ring, a thioxanthene ring, a phosphacyclopentadiene ring, a dibenzophosphacyclopentadiene ring, a benzophosphacyclopentadiene oxide ring, a furazan ring, a thianthrene ring, an indolocarbazole ring, a benzindoindolocarbazole ring, an imidazoline ring, or an oxazoline ring.
In addition, the following structures are also included in the "heteroaryl ring": at least one hydrogen in the heteroaryl ring is substituted with an aryl group such as a phenyl group (specifically, a group described later), an alkyl group such as a methyl group (specifically, a group described later), or a cycloalkyl group such as a cyclohexyl group or an adamantyl group (specifically, a group described later).
For example, a 9- (phenyl, methyl, cyclohexyl, or adamantyl) carbazole ring in which hydrogen in the 9-position of the carbazole ring is substituted with a phenyl group, a methyl group, a cyclohexyl group, or an adamantyl group is also included in the heteroaryl ring. In addition, a dimethyldihydroacridine ring, a dimethylxanthene ring, or a dimethylthioxanthene ring in which two hydrogens of a methylene group in an acridine ring, a xanthene ring, or a thioxanthene ring are substituted with methyl groups is also included in the heteroaryl ring.
The "aryl group" is, for example, an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 20 carbon atoms, an aryl group having 6 to 18 carbon atoms, an aryl group having 6 to 16 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryl group having 6 to 10 carbon atoms, or the like.
Specific "aryl" groups are for example: a phenyl group as a monocyclic system, a biphenyl group (2-biphenyl, 3-biphenyl, or 4-biphenyl) as a bicyclic system, a naphthyl group (1-naphthyl or 2-naphthyl) as a condensed bicyclic system, or an indenyl group (2-indenyl, 3-indenyl, 4-indenyl, 5-indenyl, a 6-indenyl or 7-indenyl), terphenyl groups (m-terphenyl-2 '-yl, m-terphenyl-4' -yl, m-terphenyl-5 '-yl, o-terphenyl-3' -yl, o-terphenyl-4 '-yl, p-terphenyl-2' -yl, m-terphenyl-2-yl, as tricyclic systems m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl-2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, or p-terphenyl-4-yl), an acenaphthylene- (1-, 3-, 4-, or 5-) yl, a fluorene- (1-, 2-, 3-, 4-, or 9-) yl, a phenalene- (1-or 2-) yl, a phenanthrene- (1-, 2-, 3-, 4-, or 9-) yl, or 9, 10-dihydroanthracene- (1-, 2-, 3-, 4-, 5-), 6-, 7-or 8-) group, a tetrabiphenyl group (5 ' -phenyl-m-terphenyl-2-yl, 5' -phenyl-m-terphenyl-3-yl, 5' -phenyl-m-terphenyl-4-yl, or m-tetrabiphenyl group) as a four-ring system, a triphenylene- (1-or 2-) group, a pyrene- (1-, 2-, or 4-) group, or a tetracene- (1-, 2-, or 5-) group as a condensed four-ring system, or a perylene- (1-, 2-, or 3-) group, or a pentacene- (1-, 2-, 5-, or 6-) group as a condensed five-ring system, and the like.
In addition, the following structure is also included in "aryl group": at least one hydrogen in the aryl group is substituted with an aryl group such as a phenyl group (specifically, the group mentioned above), an alkyl group such as a methyl group (specifically, a group described later), or a cycloalkyl group such as a cyclohexyl group or an adamantyl group (specifically, a group described later).
For example, a dimethylfluorenyl group, a dimethylbenzofluorenyl group, and a dimethylindenyl group in which two hydrogens of methylene groups in the fluorenyl group, the benzofluorenyl group, and the indenyl group are substituted with a methyl group are also included in the aryl group. In addition, 9, 10-tetramethyl-9, 10-dihydroanthracenyl in which four hydrogens of two methylene groups in the 9, 10-dihydroanthracenyl group are substituted with methyl groups is also included in the aryl group.
The "arylene group (ring)" is, for example, an arylene group having 6 to 30 carbon atoms, preferably an arylene group having 6 to 20 carbon atoms, an arylene group having 6 to 16 carbon atoms, an arylene group having 6 to 12 carbon atoms, an arylene group having 6 to 10 carbon atoms, or the like.
Specific examples of the "arylene group" include a structure in which one hydrogen is removed from the "aryl group" (monovalent group) to form a divalent group.
The "heteroaryl group" is, for example, a heteroaryl group having 2 to 30 carbon atoms, preferably a heteroaryl group having 2 to 25 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, or a heteroaryl group having 2 to 10 carbon atoms. The "heteroaryl group" is, for example, a monovalent group such as a heterocyclic ring containing, as a ring-constituting atom, one to five heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon.
As specific "heteroaryl", for example: monovalent benzoxazolyl, pyrazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, phenanthrolinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxathiyl, phenoxazinyl, phenothiazinyl, phenazinyl azasilyl (phenazasilinyl), indolizinyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, naphthobenzofuryl, xanthenyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, naphthobenzothienyl, benzothienyl, thioxanthyl, benzothienyl, dibenzocyclopentadienyl, phosphooxolanyl, benzooxoazolyl, benzooxoindolyl, benzothienyl, benzooxoindolyl, and the like.
In addition, the following structures are also included in "heteroaryl": at least one hydrogen in the heteroaryl group is substituted with an aryl group such as a phenyl group (specifically, the group mentioned above), an alkyl group such as a methyl group (specifically, the group mentioned below), or a cycloalkyl group such as a cyclohexyl group or an adamantyl group (specifically, the group mentioned below).
For example, 9- (phenyl, methyl, cyclohexyl, or adamantyl) carbazolyl, in which hydrogen at position 9 of carbazolyl is substituted with phenyl, methyl, cyclohexyl, or adamantyl, is also included in heteroaryl. In addition, a heteroaryl group includes a dimethyldihydroacridinyl group, a dimethylxanthenyl group, and a dimethylthioxanthyl group in which two hydrogens of a methylene group in an acridinyl group, a xanthenyl group, or a thioxanthyl group are substituted with a methyl group.
The "heteroarylene (ring)" is, for example, a heteroarylene group having 2 to 30 carbon atoms, preferably a heteroarylene group having 2 to 25 carbon atoms, a heteroarylene group having 2 to 20 carbon atoms, a heteroarylene group having 2 to 15 carbon atoms, or a heteroarylene group having 2 to 10 carbon atoms. The "heteroarylene group" is, for example, a divalent group of a heterocyclic ring or the like containing one to five heteroatoms selected from oxygen, sulfur and nitrogen as ring-structure atoms in addition to carbon.
Specific examples of the "heteroarylene group" include structures in which one hydrogen is removed from the "heteroaryl group" (monovalent group) to form a divalent group.
"diarylamino" is an amino group substituted with two aryl groups, and the details of the aryl groups can be referred to the description of the "aryl groups".
"Diheteroarylamino" is an amino group substituted with two heteroaryl groups, and the description of the "heteroaryl" can be cited for the details of the heteroaryl group.
The "arylheteroarylamino group" is an amino group substituted with an aryl group or a heteroaryl group, and the details of the aryl group or the heteroaryl group can be referred to the descriptions of the "aryl group" and the "heteroaryl group".
Two aryl groups of a "diarylamino group" may be bonded via a linking group, two heteroaryl groups of a "diheteroarylamino group" may be bonded via a linking group, and an aryl and heteroaryl group of an "arylheteroarylamino group" may be bonded via a linking group. Examples of the linking group include: single bond, -CH 2 -CH 2 -、-CHR-CHR-、-CR 2 -CR 2 -、-CH＝CH-、-CR＝CR-、-C≡C-、-N(-R)-、-O-、-S-、-C(-R) 2 -、-Si(-R) 2 -, or-Se-. Furthermore, the R, "-CR of the" -CHR- " 2 -CR 2 R of- "," -CR = CR- "," -R of N (-R) - ", and" -C (-R) 2 - "R, and" -Si (-R) 2 Each R of-is independently hydrogen, aryl, heteroaryl, alkyl, alkenyl, alkynyl, or cycloalkyl, at least one of which may be substituted with alkyl or cycloalkyl. Further, "-CHR-CHR-", "-CR 2 -CR 2 -”、“-CR＝CR-”、“-C(-R) 2 - ", and" -Si (-R) 2 Two adjacent R's in- "may be bonded to each other to form a cycloalkylene ring, an arylene ring, and a heteroarylene ring. As for details of the substituents listed here, the descriptions of the "aryl", "arylene", "heteroaryl", and "heteroarylene" and the descriptions of the "alkyl", "alkenyl", "alkynyl", "cycloalkyl", and "cycloalkylene" described later may be cited.
The "diarylboron group" is a boron group in which two aryl groups are substituted, and as details of the aryl group, the description of the "aryl group" can be cited.
Two aryl groups of the "diarylboron group" may be bonded via a linking group. Examples of the linking group include: single bond, -CH 2 -CH 2 -、-CHR-CHR-、-CR 2 -CR 2 -、-CH＝CH-、-CR＝CR-、-C≡C-、-N(-R)-、-O-、-S-、-C(-R) 2 -、-Si(-R) 2 -, or-Se-. Furthermore, the R, "-CR of the" -CHR- " 2 -CR 2 R of- "," -CR = CR- "," -R of N (-R) - "," -C (-R) 2 - "R, and" -Si (-R) 2 Each R of-is independently hydrogen, aryl, heteroaryl, alkyl, alkenyl, alkynyl, or cycloalkyl, at least one of which may be substituted with alkyl or cycloalkyl. Further, "-CHR-CHR-", "-CR 2 -CR 2 -”、“-CR＝CR-”、“-C(-R) 2 - ", and" -Si (-R) 2 Two adjacent R's in the group "may be bonded to each other to form a cycloalkylene ring, an arylene ring, and a heteroarylene ring. As for details of the substituents listed here, the descriptions of the "aryl", "arylene", "heteroaryl", and "heteroarylene" and the descriptions of the "alkyl", "alkenyl", "alkynyl", "cycloalkyl", and "cycloalkylene" described later may be cited.
The "alkyl group" may be either a straight chain or a branched chain, and is, for example, a straight-chain alkyl group having 1 to 24 carbon atoms or a branched-chain alkyl group having 3 to 24 carbon atoms, preferably an alkyl group having 1 to 18 carbon atoms (branched-chain alkyl group having 3 to 18 carbon atoms), an alkyl group having 1 to 12 carbon atoms (branched-chain alkyl group having 3 to 12 carbon atoms), an alkyl group having 1 to 6 carbon atoms (branched-chain alkyl group having 3 to 6 carbon atoms), an alkyl group having 1 to 5 carbon atoms (branched-chain alkyl group having 3 to 5 carbon atoms), an alkyl group having 1 to 4 carbon atoms (branched-chain alkyl group having 3 to 4 carbon atoms), or the like.
Specific "alkyl" groups are for example: <xnotran> , , , ,1- -1- ,1,1- ,1,1,2- ,1,1,2,2- ,1- -1,2,2- , , , , ,2- ,1,1- ,3,3- ,1,1- ,1- -1- ,1- -1- ,1,1,3- ,1- -1,3- , , , , (t-pentyl) ( (t-amyl)), 1- ,2- ,1,1- ,1- -1- ,1- -1- ,1- -1- ,1,1,4- , ,1- ,2- ,1,1- ,1- -1- ,1,1,5- ,3,5,5- , ,1- ,1- ,1,1- ,2,2- ,2,6- -4- , , (1,1,3,3- ), 1,1- , , ,1- , </xnotran> N-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, or n-eicosyl, and the like.
The "alkenyl group" refers to the explanation of the "alkyl group" and includes a group in which a C — C single bond in the structure of the "alkyl group" is substituted with a C = C double bond, and a group in which not only one but also two or more single bonds are substituted with a double bond (also referred to as a diene-group or a triene-group).
As for the "alkynyl group", reference may be made to the description of the "alkyl group" which is a group in which a single C — C bond is substituted by a triple C ≡ C bond in the structure of the "alkyl group", and a group in which not only one but two or more single bonds are substituted by a triple bond (also referred to as a diyne-group or a triyne-group) is also included.
The "cycloalkyl group" is, for example, a cycloalkyl group having 3 to 24 carbon atoms, preferably a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 16 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, or a cycloalkyl group having 5 carbon atoms. At least one hydrogen of these cycloalkyl groups may be substituted with an alkyl group (specifically, the group, such as methyl).
Specific "cycloalkyl" groups are for example: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, or an alkyl (particularly methyl) substituent having 1 to 5 or 1 to 4 carbon atoms of these groups, norbornenyl, bicyclo [1.1.0] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.1.0] pentyl, bicyclo [2.1.1] hexyl, bicyclo [3.1.0] hexyl, bicyclo [2.2.1] heptyl, bicyclo [2.2.2] octyl, adamantyl, diamantanyl, decahydronaphthyl, or decahydroazulenyl group.
Among them, the compound of the present invention has an adamantyl group represented by the formula (G), and therefore, it is preferable that the adamantyl group is removed from the definition of the cycloalkyl group as the first substituent and the second substituent.
The "cycloalkylene (ring)" is, for example, a cycloalkylene group having 3 to 24 carbon atoms, preferably a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkylene group having 3 to 16 carbon atoms, a cycloalkylene group having 3 to 14 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, a cycloalkylene group having 5 to 10 carbon atoms, a cycloalkylene group having 5 to 8 carbon atoms, a cycloalkylene group having 5 to 6 carbon atoms, or a cycloalkylene group having 5 carbon atoms.
Specific examples of the "cycloalkylene group" include a structure in which one hydrogen is removed from the "cycloalkyl group" (monovalent group) to form a divalent group.
The "alkoxy group" may be either a linear alkoxy group or a branched alkoxy group having 1 to 24 carbon atoms, for example, a linear alkoxy group having 1 to 24 carbon atoms or a branched alkoxy group having 3 to 24 carbon atoms, and preferably an alkoxy group having 1 to 18 carbon atoms (a branched alkoxy group having 3 to 18 carbon atoms), an alkoxy group having 1 to 12 carbon atoms (a branched alkoxy group having 3 to 12 carbon atoms), an alkoxy group having 1 to 6 carbon atoms (a branched alkoxy group having 3 to 6 carbon atoms), an alkoxy group having 1 to 5 carbon atoms (a branched alkoxy group having 3 to 5 carbon atoms), an alkoxy group having 1 to 4 carbon atoms (a branched alkoxy group having 3 to 4 carbon atoms), and the like.
Specific "alkoxy" groups are for example: <xnotran> , , , ,1- -1- ,1,1- ,1,1,2- ,1,1,2,2- ,1- -1,2,2- , , , , ,2- ,1,1- ,3,3- ,1,1- ,1- -1- ,1- -1- ,1,1,3- ,1- -1,3- , , , , (t-pentyloxy) ( (t-amyloxy)), 1- ,2- ,1,1- ,1- -1- ,1- -1- ,1- -1- ,1,1,4- , ,1- ,2- ,1,1- ,1- -1- ,1,1,5- ,3,5,5- , ,1- ,1- ,1,1- ,2,2- ,2,6- -4- , </xnotran> N-octyloxy, t-octyloxy (1, 3-tetramethylbutoxy), 1-dimethyloctyloxy, n-nonyloxy, n-decyloxy, 1-methyldecyloxy, n-undecyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy, or n-eicosyloxy, and the like.
The "aryloxy group" is a group represented by "Ar-O- (Ar is an aryl group)", and as for the details of the aryl group, the description of the "aryl group" can be cited.
The "arylthio group" is a group represented by "Ar-S- (Ar is an aryl group)", and with respect to the details of the aryl group, the description of the "aryl group" can be cited.
The "substituted silyl group" is, for example, a silyl group substituted with at least one of an aryl group, an alkyl group, and a cycloalkyl group, and is preferably a triarylsilyl group, a trialkylsilyl group, a tricycloalkylsilyl group, a dialkylcycloalkylsilyl group, or an alkylbicycloalkylsilyl group.
"Triarylsilyl" is a silyl group substituted with three aryl groups, and for details of the aryl groups, reference may be made to the description of the "aryl group".
Specific "triarylsilyl" groups are, for example: triphenylsilyl, diphenylmononaphthylsilyl, monophenyldinaphthylsilyl, or trinaphthylsilyl groups, and the like.
"Trialkylsilyl" is a silyl group substituted with three alkyl groups, and for details of the alkyl groups, reference may be made to the description of the "alkyl groups".
Specific "trialkylsilyl groups" are, for example: trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, triisobutylsilyl group, tri-sec-butylsilyl group, tri-tert-butylsilyl group, ethyldimethylsilyl group, n-propyldimethylsilyl group, isopropyldimethylsilyl group, n-butyldimethylsilyl group, isobutyldimethylsilyl group, sec-butyldimethylsilyl group, tert-butyldimethylsilyl group, n-propyldiethylsilyl group, isopropyl diethylsilyl group, n-butyldiethylsilyl group, tert-butyldiethylsilyl group, methyldi-n-propylsilyl group, ethyldi-n-propylsilyl group, n-butyldi-n-propylsilyl group, sec-butyldi-n-propylsilyl group, tert-butyldi-n-propylsilyl group, methyldiisopropylsilyl group, ethyldiisopropylsilyl group, n-butyldiisopropylsilyl group, sec-butyldiisopropylsilyl group, or tert-butyldiisopropylsilyl group.
"Tricycloalkylsilyl" is a silyl group substituted with three cycloalkyl groups, and for the details of the cycloalkyl groups, reference may be made to the description of the "cycloalkyl groups".
Specific "tricycloalkylsilyl group" is, for example, tricyclopentylsilyl group, tricyclohexylsilyl group or the like.
"Dialkylcycloalkylsilyl" is a silyl group substituted with two alkyl groups and one cycloalkyl group, and reference may be made to the description of the "alkyl" and "cycloalkyl" groups for details of the alkyl and cycloalkyl groups.
"Alkylbicycloalkylsilyl" is a silyl group substituted with one alkyl group and two cycloalkyl groups, and for details of the alkyl and cycloalkyl groups, reference may be made to descriptions of the "alkyl" and "cycloalkyl" groups.
Examples of the "aryl" and "heteroaryl" include a group represented by the following formula (a) or (B).
[ solution 41]
Figure BDA0003862503640000391
In the formula (A) and the formula (B),
x is > N-R, > O, > S, > C (-R) 2 、＞Si(-R) 2 Or > Se, said "> R of N-R" > C (-R) 2 "R, and" > Si (-R) 2 R of "are each independently hydrogen, aryl which may be substituted, heteroaryl which may be substituted, alkyl which may be substituted, or cycloalkyl which may be substituted,
Further, the "> C (-R) as X 2 "two R of each other and" > Si (-R) 2 "two R's may be independently bonded to each other via a linking group,
R a and R b Each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboron, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, or alkylbicycloalkylsilyl, R a And R b At least one hydrogen in the diarylamino group can be independently substituted with an aryl group, a heteroaryl group, an alkyl group, or a cycloalkyl group, two aryl groups of the diarylamino group can be bonded via a linking group, two heteroaryl groups of the diheteroarylamino group can be bonded via a linking group, an aryl group and a heteroaryl group of the arylheteroarylamino group can be bonded via a linking group, two aryl groups of the diarylboron group can be bonded via a linking group,
in addition, R a In (2) is adjacent toRadicals attached to each other, or R b Wherein adjacent groups in (a) may be bonded to each other and form an aryl ring or a heteroaryl ring together with the a1 ring and the b1 ring, respectively, at least one hydrogen in the formed ring may be independently substituted with an aryl group, a heteroaryl group, a diarylamino group, a diheteroarylamino group, an arylheteroarylamino group, a diarylboron group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group, an arylthio group, a triarylsilyl group, a trialkylsilyl group, a tricycloalkylsilyl group, a dialkylcycloalkylsilyl group, or an alkylbicycloalkylsilyl group, at least one of these substituents may be independently substituted with an aryl group, a heteroaryl group, an alkyl group, or a cycloalkyl group, two aryl groups of the diarylamino group may be bonded via a linking group, two heteroaryl groups of the diheteroarylamino group may be bonded via a linking group, an aryl group and a heteroaryl group of the arylheteroarylamino group may be bonded via a linking group, two aryl groups of the diarylboron group may be bonded via a linking group,
any of the "C (-R) s in the a1 Ring a ) = ", or any of the b1 rings" -C (-R) b ) = "may be substituted for" -N = ".
The specific description of the above definitions in the formulae (a) and (B) can refer to the same description in the formulae (1) and (2).
As an embodiment in which the group represented by formula (a) or formula (B) is bonded to a compound or a multimer thereof, the following can be mentioned: x in the formula (1) or the formula (2) 1 And X 2 Are all > N-R, and X 1 And X 2 One > R of N-R, i.e., at least one hydrogen of "aryl" or "heteroaryl", is substituted with a group represented by the formula (G), and the other > R of N-R is a group represented by the formula (A) or (B).
In the case where the group represented by the formula (A) is R or any R > N-R as X in the formula (A) a And as X in formula (1) or formula (2) 1 Or X 2 A group represented by the formula (B) is any R in the formula (B) b And as X in formula (1) or formula (2) 1 Or X 2 N-R is a nitrogen bond.
In this case, the following modes may be mentioned: at least one of the rings B and C in formula (1), or at least one of the rings B and C in formula (2) is a heteroaryl ring (e.g., a benzofuran ring or a benzothiophene ring).
The substituent (including the first substituent and the second substituent) affects the emission wavelength of the polycyclic aromatic compound by the steric resistance, electron donating property, and electron withdrawing property of the structure, and thus the emission wavelength can be adjusted by the selection of the substituent. Preferably, the group is represented by the following structural formula, more preferably methyl, t-butyl, bicyclooctyl, cyclohexyl, adamantyl, phenyl, o-tolyl, p-tolyl, 2, 4-xylyl, 2, 5-xylyl, 2, 6-xylyl, 2,4, 6-mesitylene, diphenylamino, di-p-tolylamino, bis (p- (t-butyl) phenyl) amino, diphenylboryl, ditrimethylphenylboronyl, dibenzooxaboryl, phenyldibenzodibenzodibenzothiaphenyl (phenyldibenzothiazyl), carbazolyl, 3, 6-dimethylcarbazolyl, 3, 6-di-t-butylcarbazolyl and phenoxy, further preferably methyl, t-butyl, phenyl, o-tolyl, 2, 6-xylyl, 2,4, 6-mesityl, diphenylamino, di-p-tolylamino, bis (p- (t-butyl) phenyl) amino, carbazolyl, 3, 6-dimethylcarbazolyl, 3, 6-di-t-butylcarbazolyl, and diazo-nitro. From the viewpoint of ease of synthesis, a group having a large steric hindrance is preferred for selective synthesis, and specifically, t-butyl group, o-tolyl group, p-tolyl group, 2, 4-xylyl group, 2, 5-xylyl group, 2, 6-xylyl group, 2,4, 6-mesityl group, di-p-tolylamino group, bis (p- (t-butyl) phenyl) amino group, 3, 6-dimethylcarbazolyl group, and 3, 6-di-t-butylcarbazolyl group are preferred.
In the following structural formulae, "Me" represents a methyl group, "tBu" represents a tert-butyl group, "tAm" represents a tert-pentyl group, "thoct" represents a tert-octyl group, and "-" represents a bonding position.
[ solution 42]
Figure BDA0003862503640000401
[ solution 43]
Figure BDA0003862503640000402
[ solution 44]
Figure BDA0003862503640000411
[ solution 45]
Figure BDA0003862503640000421
[ solution 46]
Figure BDA0003862503640000431
[ solution 47]
Figure BDA0003862503640000432
[ solution 48]
Figure BDA0003862503640000441
[ solution 49]
Figure BDA0003862503640000442
[ solution 50]
Figure BDA0003862503640000451
[ solution 51]
Figure BDA0003862503640000452
[ solution 52]
Figure BDA0003862503640000461
[ Hua 53]
Figure BDA0003862503640000462
[ solution 54]
Figure BDA0003862503640000471
[ solution 55]
Figure BDA0003862503640000472
[ solution 56]
Figure BDA0003862503640000481
/>
[ solution 57]
Figure BDA0003862503640000491
[ solution 58]
Figure BDA0003862503640000501
[ chemical 59]
Figure BDA0003862503640000502
[ chemical formula 60]
Figure BDA0003862503640000511
< description of multimer of polycyclic aromatic Compound >
The present invention is also directed to a polymer of a polycyclic aromatic compound having a plurality of unit structures represented by formula (1), preferably a polymer of a polycyclic aromatic compound having a plurality of unit structures represented by formula (2). The multimer is preferably a dimer to hexamer, more preferably a dimer to trimer, and particularly preferably a dimer. The polymer may be a polymer having a plurality of unit structures as long as it is a polymer having a plurality of unit structures in one compound, and for example, in addition to a form in which a plurality of unit structures are bonded by a single bond, a linking group having 1 to 3 carbon atoms such as alkylene, phenylene, naphthylene, or the like (a-ring, B-ring, or C-ring, a-ring, B-ring, or C-ring) included in the unit structure are shared by a plurality of unit structures (a-ring, B-ring, or C-ring) (ring-shared polymer), or a form in which arbitrary rings included in the unit structure (a-ring, B-ring, or C-ring), a-ring, B-ring, or C-ring) are condensed with each other (ring-condensed polymer) may be bonded, but a ring-shared polymer and a ring-condensed polymer are preferable, and a ring-shared polymer is more preferable.
Examples of such multimers include multimer compounds represented by the following formula (2 ' -M1-1), formula (2 ' -M1-2), formulae (2 ' -M2-1) to (2 ' -M2-4), and formula (2 ' -M3). The multimeric compound represented by the formula (2 '-M1-1) or the formula (2' -M1-2) is, in the case of the multimeric compound represented by the formula (2), a multimeric compound having a plurality of unit structures represented by the formula (2) in one compound structure so as to share a benzene ring as an a-ring (ring-sharing multimeric compound). In addition, the following formula (2 '-M2-1) -formula (2' -M2-4) expressed by the polymer compounds described in formula (2) is described as the b ring or c ring benzene ring, in a compound structure having a plurality of formula (2) unit structure polymer (ring shared polymer). In addition, the following formula (2' -M3) expressed polymer compounds are described as the type (2), for example, as a unit structure of b ring (or a ring, c ring) benzene ring and a unit structure of b ring (or a ring, c ring) benzene ring condensation, in a compound structure with a plurality of type (2) unit structure of polymer compounds (ring condensation type polymer).
[ solution 61]
Figure BDA0003862503640000521
The multimeric compound may be a multimeric complex in which the multimerization pattern expressed by the formula (2 ' -M1-1) or the formula (2 ' -M1-2) is combined with any one of the formulae (2 ' -M2-1) to (2 ' -M2-4) or the formula (2 ' -M3), a multimeric complex in which the multimerization pattern expressed by any one of the formulae (2 ' -M2-1) to (2 ' -M2-4) is combined with the multimerization pattern expressed by the formula (2 ' -M3), or a multimeric complex in which the multimerization pattern expressed by the formula (2 ' -M1-1) or the formula (2 ' -M1-2) is combined with the multimerization pattern expressed by any one of the formulae (2 ' -M2-1) to (2 ' -M2-4) or the multimerization pattern expressed by the formula (2 ' -M3).
< description of Cycloalkane condensation >
In addition, at least one of the aromatic ring and the heteroaromatic ring in the chemical structure of the polycyclic aromatic compound of the present invention may be condensed with at least one cycloalkane.
For example, with respect to the aryl ring and heteroaryl ring as the a, B, and C rings, the aryl (aryl moiety in aryl, diarylamino, arylheteroarylamino, diarylboron, aryloxy, arylthio, or triarylsilyl) and heteroaryl (heteroaryl moiety in heteroaryl, diheteroarylamino, or arylheteroarylamino) as the first substituent and the second substituent on these rings, the aryl ring and heteroaryl ring as the a, B, and C rings, the aryl or heteroaryl ring formed by bonding adjacent substituents in the a, B, and C rings to each other, the aryl ring or heteroaryl ring as the first substituent and the second substituent on the a, B, and C rings (the same as described above), and the heteroaryl (the same as described above), as the aryl ring and the heteroaryl ring as the Y ring 1 Aryl of R > Si (-R) - "and R > Ge (-R) -" of (1)Heteroaryl as a group X 1 And X 2 "> R of N-R" > C (-R) 2 "R, and" > Si (-R) 2 At least one of the aryl or heteroaryl group of R, the aryl group (same as described) and the heteroaryl group (same as described) as the first substituent and the second substituent on the adamantyl group of the formula (G), and the like, may be condensed with at least one cycloalkane.
Preferred examples of the aryl ring and heteroaryl ring include those as the a, B, and C rings, those as the first substituents on these rings, that is, aryl (aryl moiety in aryl, diarylamino, diarylboron, aryloxy, or arylthio) and heteroaryl (heteroaryl moiety in heteroaryl or diheteroarylamino), those as the a, B, and C rings, those as the first substituents on the a, B, and C rings (the same as above), those as the heteroaryl (the same as above), those as the first substituents on the a, B, and C rings 1 And X 2 "> R of N-R" > C (-R) 2 "R, and" > Si (-R) 2 At least one of the aryl or heteroaryl groups of R of "may be condensed with at least one cycloalkane.
More preferably, the aryl rings of ring A, ring B and ring C, the aryl (aryl moiety of aryl or diarylamino) and heteroaryl (heteroaryl moiety of heteroaryl) as the first substituents on these rings, the aryl rings of ring a, ring B and ring C, the aryl rings formed by bonding adjacent substituents in ring a, ring B and ring C, the aryl rings of ring a, ring B and ring C, the aryl (same as above) and heteroaryl (same as above) as the first substituents on ring a, ring B and ring C, and the heteroaryl (same as above) as X 1 And X 2 At least one of the aryl groups of R of "> N-R" may be condensed with at least one cycloalkane.
Further preferred are aryl rings as rings A, B and C, aryl groups as first substituents on these rings (aryl groups or aryl moieties in diarylamino groups), aryl rings as rings a, B and C, aryl groups as first substituents on rings a, B and C (the same as described above), and aryl groups as first substituents on rings X 1 And X 2 Is "At least one of the aryl groups of R > N-R "may be condensed with at least one cycloalkane.
Preferably, at least one of the aryl rings of ring B and ring C and the aryl rings of ring B and ring C is condensed with at least one cycloalkane.
Further, as an embodiment in which cycloalkane is condensed, the following can be mentioned: at X 1 And X 2 When at least one hydrogen of an "aryl" or "heteroaryl" (particularly "aryl") group which is > N-R and is R of said > N-R (one or two > N-R) is substituted with a group represented by the formula (G), both of the ring B and the ring C, or the ring B and the ring C are condensed with cycloalkane.
Examples of the "cycloalkane" include: cycloalkane having 3 to 24 carbon atoms, cycloalkane having 3 to 20 carbon atoms, cycloalkane having 3 to 16 carbon atoms, cycloalkane having 3 to 14 carbon atoms, cycloalkane having 5 to 10 carbon atoms, cycloalkane having 5 to 8 carbon atoms, cycloalkane having 5 to 6 carbon atoms, cycloalkane having 5 carbon atoms, and the like.
Specific examples of the cycloalkane include: cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, norbornene, bicyclo [1.1.0] butane, bicyclo [1.1.1] pentane, bicyclo [2.1.0] pentane, bicyclo [2.1.1] hexane, bicyclo [3.1.0] hexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, adamantane, bisadamantane, decahydronaphthalene and decahydroazulene, and alkyl (particularly methyl) substituents, halogen (particularly fluorine) substituents and deuterium substituents having 1 to 5 carbon atoms of these.
Among these, for example, a structure in which at least one hydrogen in the carbon at the α -position of cycloalkane (in cycloalkyl groups condensed with an aromatic ring or a heteroaromatic ring, the carbon at a position adjacent to the carbon at the condensation site) is substituted as shown in the following structural formula is preferable, a structure in which two hydrogens in the carbon at the α -position are substituted is more preferable, and a structure in which four hydrogens in total are substituted in the two carbons at the α -position is further preferable. Examples of the substituent include an alkyl (particularly methyl) substituent having 1 to 5 carbon atoms, a halogen (particularly fluorine) substituent, and a deuterium substituent.
[ solution 62]
Figure BDA0003862503640000541
The number of cycloalkanes condensed on one aromatic ring or heteroaromatic ring is preferably one to three, more preferably one or two, and still more preferably one. For example, an example in which one or more cycloalkanes are condensed on one benzene ring (phenyl group) is shown below. In the respective structural formulae, when benzene ring is used, it means a benzene ring included in the skeleton structure of the compound, and when phenyl group is used, it means a bond substituted in the skeleton structure of the compound. The condensed cycloalkanes may be condensed with each other as shown in the formulae (Cy-1-4) and (Cy-2-4). The same applies to the case where the condensed ring (group) is an aromatic ring or a heteroaromatic ring other than a benzene ring (phenyl group), and the case where the cycloalkane to be condensed is cyclopentane or a cycloalkane other than cyclohexane.
[ solution 63]
Figure BDA0003862503640000542
At least one-CH in cycloalkanes 2 -may be substituted by-O-. In which a plurality of-CH 2 -when substituted by-O-, adjacent-CH 2 -is not substituted by-O-. For example, the following shows one or more-CH's in cycloalkanes condensed on one benzene ring (phenyl group) 2 Examples of-O-substitution. In the respective structural formulae, when the compound is a benzene ring, the compound refers to a benzene ring included in the skeleton structure of the compound, and when the compound is a phenyl group, the compound refers to a bond substituted in the skeleton structure of the compound. The same applies to the case where the condensed ring (group) is an aromatic ring or a heteroaromatic ring other than a benzene ring (phenyl group), and the case where the cycloalkane to be condensed is cyclopentane or a cycloalkane other than cyclohexane.
[ chemical formula 64]
Figure BDA0003862503640000543
At least one hydrogen in the cycloalkane may be substituted, and as the substituent, for example: aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, substituted silyl, deuterium, cyano or halogen, wherein two aryl groups of the diarylamino may be bonded via a linking group, two heteroaryl groups of the diheteroarylamino may be bonded via a linking group, wherein an aryl group and a heteroaryl group of the arylheteroarylamino may be bonded via a linking group, and wherein two aryl groups of the diarylboryl may be bonded via a linking group, as the details of which can be cited for the description of the first substituent. Among these substituents, preferred are alkyl groups (for example, alkyl groups having 1 to 6 carbon atoms), cycloalkyl groups (for example, cycloalkyl groups having 3 to 14 carbon atoms), halogens (for example, fluorine), deuterium, and the like. In addition, when the cycloalkyl group is substituted, a spiro structure may be formed by a substitution pattern, and examples of the spiro structure formed by cycloalkane condensed on one benzene ring (phenyl group) are shown below. In the respective structural formulae, when the compound is a benzene ring, the compound refers to a benzene ring included in the skeleton structure of the compound, and when the compound is a phenyl group, the compound refers to a bond substituted in the skeleton structure of the compound.
[ solution 65]
Figure BDA0003862503640000551
Other modes of condensation of cycloalkanes include the following: the polycyclic aromatic compound represented by formula (1) or formula (2) is substituted with, for example, a diarylamino group (condensed to an aryl portion thereof) condensed with a cycloalkane, a carbazolyl group (condensed to a benzene ring portion thereof) condensed with a cycloalkane, or a benzocarbazolyl group (condensed to a benzene ring portion thereof) condensed with a cycloalkane. As the "diarylamino group", the groups described as the "first substituent" can be mentioned.
Further, as more specific examples, the following may be mentioned: polycyclic aromatic hydrocarbon represented by the formula (2)R in aromatic compounds 1 ～R 3 (particularly with respect to Y) 1 And Y 2 And is para-to R 2 ) Is a diarylamino group (condensed to its aryl moiety) condensed from a cycloalkane, or a carbazolyl group (condensed to its benzene ring moiety) condensed from a cycloalkane.
< description of substitution with deuterium, cyano, or halogen >
At least one hydrogen in the polycyclic aromatic compound of the present invention may be substituted with deuterium, cyano, or halogen. Halogen is fluorine, chlorine, bromine, or iodine, preferably fluorine, chlorine, or bromine, more preferably fluorine or chlorine.
< description of specific examples of polycyclic aromatic Compounds of the present invention >
Specific examples of the polycyclic aromatic compound include compounds represented by the following structural formulae. In the following structural formulae, "Me" represents a methyl group, "tBu" represents a tert-butyl group, and "D" represents deuterium.
[ chemical formula 66]
Figure BDA0003862503640000561
[ formula 67]
Figure BDA0003862503640000571
[ solution 68]
Figure BDA0003862503640000581
[ chemical 69]
Figure BDA0003862503640000591
[ solution 70]
Figure BDA0003862503640000601
[ solution 71]
Figure BDA0003862503640000611
[ chemical formula 72]
Figure BDA0003862503640000621
/>
[ solution 73]
Figure BDA0003862503640000631
[ chemical formula 74]
Figure BDA0003862503640000641
[ solution 75]
Figure BDA0003862503640000651
[ 76]
Figure BDA0003862503640000661
[ chemical 77]
Figure BDA0003862503640000671
[ solution 78]
Figure BDA0003862503640000681
[ solution 79]
Figure BDA0003862503640000691
[ solution 80]
Figure BDA0003862503640000701
[ solution 81]
Figure BDA0003862503640000711
[ solution 82]
Figure BDA0003862503640000721
[ solution 83]
Figure BDA0003862503640000731
[ solution 84]
Figure BDA0003862503640000741
[ solution 85]
Figure BDA0003862503640000751
[ solution 86]
Figure BDA0003862503640000761
[ solution 87]
Figure BDA0003862503640000771
[ 88]
Figure BDA0003862503640000781
[ solution 89]
Figure BDA0003862503640000791
[ solution 90]
Figure BDA0003862503640000801
[ solution 91]
Figure BDA0003862503640000811
[ solution 92]
Figure BDA0003862503640000821
[ solution 93]
Figure BDA0003862503640000831
[ chemical 94]
Figure BDA0003862503640000841
[ solution 95]
Figure BDA0003862503640000851
[ solution 96]
Figure BDA0003862503640000861
[ solution 97]
Figure BDA0003862503640000871
[ solution 98]
Figure BDA0003862503640000881
[ solution 99]
Figure BDA0003862503640000891
[ solution 100]
Figure BDA0003862503640000901
[ chemical formula 101]
Figure BDA0003862503640000911
[ solution 102]
Figure BDA0003862503640000921
[ solution 103]
Figure BDA0003862503640000931
[ solution 104]
Figure BDA0003862503640000941
[ chemical 105]
Figure BDA0003862503640000951
[ chemical 106]
Figure BDA0003862503640000952
[ chemical No. 107]
Figure BDA0003862503640000961
[ solution 108]
Figure BDA0003862503640000971
[ chemical 109]
Figure BDA0003862503640000981
[ solution 110]
Figure BDA0003862503640000991
[ solution 111]
Figure BDA0003862503640001001
[ chemical 112]
Figure BDA0003862503640001011
[ solution 113]
Figure BDA0003862503640001021
[ chemical formula 114]
Figure BDA0003862503640001031
[ solution 115]
Figure BDA0003862503640001041
[ solution 116]
Figure BDA0003862503640001051
[ solution 117]
Figure BDA0003862503640001061
Application of polycyclic aromatic compound in polymer
The polycyclic aromatic compound of the present invention may be used as a polymer compound obtained by polymerizing a reactive compound having a reactive substituent substituted in the polycyclic aromatic compound of the present invention as a monomer, or a crosslinked polymer compound obtained by further crosslinking a main chain type polymer with a reactive compound, or a suspended type polymer compound obtained by further crosslinking a reactive compound, wherein the reactive compound has a crosslinkable substituent in the polycyclic aromatic compound of the present invention as a monomer, and wherein the suspended type polymer compound has a crosslinkable substituent in the crosslinked polymer compound of the present invention (the reactive compound has a reactive substituent in the suspended type polymer compound) or a suspended type polymer compound obtained by crosslinking a reactive compound having a reactive substituent in the suspended type polymer compound of the present invention as a monomer, for example, a material for an organic electroluminescent element, a material for an organic field effect transistor, a material for an organic thin-film solar cell, or a wavelength conversion filter.
The reactive substituent (including the polymerizable substituent, the crosslinkable substituent, and the reactive substituent for obtaining a pendant polymer, hereinafter also simply referred to as "reactive substituent") is not particularly limited as long as it is a substituent capable of imparting a high molecular weight to the polycyclic aromatic compound, a substituent capable of further crosslinking the polymer compound obtained in this manner, and a substituent capable of imparting a pendant reaction to a main chain polymer. Each structural formula represents a bonding site.
[ chemical formula 118]
Figure BDA0003862503640001071
L is each independently a single bond, -O-, -S-, or C = O, -O-C (= O) -, or alkylene having 1 to 12 carbon atoms, oxyalkylene having 1 to 12 carbon atoms and polyoxyalkylene having 1 to 12 carbon atoms. Among the substituents, preferred is a group represented by formula (XLS-1), formula (XLS-2), formula (XLS-3), formula (XLS-9), formula (XLS-10) or formula (XLS-17), and more preferred is a group represented by formula (XLS-1), formula (XLS-3) or formula (XLS-17).
Such a polymer compound, a polymer crosslinked body, a pendant polymer compound, and a pendant polymer crosslinked body may contain, as a repeating unit, at least one selected from the group of compounds comprising substituted or unsubstituted triarylamine, substituted or unsubstituted fluorene, substituted or unsubstituted anthracene, substituted or unsubstituted tetracene, substituted or unsubstituted triazine, substituted or unsubstituted carbazole, substituted or unsubstituted tetraphenylsilane, substituted or unsubstituted spirofluorene, substituted or unsubstituted triphenylphosphine, substituted or unsubstituted dibenzothiophene, and substituted or unsubstituted dibenzofuran, in addition to the repeating unit containing the polycyclic aromatic compound of the present invention.
Examples of the substituent in these repeating units include: an aryl group, a heteroaryl group, a diarylamino group (two aryl groups may be bonded via a linking group), a diheteroarylamino group (two heteroaryl groups may be bonded via a linking group), an arylheteroarylamino group (an aryl group and a heteroaryl group may be bonded via a linking group), a diarylboron group (two aryl groups may be bonded via a linking group), an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, a triarylsilyl group, a trialkylsilyl group, a tricycloalkylsilyl group, a dialkylcycloalkylsilyl group, or an alkylbicycloalkylsilyl group, etc. The details of the "aryl group" of triarylamine or the substituents may be referred to the description of the polycyclic aromatic compound of the present invention.
The use of such a polymer compound, crosslinked polymer, pendant polymer compound and crosslinked pendant polymer (hereinafter, also simply referred to as "polymer compound and crosslinked polymer") will be described in detail later.
2. A method for producing a polycyclic aromatic compound represented by general formula (1) or general formula (2)
The polycyclic aromatic compound represented by the general formula (1) or the general formula (2) can be produced by a method described in a large number of conventional documents, such as International publication No. 2015/102118.
Basically, first, X is used 1 Radical and X 2 The group bonding the A ring (a ring) with the B ring (B ring) and the C ring (C ring), thereby producing an intermediate (first reaction), and thereafter, utilizing a catalyst containing the central element Y 1 The group (C) bonds the ring A (ring a), the ring B (ring B), and the ring C (ring C), whereby the final product can be produced (second reaction). In the first Reaction, a general amination Reaction such as Buchwald-Hartwig Reaction, or a general etherification Reaction such as nucleophilic substitution Reaction or Ullmann Reaction can be used. In the second Reaction, a Tandem Hetero-Friedel-Crafts Reaction (consecutive aromatic electrophilic substitution Reaction, the same applies hereinafter) can be used.
Further, a compound having a group represented by the formula (G) bonded at a desired position can be produced by using a raw material having a group represented by the formula (G) at some of these reaction steps or by adding a step of introducing a group represented by the formula (G). In addition, a compound having a desired position which is deuterated, cyanated or halogenated can be produced by using a deuterated, cyanated or halogenated starting material or by adding a deuterated, cyanated or halogenated step to the reaction step.
The second reaction is to introduce a central element Y bonding the A ring (ring a), the B ring (ring B) and the C ring (ring C) as shown in the following schemes (1) and (2) 1 The reaction of (1). First, two linking elements X are bonded by n-butyllithium, sec-butyllithium, tert-butyllithium or the like 1 And X 2 The hydrogen atoms in between undergo ortho-metallation. Subsequently, boron trichloride, boron tribromide, or the like is added to carry out lithium-boron metal exchange, and then a Bronsted base (Bronsted base) such as N, N-diisopropylethylamine is added to carry out a Tandem Border-Crafft Reaction (Tandem Bora-Friedel-Crafts Reaction), whereby a target product can be obtained. In the second reaction, a Lewis acid (Lewis acid) such as aluminum trichloride may be added to accelerate the reaction.
[ solution 119]
Flow path (1)
Figure BDA0003862503640001091
Flow (2)
Figure BDA0003862503640001092
In the above-described scheme, although the method for producing a polycyclic aromatic compound represented by formula (1) or formula (2) which is not a multimer is mainly shown, the multimer can be produced by using an intermediate having a plurality of rings a, B and C. In this case, the target product can be obtained by setting the amount of the reagent such as butyllithium to 2 times or 3 times the amount of the reagent.
Specific examples of the solvent used in the above reaction include tert-butyl benzene, xylene, and the like.
In addition, examples of the ortho-metallation reagent include: alkyllithium such as methyllithium, n-butyllithium, sec-butyllithium and tert-butyllithium, and organic basic compounds such as lithium diisopropylamide, lithium tetramethylpiperidide, lithium hexamethyldisilazide and potassium hexamethyldisilazide.
In addition, as the metal-Y 1 The metal exchange reagent of (2) includes: y is 1 Of (b) a trifluoride, Y 1 Trichloride of (a) and Y 1 Tribromide of (5), Y 1 Y being triiodide or the like 1 Halide of (2), CIPN (NEt) 2 ) 2 Equal Y 1 Of aminated halides of, Y 1 Alkoxylates of (2), Y 1 Aryloxy compounds of (a) and the like.
Further, as the bronsted base, there can be mentioned: n, N-diisopropylethylamine, triethylamine, 2, 6-tetramethylpiperidine, 1,2, 6-pentamethylpiperidine, N-dimethylaniline, N, N-dimethyltoluidine, 2, 6-lutidine, sodium tetraphenylborate, potassium tetraphenylborate, triphenylborane, tetraphenylsilane, ar 4 BNa、Ar 4 BK、Ar 3 B、Ar 4 Si (Ar is an aryl group such as phenyl) and the like.
Further, as the lewis acid, there can be mentioned: alCl 3 、AlBr 3 、AlF 3 、BF 3 ·OEt 2 、BCl 3 、BBr 3 、GaCl 3 、GaBr 3 、InCl 3 、InBr 3 、In(OTf) 3 、SnCl 4 、SnBr 4 、AgOTf、ScCl 3 、Sc(OTf) 3 、ZnCl 2 、ZnBr 2 、Zn(OTf) 2 、MgCl 2 、MgBr 2 、Mg(OTf) 2 、LiOTf、NaOTf、KOTf、Me 3 SiOTf、Cu(OTf) 2 、CuCl 2 、YCl 3 、Y(OTf) 3 、TiCl 4 、TiBr 4 、ZrCl 4 、ZrBr 4 、FeCl 3 、FeBr 3 、CoCl 3 、CoBr 3 And so on.
In each of the schemes described above, a Bronsted base or a Lewis acid may also be used in order to promote the tandem hetero-Friedel-crafts reaction. Wherein, inUsing Y 1 Of (b) a trifluoride, Y 1 Trichloride of (a) and Y 1 Tribromide of (5), Y 1 Y being triiodide or the like 1 In the case of the halide of (3), since an acid such as hydrogen fluoride, hydrogen chloride, hydrogen bromide, or hydrogen iodide is generated as the aromatic electrophilic substitution reaction proceeds, the use of a Bronsted base which traps an acid is effective. On the other hand, in the use of Y 1 Aminated halide of (2), Y 1 In the case of the alkoxylate (b), since an amine or an alcohol is produced as the aromatic electrophilic substitution reaction proceeds, it is not necessary to use a bronsted base in many cases, but since the ability to remove an amino group or an alkoxy group is low, it is effective to use a lewis acid for accelerating the removal.
3. Organic devices
In the chemical structural formulae exemplified hereinafter, "Me" represents a methyl group and "tBu" represents a tert-butyl group.
The polycyclic aromatic compound of the present invention is useful as a material for organic devices. As the organic device, for example, there can be mentioned: organic electroluminescent elements, organic field effect transistors, organic thin film solar cells, wavelength conversion filters, or the like.
3-1. Organic electroluminescent element
The polycyclic aromatic compound of the present invention is useful, for example, as a material for an organic electroluminescent element. Hereinafter, the organic EL device of the present embodiment will be described in detail with reference to the drawings. Fig. 1 is a schematic sectional view showing an organic EL element according to the present embodiment.
< Structure of organic electroluminescent element >
The organic EL element 100 shown in fig. 1 includes: the light-emitting device comprises a substrate 101, an anode 102 disposed on the substrate 101, a hole injection layer 103 disposed on the anode 102, a hole transport layer 104 disposed on the hole injection layer 103, a light-emitting layer 105 disposed on the hole transport layer 104, an electron transport layer 106 disposed on the light-emitting layer 105, an electron injection layer 107 disposed on the electron transport layer 106, and a cathode 108 disposed on the electron injection layer 107.
In addition, the organic EL element 100 may be formed by reversing the manufacturing order, for example, by a structure including: the organic light emitting diode comprises a substrate 101, a cathode 108 arranged on the substrate 101, an electron injection layer 107 arranged on the cathode 108, an electron transport layer 106 arranged on the electron injection layer 107, a light emitting layer 105 arranged on the electron transport layer 106, a hole transport layer 104 arranged on the light emitting layer 105, a hole injection layer 103 arranged on the hole transport layer 104, and an anode 102 arranged on the hole injection layer 103.
All of the layers are not indispensable, and the minimum structural unit is a structure including the anode 102, the light-emitting layer 105, and the cathode 108, and the hole injection layer 103, the hole transport layer 104, the electron transport layer 106, and the electron injection layer 107 are layers that can be arbitrarily provided. In addition, the layers may each comprise a single layer, or may comprise multiple layers.
As a method of forming the layers of the organic EL element, in addition to the structural method of "substrate/anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode", there may be mentioned a structural method of "substrate/anode/hole transport layer/light-emitting layer/electron transport layer/cathode", "substrate/anode/hole injection layer/light-emitting layer/electron transport layer/electron injection layer/cathode", "substrate/anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/cathode", "substrate/anode/light-emitting layer/electron injection layer/cathode", "substrate/anode/hole transport layer/light-emitting layer/hole injection layer/light-emitting layer/electron injection layer/cathode", "substrate/anode/hole injection layer/electron transport layer/cathode", "substrate/anode/hole injection layer/electron transport layer/electron-emitting layer/cathode", "substrate/anode/electron transport layer/electron injection layer/cathode", "substrate/cathode" and "may be mentioned.
< substrate in organic electroluminescent element >
The substrate 101 is a support of the organic EL element 100, and quartz, glass, metal, plastic, or the like is generally used. The substrate 101 is formed in a plate shape, a film shape or a sheet shape according to purposes, for example, a glass plate,Metal plates, metal foils, plastic films, plastic sheets, and the like. Among them, glass plates and plates made of transparent synthetic resins such as polyester, polymethacrylate, polycarbonate, and polysulfone are preferable. In the case of a glass substrate, soda-lime glass, alkali-free glass, or the like can be used, and the thickness is sufficient to maintain mechanical strength, and therefore, for example, it is sufficient if the thickness is 0.2mm or more. The upper limit of the thickness is, for example, 2mm or less, preferably 1mm or less. The material of the glass is preferably alkali-free glass because it is preferable that the amount of eluted ions from the glass is small, and SiO is added 2 Etc. soda lime glass for barrier coating (barrier coat) is also commercially available, and therefore the soda lime glass can be used. In addition, in order to improve the gas barrier property, a gas barrier film such as a fine silicon oxide film may be provided on at least one surface of the substrate 101, and when a synthetic resin plate, film or sheet having low gas barrier property is used as the substrate 101, it is particularly preferable to provide a gas barrier film.
< Anode in organic electroluminescent element >
The anode 102 functions to inject holes into the light-emitting layer 105. When at least one of the hole injection layer 103 and the hole transport layer 104 is provided between the anode 102 and the light-emitting layer 105, holes are injected into the light-emitting layer 105 through these layers.
As a material for forming the anode 102, an inorganic compound and an organic compound can be cited. Examples of the inorganic compound include: metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (Indium Oxide, tin Oxide, indium Tin Oxide (ITO), indium Zinc Oxide (IZO), etc.), metal halides (copper iodide, etc.), copper sulfide, carbon black, ITO glass, or NESA glass, etc. Examples of the organic compound include: polythiophene such as poly (3-methylthiophene), and conductive polymers such as polypyrrole and polyaniline. Further, the organic EL element can be used by being appropriately selected from substances used as an anode of the organic EL element.
The resistance of the transparent electrode is not limited as long as it can supply a sufficient current for light emission of the light-emitting element, but is preferably low in terms of power consumption of the light-emitting element. For example, an ITO substrate of 300 Ω/γ or less functions as an element electrode, but it is currently available as a substrate of about 10 Ω/γ, and therefore, it is particularly preferable to use a low-resistance product of, for example, 100 Ω/γ to 5 Ω/γ, preferably 50 Ω/γ to 5 Ω/γ. The thickness of ITO can be arbitrarily selected depending on the resistance value, but usually 50nm to 300nm is used in many cases.
< hole injection layer and hole transport layer in organic electroluminescent element >
The hole injection layer 103 functions to efficiently inject holes transferred from the anode 102 into the light-emitting layer 105 or the hole transport layer 104. The hole transport layer 104 functions to efficiently transport holes injected from the anode 102 or holes injected from the anode 102 through the hole injection layer 103 to the light-emitting layer 105. The hole injection layer 103 and the hole transport layer 104 are formed by laminating and mixing one or more kinds of hole injection/transport materials, or are formed by mixing a hole injection/transport material and a polymer binder. Further, an inorganic salt such as iron (III) chloride may be added to the hole injection/transport material to form a layer.
As the hole injecting/transporting substance, it is necessary to efficiently inject/transport holes from the positive electrode between the electrodes to which an electric field is applied, and it is desirable that the hole injecting efficiency is high and the injected holes are efficiently transported. Therefore, a substance which has a small ionization potential, a large hole mobility, and excellent stability and in which impurities which become traps are not easily generated at the time of production or use is preferable.
As a material (hole transport material) for forming the hole injection layer 103 and the hole transport layer 104, any compound can be selected and used from compounds conventionally used as charge transport materials for holes in photoconductive materials and conventional compounds used for hole injection layers and hole transport layers of p-type semiconductors and organic EL devices. In the present invention, as the hole transport material, a polycyclic aromatic compound represented by the general formula (1) or the general formula (2) may be used.
Specific examples of these are: carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), bis (N-aryl)Carbazole), bis-carbazole derivatives such as bis (N-alkyl carbazole), triarylamine derivatives (polymers having an aromatic tertiary amino group in the main chain or side chain, 1-bis (4-di-p-tolylaminophenyl) cyclohexane, N '-diphenyl-N, N' -bis (3-methylphenyl) -4,4 '-diaminobiphenyl, N' -diphenyl-N, N '-dinaphthyl-4, 4' -diaminobiphenyl, N '-diphenyl-N, N' -bis (3-methylphenyl) -4,4 '-diphenyl-1, 1' -diamine, N '-dinaphthyl-N, N' -diphenyl-4, 4 '-diphenyl-1, 1' -diamine, N 4 ,N 4' -diphenyl-N 4 ,N 4' -bis (9-phenyl-9H-carbazol-3-yl) - [1,1' -biphenyl]4,4' -diamine, N 4 ,N 4 ,N 4' ,N 4' -tetrakis ([ 1,1' -biphenyl)]-4-yl) - [1,1' -biphenyl]Triphenylamine derivatives such as-4, 4 '-diamine, 4' -tris (3-methylphenyl (phenyl) amino) triphenylamine, starburst amine derivatives, etc.), stilbene derivatives, phthalocyanine derivatives (metal-free, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone-based compounds, benzofuran derivatives or thiophene derivatives, oxadiazole derivatives, quinoxaline derivatives (for example, 1,4,5,8,9, 12-hexaazatriphenylene-2, 3,6,7,10, 11-hexachloronitrile, etc.), heterocyclic compounds such as porphyrin derivatives, polysilanes, etc. In the polymer system, polycarbonate or styrene derivative, polyvinylcarbazole, polysilane, or the like having the monomer in the side chain is preferable, but there is no particular limitation as long as it is a compound which forms a thin film necessary for manufacturing a light-emitting element, can inject holes from an anode, and can transport holes.
Further, it is also known that the conductivity of an organic semiconductor is strongly affected by doping. Such an organic semiconductor matrix material contains a compound having a good electron donating property or a compound having a good electron accepting property. For doping electron-donating substances, strong electron acceptors such as Tetracyanoquinodimethane (TCNQ) and 2,3,5, 6-tetrafluorotetracyanoquinodimethane-1, 4-benzoquinodimethane (2, 3,5, 6-tetrafluorotetracyanodimethane-1, 4-benzoquinodimethane, F4 TCNQ) are known (for example, see documents "m. Faefer, a. Bayer, t. Frietz, k. Rior (m. Pfeiffer, beyer, t.fritz, k.leo)," application physics flash "(appl.phys.lett.), 73 (22), 3202-3204 (1998)" and "j. Bloschvitz, m. Fajaffer, t. Floritz, k. Rio (j.blochwitz, m.pfeiffer, t.fritz, k.leo)," application physics flash "(appl.phys.lett.), 73 (6), 729-731 (1998)"). These generate so-called holes by an electron transfer process in an electron-donating base substance (hole-transporting substance). The conductivity of the base material varies considerably depending on the number and mobility of holes. As a matrix material having a hole transporting property, for example, a benzidine derivative (TPD, etc.) or a starburst amine derivative (4,4', 4 ″ -tris (N, N-diphenylamino) triphenylamine, TDATA, etc.), or a specific metal phthalocyanine (in particular, zinc phthalocyanine (ZnPc), etc.) is known (japanese patent laid-open No. 2005-167175).
The hole injection layer material and the hole transport layer material may be used as a hole layer material as a polymer compound obtained by polymerizing a reactive compound, as a monomer, in which a reactive substituent is substituted in the hole injection layer material and the hole transport layer material, or as a polymer cross-linked product thereof obtained by reacting a main chain polymer with the reactive compound, or as a pendant-type polymer compound obtained by polymerizing a reactive compound or a pendant-type polymer cross-linked product thereof. As the reactive substituent in such a case, the description of the polycyclic aromatic compound represented by the above general formula (1) can be cited.
The use of such a polymer compound and a crosslinked polymer will be described in detail later.
< light-emitting layer in organic electroluminescent element >
The light-emitting layer 105 emits light by recombination of holes injected from the anode 102 and electrons injected from the cathode 108 between electrodes to which an electric field is applied. The material for forming the light-emitting layer 105 may be a compound that emits light by being excited by recombination of holes and electrons (light-emitting compound), and is preferably a compound that can be formed into a stable thin film shape and that exhibits strong light emission (fluorescence) efficiency in a solid state. In the present invention, as the material for the light-emitting layer, a polycyclic aromatic compound represented by the general formula (1) or the general formula (2) can be used.
The light-emitting layer may be a single layer or may include multiple layers, and each of the light-emitting layers is formed of a material (host material or dopant material) for the light-emitting layer. The host material and the dopant material may be one kind or a combination of two or more kinds, respectively. The host material may be mixed with a material for a hole transport layer or a material for an electron transport layer, or may be a combination of these materials. The dopant material may be contained within the bulk of the host material, or may be contained within a portion of the host material, either. The doping method may be a co-evaporation method with the host material, a simultaneous evaporation method after mixing with the host material in advance, or a wet film-forming method after mixing with the host material in advance together with an organic solvent.
The amount of the host material to be used differs depending on the type of the host material, and may be determined in accordance with the characteristics of the host material. The amount of the host material used is preferably 50 to 99.999 wt%, more preferably 80 to 99.95 wt%, and still more preferably 90 to 99.9 wt% of the total amount of the light-emitting layer material.
The amount of the dopant material used varies depending on the kind of the dopant material, and may be determined by matching the characteristics of the dopant material. The amount of the dopant used is preferably 0.001 to 50 wt%, more preferably 0.05 to 20 wt%, and still more preferably 0.1 to 10 wt% of the total material for the light-emitting layer. In the above range, for example, concentration quenching is preferably prevented. In addition, from the viewpoint of durability, a case where a part or all of hydrogen atoms of the dopant material are deuterated is also preferable.
On the other hand, in the organic EL element using the thermally active type delayed fluorescence dopant material, the amount of the dopant material used is preferably low in terms of preventing the concentration quenching phenomenon, but is preferably high in terms of the efficiency of the thermally active type delayed fluorescence mechanism. In an organic EL device using a thermally active delayed fluorescence auxiliary dopant material, it is preferable that the amount of the dopant material used is lower than the amount of the auxiliary dopant material used in terms of the efficiency of the thermally active delayed fluorescence mechanism of the auxiliary dopant material. The polycyclic aromatic compound of the present invention can be used as a dopant (also referred to as an emission dopant) in an organic EL element using a thermally active delayed fluorescence auxiliary dopant material.
When the auxiliary dopant material is used, the amounts of the host material, the auxiliary dopant material, and the dopant material used are 40 to 99.999 wt%, 59 to 1 wt%, and 20 to 0.001 wt%, preferably 60 to 99.99 wt%, 39 to 5 wt%, and 10 to 0.01 wt%, more preferably 70 to 99.95 wt%, 29 to 10 wt%, and 5 to 0.05 wt%, of the total material for the light-emitting layer, respectively.
As the host material, anthracene, pyrene, dibenzo known as a light-emitting body from the past can be mentioned
Figure BDA0003862503640001131
Or fused ring derivatives such as fluorene, bisstyryl derivatives such as bisstyrylanthracene derivatives or distyrylbenzene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, and the like. Particularly preferably an anthracene compound, a fluorene compound or a dibenzo->
Figure BDA0003862503640001132
Is a compound. In addition, from the viewpoint of durability, it is also preferable that some or all of the hydrogen atoms of the host material be deuterated. Further, it is also preferable that the light-emitting layer is formed by a combination of a host compound in which some or all of hydrogen atoms are deuterated and a dopant compound in which some or all of hydrogen atoms are deuterated.
From the viewpoint of promoting but not inhibiting the generation of Thermally Activated Delayed Fluorescence (TADF) in the light-emitting layer, the triplet energy of the host material is preferably higher than that of the dopant or the assist dopant having the highest triplet energy in the light-emitting layer, and specifically, the triplet energy of the host material is preferably 0.01eV or more, more preferably 0.03eV or more, and still more preferably 0.1eV or more. In addition, TADF active compounds may also be used in the host material.
Examples of host materials include: a compound represented by the following general formula (H1), a compound represented by the following general formula (H2), a compound represented by the following general formula (H3), a compound having a structure represented by the following general formula (H4), a compound represented by the following general formula (H5), a compound represented by the following general formula (H6), a TADF material (for example, a compound represented by the following general formula (H7)), and a compound represented by the following general formula (H8). Preferred is a compound represented by the general formula (H1).
[ chemical formula 120]
Figure BDA0003862503640001141
< Compounds represented by the general formula (H1) >
[ solution 121]
Figure BDA0003862503640001142
In the formula (H1), L 1 The arylene group having 6 to 30 carbon atoms or the heteroarylene group having 2 to 30 carbon atoms is preferably an arylene group having 6 to 24 carbon atoms, more preferably an arylene group having 6 to 16 carbon atoms, further preferably an arylene group having 6 to 12 carbon atoms, particularly preferably an arylene group having 6 to 10 carbon atoms, further preferably a heteroarylene group having 2 to 25 carbon atoms, more preferably a heteroarylene group having 2 to 20 carbon atoms, further preferably a heteroarylene group having 2 to 15 carbon atoms, and particularly preferably a heteroarylene group having 2 to 10 carbon atoms. Specific examples of the arylene group include: a divalent group such as a benzene ring, a biphenyl ring, a naphthalene ring, a tribiphenyl ring, an acenaphthene ring, a fluorene ring, a phenalene ring, a phenanthrene ring, a triphenylene ring, a pyrene ring, a tetracene ring, a perylene ring, and a pentacene ring. Specific examples of the heteroarylene group include: pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, or the like, A divalent group such as an oxadiazole ring, a thiadiazole ring, a triazole ring, a tetrazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring, an indole ring, an isoindole ring, a 1H-indazole ring, a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, a 1H-benzotriazole ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinazoline ring, a quinoxaline ring, a phthalazine ring, a naphthyridine ring, a purine ring, a pteridine ring, a carbazole ring, an acridine ring, a phenoxathiin ring, a phenothiazine ring, a phenazine ring, a furan ring, a benzofuran ring, an isobenzofuran ring, a dibenzofuran ring, a thiophene ring, a benzothiophene ring, a dibenzothiophene ring, a furan ring, an anthracene ring, an indolocarbazole ring, a benzindole-carbazole ring, a benzindole-benzazolo-carbazole ring, and a naphthobenzofuran ring.
At least one hydrogen in the compound represented by the formula (H1) may be substituted with an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, a cyano group, a halogen or deuterium.
< Compounds represented by the general formula (H2) > (
[ chemical 122]
Figure BDA0003862503640001151
In the formula (H2), L 2 And L 3 Each independently an aryl group having 6 to 30 carbon atoms or a heteroaryl group having 2 to 30 carbon atoms, L 4 Hydrogen, aryl having 6 to 30 carbon atoms, or heteroaryl having 2 to 30 carbon atoms. The aryl group is preferably an aryl group having 6 to 24 carbon atoms, more preferably an aryl group having 6 to 16 carbon atoms, still more preferably an aryl group having 6 to 12 carbon atoms, particularly preferably an aryl group having 6 to 10 carbon atoms, and specifically, there may be mentioned: a monovalent group such as a benzene ring, a biphenyl ring, a naphthalene ring, a tribiphenyl ring, an acenaphthene ring, a fluorene ring, a phenalene ring, a phenanthrene ring, a triphenylene ring, a pyrene ring, a tetracene ring, a perylene ring, and a pentacene ring. The heteroaryl group is preferably a heteroaryl group having 2 to 25 carbon atoms, more preferably a heteroaryl group having 2 to 20 carbon atoms, still more preferably a heteroaryl group having 2 to 15 carbon atoms, particularly preferably a heteroaryl group having 2 to 10 carbon atoms, and specifically, there may be mentioned: pyrrole ring, oxazole ring, isoxazole ring, thiazole ring A monovalent group such as an isothiazole ring, an imidazole ring, an oxadiazole ring, a thiadiazole ring, a triazole ring, a tetrazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring, an indole ring, an isoindole ring, a 1H-indazole ring, a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, a 1H-benzotriazole ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinazoline ring, a quinoxaline ring, a phthalazine ring, a naphthyridine ring, a purine ring, a pteridine ring, a carbazole ring, an acridine ring, a phenoxathiin ring, a phenoxazine ring, a phenothiazine ring, a phenazine ring, an indolizine ring, a furan ring, a benzofuran ring, an isobenzofuran ring, a dibenzofuran ring, a thiophene ring, a benzothiophene ring, a dibenzothiophene ring, a diazo ring, an indole carbazole ring, a benzindole-carbazole ring, and a benzoxazole ring.
At least one hydrogen in the compound represented by the formula (H2) may be substituted with an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, a cyano group, a halogen or deuterium.
< Compound represented by the general formula (H3) > (an example of a Polymer host Material)
[ 123]
Figure BDA0003862503640001152
In the formula (H3), the compound represented by the formula,
each MU is independently a divalent group represented by removing any two hydrogen atoms from the aromatic compound, each EC is independently a monovalent group represented by removing any one hydrogen atom from the aromatic compound, two hydrogens in the MU are replaced with EC or MU, and k is an integer of 2 to 50000.
More specifically, the present invention is to provide a novel,
MU is independently arylene, heteroarylene, diarylenearylamino, diarylenearylboranyl, oxahydrocarbyl-boron-diyl, azahydrocarbyl boron-diyl,
EC are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, or aryloxy,
at least one hydrogen in the MU and EC may be further substituted with aryl, heteroaryl, diarylamino, alkyl, and cycloalkyl groups,
k is an integer of 2 to 50000.
k is preferably an integer of 20 to 50000, more preferably an integer of 100 to 50000.
At least one hydrogen of MU and EC in the formula (H3) may be substituted by an alkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms, a halogen or deuterium, and any-CH in the alkyl group 2 May be-O-or-Si (CH) 3 ) 2 -substitution, of the alkyl group other than the-CH directly bound to EC in formula (H3) 2 Any other than-CH 2 -optionally substituted by an arylene group having 6 to 24 carbon atoms, any hydrogen of the alkyl group being optionally substituted by fluorine.
Examples of the MU include divalent groups represented by removing any two hydrogen atoms from any of the following compounds.
[ solution 124]
Figure BDA0003862503640001171
More specifically, divalent groups represented by any one of the following structures are included. In these structures, MUs are bonded at one star to other MUs or ECs.
[ solution 125]
Figure BDA0003862503640001181
[ solution 126]
Figure BDA0003862503640001182
[ solution 127]
Figure BDA0003862503640001191
[ solution 128]
Figure BDA0003862503640001201
[ solution 129]
Figure BDA0003862503640001202
[ solution 130]
Figure BDA0003862503640001203
[ solution 131]
Figure BDA0003862503640001211
[ solution 132]
Figure BDA0003862503640001212
[ solution 133]
Figure BDA0003862503640001213
Examples of EC include monovalent groups represented by any of the following structures. In these structures, EC is bonded to MU at x.
[ solution 134]
Figure BDA0003862503640001221
[ chemical 135]
Figure BDA0003862503640001222
From the viewpoint of solubility and coating film formation properties, the compound represented by formula (H3) is preferably an alkyl group having 1 to 24 carbon atoms in 10 to 100% of MUs of the total number of MUs (k) in the molecule, more preferably an alkyl group having 1 to 18 carbon atoms (branched alkyl group having 3 to 18 carbon atoms) in 30 to 100% of MUs of the total number of MUs (k) in the molecule, and still more preferably an alkyl group having 1 to 12 carbon atoms (branched alkyl group having 3 to 12 carbon atoms) in 50 to 100% of MUs of the total number of MUs (k) in the molecule. On the other hand, from the viewpoint of in-plane orientation and charge transport, it is preferable that 10% to 100% of MUs of the total number of MUs (k) in a molecule have an alkyl group having 7 to 24 carbon atoms, and more preferably 30% to 100% of MUs of the total number of MUs (k) in a molecule have an alkyl group having 7 to 24 carbon atoms (branched alkyl group having 7 to 24 carbon atoms).
< Compound having a structure represented by the general formula (H4) >
The compound is a compound including a structure represented by the following formula (H4), and includes a plurality of the structures, preferably one to five, more preferably one to three, further preferably one to two, most preferably one, and in the case of including a plurality of the structures, the structures are bonded to each other directly by a single bond or by a specific linking group.
[ solution 136]
Figure BDA0003862503640001231
In the general formula (H4), G is each independently "= C (-H) -" or "= N-", and H in the "= C (-H) -" may be substituted with a substituent or another structure represented by the formula (H4).
The compound having a structure represented by general formula (H4) can be produced, for example, by using a compound described in international publication No. 2012/153780, international publication No. 2013/038650, or the like, and a method described in the above-mentioned document.
Examples of the substituent when H in "= C (-H) -" of G is substituted are, for example, as follows, but not limited thereto.
Specific examples of the "aryl" as a substituent include: phenyl, tolyl, xylyl, naphthyl, phenanthryl, pyreneA base,
Figure BDA0003862503640001232
Radical, benzo [ c ]]Phenanthryl, benzo [ g ]]/>
Figure BDA0003862503640001233
A benzanthracene group, a triphenylene group, a fluorenyl group, a 9, 9-dimethylfluorenyl group, a benzofluorenyl group, a dibenzofluorenyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, a fluoranthenyl group, and the like, and preferable examples thereof include: phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, triphenylene, fluoranthenyl, and the like. As the aryl group having a substituent, there may be mentioned: tolyl group, xylyl group, and 9, 9-dimethylfluorenyl group, and the like. As shown in the specific examples, the aryl group includes both condensed aryl groups and non-condensed aryl groups.
Specific examples of the "heteroaryl" as the substituent include: pyrrolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyridyl, triazinyl, indolyl, isoindolyl, imidazolyl, benzimidazolyl, indazolyl, imidazo [1,2-a ] pyridyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, azabenzofuryl, thienyl, benzothienyl, dibenzothienyl, azabenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, naphthyridinyl, carbazolyl, azacarbazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxazinyl, oxazolyl, oxadiazolyl, furazanyl, benzoxazolyl, thiazolyl, thiadiazolyl, benzothiazolyl, triazolyl, tetrazolyl and the like, preferably: dibenzofuranyl, dibenzothienyl, carbazolyl, pyridyl, pyrimidinyl, triazinyl, azabenzofuranyl, and azabenzothienyl, and the like. Further preferred is a dibenzofuranyl group, a dibenzothienyl group, an azabenzofuranyl group, or an azabenzothienyl group.
The "substituted silyl group" as the substituent is also preferably a group selected from the group consisting of a substituted or unsubstituted trialkylsilyl group, a substituted or unsubstituted arylalkylsilyl group, and a substituted or unsubstituted triarylsilyl group.
Specific examples of the substituted or unsubstituted trialkylsilyl group include a trimethylsilyl group and a triethylsilyl group. Specific examples of the substituted or unsubstituted arylalkylsilyl group include a diphenylmethylsilyl group, a ditolylmethylsilyl group, and a phenyldimethylsilyl group. Specific examples of the substituted or unsubstituted triarylsilyl group include a triphenylsilyl group and a tritolylsilyl group.
The "substituted phosphinoxide group" as a substituent is also preferably a substituted or unsubstituted diarylphosphinoxide group. Specific examples of the substituted or unsubstituted diarylphosphinoxide group include diphenylphosphine oxide and xylylphosphine oxide.
Examples of the "substituted carboxyl group" as a substituent include a benzoyloxy group and the like.
Examples of the linking group for bonding the plurality of structures represented by the formula (H4) include divalent to tetravalent, divalent to trivalent, or divalent derivatives of the above-mentioned aryl or heteroaryl groups.
Specific examples of the compound having a structure represented by general formula (H4) are shown below.
[ solution 137]
Figure BDA0003862503640001241
[ 138]
Figure BDA0003862503640001251
< Compound represented by the general formula (H5) >
[ solution 139]
Figure BDA0003862503640001252
In the formula (H5), the compound represented by the formula (I),
R 1 ～R 11 Are respectively and independentlyIs hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl or cycloalkyl (above, the first substituent), R 1 ～R 11 At least one hydrogen in (b) may be further substituted with an aryl, heteroaryl, diarylamino, alkyl, or cycloalkyl group (above, the second substituent),
R 1 ～R 11 may be bonded to each other and together with the a-ring, b-ring or c-ring form an aryl or heteroaryl ring, at least one hydrogen in the ring formed may be substituted by aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl or cycloalkyl (above, the first substituent), at least one of these substituents may be further substituted by aryl, heteroaryl, diarylamino, alkyl or cycloalkyl (above, the second substituent),
any of the a ring, the b ring, and the C ring "-C (-R) =" (here, R is R) 1 ～R 11 ) May be substituted by "-N =",
at least one hydrogen in the compound represented by formula (H5) may be independently substituted with halogen or deuterium, respectively.
Any of the rings a, b, and C in the formula (H5) — C (-R) = "(where R is R 1 ～R 11 ) May be substituted with "-N =" to change to a pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, other nitrogen containing heteroaryl ring.
Preferably in said formula (H5),
R 1 ～R 11 independently represents hydrogen, aryl group having 6 to 30 carbon atoms, heteroaryl group having 2 to 30 carbon atoms, diarylamino group (wherein the aryl group is aryl group having 6 to 12 carbon atoms), alkyl group having 1 to 12 carbon atoms or cycloalkyl group having 3 to 16 carbon atoms, and R 1 ～R 11 Wherein at least one hydrogen in the aromatic ring may be further substituted by an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a diarylamino group (wherein the aryl group is an aryl group having 6 to 12 carbon atoms), an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 16 carbon atoms,
R 1 ～R 11 wherein adjacent groups may be bonded to each other and form an aryl ring having 9 to 16 carbon atoms together with the a-ring, the b-ring or the c-ringOr a heteroaryl ring having 6 to 15 carbon atoms, wherein at least one hydrogen in the ring is substituted by an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a diarylamino group (wherein the aryl group is an aryl group having 6 to 12 carbon atoms), an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 16 carbon atoms, and at least one hydrogen in these substituents is further substituted by an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a diarylamino group (wherein the aryl group is an aryl group having 6 to 12 carbon atoms), an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 16 carbon atoms.
Still more preferably, in the formula (H5),
R 1 ～R 11 each independently represents hydrogen, aryl having 6 to 16 carbon atoms, heteroaryl having 2 to 15 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 10 carbon atoms), alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms, and R is 1 ～R 11 Wherein at least one hydrogen in the above-mentioned group is further substituted by an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, a diarylamino group (wherein the aryl group is an aryl group having 6 to 10 carbon atoms), an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 14 carbon atoms,
R 1 ～R 11 wherein adjacent groups in (a) may be bonded to each other to form an aryl ring having 9 to 12 carbon atoms or a heteroaryl ring having 6 to 12 carbon atoms together with the a, b or c ring, at least one hydrogen in the formed ring may be substituted by an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, a diarylamino group (wherein the aryl group is an aryl group having 6 to 10 carbon atoms), an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 14 carbon atoms, and at least one hydrogen in these substituents may be further substituted by an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, a diarylamino group (wherein the aryl group is an aryl group having 6 to 10 carbon atoms), an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 14 carbon atoms.
In the first substituent and the second substituent, the "aryl" or the "heteroaryl" in the aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino may be exemplified as follows.
Specific examples of the "aryl group" include aryl groups having 6 to 30 carbon atoms, preferably 6 to 24 carbon atoms, more preferably 6 to 20 carbon atoms, still more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, and most preferably 6 to 10 carbon atoms. Examples thereof include: phenyl as a monocyclic aryl group, (2-, 3-, 4-) biphenyl as a bicyclic aryl group, (1-, 2-) naphthyl as a condensed bicyclic aryl group, (m-terphenyl-2 ' -yl, m-terphenyl-4 ' -yl, m-terphenyl-5 ' -yl, o-terphenyl-3 ' -yl, o-terphenyl-4 ' -yl, p-terphenyl-2 ' -yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl-2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) as a tricyclic aryl group, acenaphthene- (1-, 3-, 4-, 5-) as condensed tricyclic aryl, fluorene- (1-, 2-, 3-, 4-, 9-) as non- (1-, 2-) as well as (1-, 2-, 3-, 4-, 9-) phenanthrene as well as tetrabiphenyl (5 ' -phenyl-m-terphenyl-2-yl, 5' -phenyl-m-terphenyl-3-yl, 5' -phenyl-m-terphenyl-4-yl and m-tetrabiphenyl) as tetracyclic aryl, triphenylene- (1-, as condensed tricyclic aryl, 2-) group, pyrene- (1-, 2-, 4-) group, tetracene- (1-, 2-, 5-) group, perylene- (1-, 2-, 3-) group as condensed pentacyclic aryl group, pentacene- (1-, 2-, 5-, 6-) group and the like.
Specific examples of the "heteroaryl group" include a heteroaryl group having 2 to 30 carbon atoms, preferably a heteroaryl group having 2 to 25 carbon atoms, more preferably a heteroaryl group having 2 to 20 carbon atoms, still more preferably a heteroaryl group having 2 to 15 carbon atoms, and particularly preferably a heteroaryl group having 2 to 10 carbon atoms. Examples thereof include: pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxathiyl, phenoxazinyl, phenothiazinyl, phenazinyl, indazolyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, naphthobenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, naphthobenzothienyl, benzophosphoryl, dibenzophosphoryl, benzophosphacyclopentadienyl, monovalent radicals of dibenzophosphole oxide ring, monovalent benzothiophenyl, thiadiazolyl, thiacarbazolyl, anthracenyl, benzindolinyl, and benzoxazolyl groups.
In the first substituent and the second substituent, the "alkyl group" may be either a straight chain or a branched chain, and examples thereof include a straight chain alkyl group having 1 to 24 carbon atoms or a branched alkyl group having 3 to 24 carbon atoms, preferably an alkyl group having 1 to 18 carbon atoms (a branched alkyl group having 3 to 18 carbon atoms), more preferably an alkyl group having 1 to 12 carbon atoms (a branched alkyl group having 3 to 12 carbon atoms), still more preferably an alkyl group having 1 to 6 carbon atoms (a branched alkyl group having 3 to 6 carbon atoms), particularly preferably an alkyl group having 1 to 5 carbon atoms (a branched alkyl group having 3 to 5 carbon atoms) or an alkyl group having 1 to 4 carbon atoms (a branched alkyl group having 3 to 4 carbon atoms), and most preferably a methyl group. Examples thereof include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl (t-amyl), n-hexyl, 1-methylpentyl, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, tert-octyl (1, 3-tetramethylbutyl), or mixtures thereof 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 2, 6-dimethyl-4-heptyl, 3, 5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl and the like. Further, for example, there can be mentioned: <xnotran> 1- -1- ,1,1- ,1,1- ,1- -1- ,1,1,4- ,1,1,2- ,1,1- ,1,1- ,1,1- ,1,1,5- ,1- -1- ,1- -1,3- ,1,1,2,2- ,1- -1- ,1,1- ,1- -1- ,1,1,3- ,1- -1- ,1,1,2- ,1- -1,2,2- ,1- -1- ,1,1- . </xnotran>
In the first substituent and the second substituent, as the "cycloalkyl group", there may be mentioned: cycloalkyl group having 3 to 24 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, cycloalkyl group having 3 to 16 carbon atoms, cycloalkyl group having 3 to 14 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms, cycloalkyl group having 5 to 8 carbon atoms, cycloalkyl group having 5 to 6 carbon atoms, cycloalkyl group having 5 carbon atoms and the like. Examples thereof include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and a substituent of an alkyl group (particularly, methyl) having 1 to 4 carbon atoms of these groups, bicyclo [1.1.0] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.1.0] pentyl, bicyclo [2.1.1] hexyl, bicyclo [3.1.0] hexyl, bicyclo [2.2.1] heptyl, bicyclo [2.2.2] octyl, adamantyl, diamantanyl, decahydronaphthyl, decahydroazulenyl, and the like.
The substitution position when the first substituent is an aryl group is preferably R 1 、R 3 、R 4 、R 5 、R 10 And R 11 For example, more preferably to R 1 And R 3 Substituted with respect to R 5 And R 10 Substituted with respect to R 4 And R 11 Aryl is preferably phenyl.
The substitution position when the first substituent is heteroaryl is preferably R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 9 、R 10 And R 11 For example, more preferably to R 1 Substituted with respect to R 2 Substituted with respect to R 3 Substituted with respect to R 1 And R 3 Substituted with respect to R 4 And R 11 Substituted with respect to R 5 And R 10 Substituted with respect to R 6 And R 9 The heteroaryl group is preferably a carbazolyl group. The heteroaryl (e.g., carbazolyl) may be substituted at that position via a phenylene group.
Specific examples of the compound represented by the formula (H5) include compounds represented by the following structural formulae. Further, "Me" in the formula is methyl.
[ solution 140]
Figure BDA0003862503640001281
[ solution 141]
Figure BDA0003862503640001282
The compound represented by formula (H5) is first prepared by bonding the a-ring to the c-ring through a bonding group (-O-) to produce an intermediate (first reaction), and then by bonding the a-ring to the c-ring through B (boron), to produce a final product (second reaction). In the first reaction, for example, a nucleophilic substitution reaction, an ullmann reaction, or other general etherification reaction can be used. In the second reaction, a cascade-type hetero-friedel-crafts reaction (a sequential aromatic electrophilic substitution reaction) can be used. The details of the first reaction and the second reaction can be found in the description of International publication No. 2015/102118.
< Compound represented by the general formula (H6) >
[ solution 142]
Figure BDA0003862503640001291
In the formula (H6) described above,
R 1 ～R 16 each independently is hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl or cycloalkyl (above, the first substituent), and R 1 ～R 16 At least one hydrogen in (b) may be further substituted with an aryl, heteroaryl, diarylamino, alkyl, or cycloalkyl group (above, the second substituent),
R 1 ～R 16 can be bonded to each other and form, together with the a-ring, b-ring, c-ring, or d-ring, an aryl or heteroaryl ring, at least one hydrogen in the formed ring being able to pass through an aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl or cycloalkyl group (above, the first taking placeSubstituent), at least one of which may be further substituted with aryl, heteroaryl, diarylamino, alkyl, or cycloalkyl (above, the second substituent),
at least one hydrogen in the compound represented by formula (H6) may be independently substituted with halogen or deuterium, respectively.
Preferably in said formula (H6),
R 1 ～R 16 independently represents hydrogen, aryl group having 6 to 30 carbon atoms, heteroaryl group having 2 to 30 carbon atoms, diarylamino group (wherein the aryl group is aryl group having 6 to 12 carbon atoms), alkyl group having 1 to 12 carbon atoms or cycloalkyl group having 3 to 16 carbon atoms, and R 1 ～R 16 Wherein at least one hydrogen in the above-mentioned group is further substituted by an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a diarylamino group (wherein the aryl group is an aryl group having 6 to 12 carbon atoms), an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 16 carbon atoms,
R 1 ～R 16 Wherein adjacent groups in (b) may be bonded to each other to form an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms together with the a, b, c, or d ring, at least one hydrogen in the formed ring may be substituted by an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a diarylamino group (wherein the aryl group is an aryl group having 6 to 12 carbon atoms), an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 16 carbon atoms, and at least one hydrogen in these substituents may be further substituted by an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a diarylamino group (wherein the aryl group is an aryl group having 6 to 12 carbon atoms), an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 16 carbon atoms.
Still more preferably, in the formula (H6),
R 1 ～R 16 each independently represents hydrogen, aryl having 6 to 16 carbon atoms, heteroaryl having 2 to 15 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 10 carbon atoms), alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms, and R is 1 ～R 16 Wherein at least one hydrogen in the above-mentioned group is further substituted by an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, a diarylamino group (wherein the aryl group is an aryl group having 6 to 10 carbon atoms), an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 14 carbon atoms,
R 1 ～R 16 wherein adjacent groups in (a) may be bonded to each other to form an aryl ring having 9 to 12 carbon atoms or a heteroaryl ring having 6 to 12 carbon atoms together with the a, b, c, or d ring, at least one hydrogen in the formed ring may be substituted by an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, a diarylamino group (wherein the aryl group is an aryl group having 6 to 10 carbon atoms), an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 14 carbon atoms, and at least one hydrogen in these substituents may be further substituted by an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, a diarylamino group (wherein the aryl group is an aryl group having 6 to 10 carbon atoms), an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 14 carbon atoms.
In the first substituent and the second substituent, the "aryl" or the "heteroaryl" in the aryl, heteroaryl, diarylamino, diheteroarylamino or arylheteroarylamino group may be exemplified as follows.
Specific examples of the "aryl group" include aryl groups having 6 to 30 carbon atoms, preferably 6 to 24 carbon atoms, more preferably 6 to 20 carbon atoms, still more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, and most preferably 6 to 10 carbon atoms. Examples thereof include: phenyl as a monocyclic aryl group, (2-, 3-, 4-) biphenyl as a bicyclic aryl group, (1-, 2-) naphthyl as a condensed bicyclic aryl group, (m-terphenyl-2 ' -yl, m-terphenyl-4 ' -yl, m-terphenyl-5 ' -yl, o-terphenyl-3 ' -yl, o-terphenyl-4 ' -yl, p-terphenyl-2 ' -yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl-2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) as a tricyclic aryl group, acenaphthene- (1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalene- (1-, 2-) yl, (1-, 2-, 3-, 4-, 9-) phenanthryl as condensed tricyclic aryl, quaterphenyl (5 ' -phenyl-m-terphenyl-2-yl, 5' -phenyl-m-terphenyl-3-yl, 5' -phenyl-m-terphenyl-4-yl, m-quaterphenyl) as tetracyclic aryl, triphenylene- (1-, acenaphthylene- (3-), acenaphthylene- (4-), and acenaphthylene- (1-), 2-) group, pyrene- (1-, 2-, 4-) group, tetracene- (1-, 2-, 5-) group, perylene- (1-, 2-, 3-) group as condensed pentacyclic aryl group, pentacene- (1-, 2-, 5-, 6-) group, and the like.
Specific examples of the "heteroaryl group" include a heteroaryl group having 2 to 30 carbon atoms, preferably a heteroaryl group having 2 to 25 carbon atoms, more preferably a heteroaryl group having 2 to 20 carbon atoms, still more preferably a heteroaryl group having 2 to 15 carbon atoms, and particularly preferably a heteroaryl group having 2 to 10 carbon atoms. Examples thereof include: pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxathiyl, phenoxazinyl, phenothiazinyl, phenazinyl, indazolyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, naphthobenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, naphthobenzothienyl, benzophosphoryl, dibenzophosphoryl, benzophosphacyclopentadienyl, monovalent radicals of dibenzophosphole oxide ring, monovalent benzothiophenyl, thiadiazolyl, thiacarbazolyl, anthracenyl, benzindolinyl, and benzoxazolyl groups.
In the first substituent and the second substituent, the "alkyl group" may be either a straight chain or a branched chain, and examples thereof include a straight chain alkyl group having 1 to 24 carbon atoms or a branched alkyl group having 3 to 24 carbon atoms, preferably an alkyl group having 1 to 18 carbon atoms (a branched alkyl group having 3 to 18 carbon atoms), more preferably an alkyl group having 1 to 12 carbon atoms (a branched alkyl group having 3 to 12 carbon atoms), still more preferably an alkyl group having 1 to 6 carbon atoms (a branched alkyl group having 3 to 6 carbon atoms), particularly preferably an alkyl group having 1 to 5 carbon atoms (a branched alkyl group having 3 to 5 carbon atoms) or an alkyl group having 1 to 4 carbon atoms (a branched alkyl group having 3 to 4 carbon atoms), and most preferably a methyl group. Examples thereof include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl (t-amyl) (tert-pentyl (t-amyl)), n-hexyl, 1-methylpentyl, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, tert-octyl (1, 3-tetramethylbutyl), 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 2, 6-dimethyl-4-heptyl, 3, 5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl and the like. Further, for example, there can be mentioned: <xnotran> 1- -1- ,1,1- ,1,1- ,1- -1- ,1,1,4- ,1,1,2- ,1,1- ,1,1- ,1,1- ,1,1,5- ,1- -1- ,1- -1,3- ,1,1,2,2- ,1- -1- ,1,1- ,1- -1- ,1,1,3- ,1- -1- ,1,1,2- ,1- -1,2,2- ,1- -1- ,1,1- . </xnotran>
In the first substituent and the second substituent, as the "cycloalkyl group", there may be mentioned: cycloalkyl group having 3 to 24 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, cycloalkyl group having 3 to 16 carbon atoms, cycloalkyl group having 3 to 14 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms, cycloalkyl group having 5 to 8 carbon atoms, cycloalkyl group having 5 to 6 carbon atoms, cycloalkyl group having 5 carbon atoms and the like. Examples thereof include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and alkyl (particularly methyl) substituents having 1 to 4 carbon atoms of these groups, or bicyclo [1.1.0] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.1.0] pentyl, bicyclo [2.1.1] hexyl, bicyclo [3.1.0] hexyl, bicyclo [2.2.1] heptyl, bicyclo [2.2.2] octyl, adamantyl, diamantanyl, decahydronaphthyl, decahydroazulenyl, and the like.
The compound represented by the formula (H6) can be produced by referring to the description described in international publication No. 2014/042197.
< TADF Material >
By reducing the energy difference between the excited singlet state and the excited triplet state, reverse energy transition from the self-excited triplet state to the excited singlet state, which is generally low in transition probability, occurs efficiently, and light emission from the singlet state (thermally active delayed fluorescence, TADF) appears. In normal fluorescence emission, 75% of triplet excitons generated by current excitation pass through a thermal deactivation path and cannot be extracted as fluorescence. On the other hand, in TADF, all excitons can be used for fluorescence emission, and a highly efficient organic EL device can be realized.
As the TADF material that can be used for such a purpose, for example, a compound represented by the following general formula (H7) or a compound having the following general formula (H7) as a partial structure can be cited.
[ solution 143]
ED-Ln-EA (H7)
In the formula (H7), ED is an electron donating group, ln is a bonding group, EA is an electron accepting group, and the singlet energy (S) of the compound represented by the formula (H7) 1 ) And triplet energy (T) 1 ) Energy difference (Δ S) of 1 T 1 ) Is below 0.2eV (Hiroki Uoyama, kenichi Goushi, zhijin Katsukumi Shizu, hiroko Haozi (Hiroko Nomura), chihaya Adachi, nature (Nature), 492,234-238 (2012). Energy difference (Δ S) 1 T 1 ) Preferably 0.15eV or less, more preferably 0.10eV or less, and still more preferably 0.08eV or less.
The TADF material is preferably a donor-acceptor type TADF compound (TADF compound of type D-a) designed to locally exist a Highest Occupied Molecular Orbital (HOMO) and a Lowest Unoccupied Molecular Orbital (LUMO) within a molecule using an electron donating substituent called a donor and an electron accepting substituent called an acceptor to produce efficient reverse intercross (reverse intercross crosslinking).
In the present specification, the term "electron-donating substituent" (donor) refers to a substituent and a partial structure that are localized in LUMO in a TADF compound molecule, and the term "electron-accepting substituent" (acceptor) refers to a substituent and a partial structure that are localized in HOMO in a TADF compound molecule.
In general, TADF compounds using a donor or acceptor have a large Spin Orbit Coupling (SOC) and a small exchange interaction between HOMO and LUMO and a small Δ E (ST) due to structural reasons, and thus can achieve a very fast reverse intersystem crossing speed. On the other hand, a TADF compound using a donor or an acceptor has a large structural relaxation in an excited state (in a molecule, since a stable structure is different between a base state and an excited state, when a transition from the base state to the excited state occurs by an external stimulus, the structure is changed to the stable structure in the excited state thereafter), and a wide emission spectrum is provided, and thus, when it is used as a light-emitting material, there is a possibility that color purity may be lowered.
When the color purity is lowered by the TADF material, a fluorescent compound may be added as another component to the light-emitting layer or a layer adjacent to the light-emitting layer. The TADF material functions as an auxiliary dopant, and the other components function as an emission dopant. The other component may be a compound having an absorption spectrum of the compound at least partially overlapping with an emission peak of the auxiliary dopant.
As the structure of the donor and acceptor used in the TADF material, for example, the structures described in "Chemistry of Materials", 2017,29,1946-1963, may be used. The ED may contain sp 3 The functional group of nitrogen, more specifically, there may be mentioned: from carbazole, dimethylcarbazole, di-tert-butylcarbazole, dimethoxycarbazole, tetramethylcarbazole, benzofluorocarbazole, benzothienocarbazole, phenylindolinocarbazole, phenylbicarbazole, bicarbazole, tertcarbazole, diphenylcarbazolylamine, tetraphenylcarbazolylamine, phenoxazine, dihydrophenazine, phenothiazine, dimethylacridine, diphenylamine, bis (tert-butylphenyl) amine, N 1 - (4- (diphenylamino) phenyl) -N 4 ,N 4 Diphenylbenzene-1, 4-diamine, dimethylanilinium dihydroacridinediamine, tetramethyl-indanoacridine and diphenylThe radical-dihydrodibenzosilatrane, etc. Further, the EA includes, for example, an sp-containing compound 2 Nitrogen aromatic rings, CN-substituted aromatic rings, ketone rings, and cyano groups, and more specifically, there are mentioned: self-sulfonyldiphenyl, benzophenone, phenylenebis (phenyl ketone), benzonitrile, isonicotinic nitrile, phthalonitrile, isophthalonitrile, terephthalonitrile, triazole, oxazole, thiadiazole, benzothiazole, benzobis (thiazole), benzoxazole, benzobis (oxazole), quinoline, benzimidazole, dibenzoquinoxaline, heptaazaphenalene, thioxanthone dioxide, dimethylanthrone, anthracenedione, pyridine, 5H-cyclopenta [1,2-b:5,4-b' ]Bipyridine, benzenetricarboxylic acid nitrile, fluorenyldicarbonitrile, pyrazindicarbonitrile, pyridinedicarbonitrile, dibenzoquinoxalinedicarbonitrile, pyrimidine, phenylpyrimidine, methylpyrimidine, triazine, triphenyltriazine, bis (phenylsulfonyl) benzene, dimethylthioxanthene dioxide, thianthrene tetraoxide, tris (dimethylphenyl) borane, and the like. Examples of Ln include a single bond and an arylene group, and more specifically, a phenylene group, a biphenylene group, a naphthylene group, and the like. In either structure, hydrogen may be substituted with alkyl, cycloalkyl, and aryl groups. Particularly preferred are compounds having at least one selected from carbazole, phenoxazine, acridine, triazine, pyrimidine, pyrazine, thioxanthene, benzonitrile, phthalonitrile, isophthalonitrile, diphenylsulfone, triazole, oxadiazole, thiadiazole and benzophenone as a partial structure.
More specifically, the compound represented by the general formula (H7) is a compound represented by any one of the following general formulae (H7-1), (H7-2) and (H7-3).
[ solution 144]
Figure BDA0003862503640001331
In the general formula (H7-1), the formula (H7-2) and the formula (H7-3),
m is each independently a single bond, -O-, > N-Ar or > C (-Ar) 2 From the viewpoint of the depth of the HOMO of the partial structure to be formed and the height of the excited singlet level and the excited triplet level, Preferably a single bond, -O-or > N-Ar,
j is a spacer structure for separating a donor partial structure from a receptor partial structure, and each independently is an arylene group having 6 to 18 carbon atoms, and is preferably an arylene group having 6 to 12 carbon atoms, more specifically, a phenylene group, a methylphenylene group, and a dimethylphenylene group,
q is independently = C (-H) -or = N-, and preferably = N-from the viewpoint of the shallowness of the LUMO forming the partial structure and the heights of the excited singlet level and the excited triplet level,
ar is independently hydrogen, an aryl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 18 carbon atoms, and from the viewpoints of the depth of the HOMO of the partial structure to be formed and the height of the excited singlet level and the excited triplet level, it is preferably hydrogen, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 14 carbon atoms, an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 6 to 10 carbon atoms, more preferably hydrogen, phenyl, tolyl, xylyl, mesityl, biphenyl, pyridyl, bipyridyl, triazinyl, carbazolyl, dimethylcarbazolyl, di-tert-butylcarbazolyl, benzimidazolyl or phenylbenzimidazolyl, further preferably hydrogen, phenyl or carbazolyl,
m is 1 or 2, and m is,
n is an integer of 2 to (6-m), and preferably an integer of 4 to (6-m) from the viewpoint of steric hindrance.
Further, at least one hydrogen in the compounds represented by each of the formulae may be substituted with halogen or deuterium.
Examples of the compound represented by the formula (H7) include compounds represented by the following structures. In the structural formula, ". Indicates a bonding position,". Me "indicates a methyl group, and" tBu "indicates a tert-butyl group.
[ solution 145]
Figure BDA0003862503640001341
[ solution 146]
Figure BDA0003862503640001351
[ chemical 147]
Figure BDA0003862503640001361
[ solution 148]
Figure BDA0003862503640001371
[ 149]
Figure BDA0003862503640001381
[ solution 150]
Figure BDA0003862503640001391
[ solution 151]
Figure BDA0003862503640001401
[ 152]
Figure BDA0003862503640001411
[ solution 153]
Figure BDA0003862503640001421
As the compound represented by the general formula (H7), among the specific compounds, 4CzBN-Ph, 5CzBN, 3Cz2DPhCzBN, 4CzIPN, 2PXZ-TAZ, cz-TRZ3, BDPCC-TPTA, MA-TA, PA-TA, FA-TA, PXZ-TRZ, DMAC-TRZ, BCzT, DCzTrz, DDCzTrz, spiro AC-TRZ, ac-HPM, ac-PPM, ac-MPM, TCzTrz, tmCzTrz and DCzmCZTrz are particularly preferable.
< Compound represented by the general formula (H8) >)
[ solution 154]
Figure BDA0003862503640001431
In the formula (H8), L 5 、L 6 And L 7 Each independently represents an aryl group having 6 to 30 carbon atoms or a heteroaryl group having 2 to 30 carbon atoms. The aryl group is preferably an aryl group having 6 to 24 carbon atoms, more preferably an aryl group having 6 to 16 carbon atoms, further preferably an aryl group having 6 to 12 carbon atoms, particularly preferably an aryl group having 6 to 10 carbon atoms, and specific examples thereof include: a monovalent group such as a benzene ring, a biphenyl ring, a naphthalene ring, a terphenyl ring, an acenaphthene ring, a fluorene ring, a phenalene ring, a phenanthrene ring, a triphenylene ring, a pyrene ring, a tetracene ring, a perylene ring, and a pentacene ring. The heteroaryl group is preferably a heteroaryl group having 2 to 25 carbon atoms, more preferably a heteroaryl group having 2 to 20 carbon atoms, still more preferably a heteroaryl group having 2 to 15 carbon atoms, particularly preferably a heteroaryl group having 2 to 10 carbon atoms, and specifically, there can be mentioned: a monovalent benzfuran ring, e.g., a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an oxadiazole ring, a thiadiazole ring, a triazole ring, a tetrazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring, an indole ring, an isoindole ring, a 1H-indazole ring, a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, a 1H-benzotriazole ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinazoline ring, a quinoxaline ring, a oxazine ring, a naphthyridine ring, a purine ring, a pteridine ring, a carbazole ring, an acridine ring, a phenoxazine ring, a phenothiazine ring, a phenazine azsilicon ring, an indolizine ring, a furan ring, a benzofuran ring, an isobenzofuran ring, a dibenzofuran ring, a benzothiophene ring, a furazan ring, an anthracene ring, an indolocarbazole ring, a benzazolo carbazole ring, a naphthocarbazole ring, and the like.
At least one hydrogen in the compound represented by the formula (H8) may be substituted with an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, a cyano group, a halogen or deuterium.
In addition, as the dopant material, a known compound can be used, and it can be selected from various materials according to a desired luminescent color. Specific examples thereof include: phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphthopyrene, dibenzopyrene, rubrene and
Figure BDA0003862503640001432
a fused ring derivative, a benzoxazole derivative, a benzothiazole derivative, a benzimidazole derivative, a benzotriazole derivative, an oxazole derivative, an oxadiazole derivative, a thiazole derivative, an imidazole derivative, a thiadiazole derivative, a triazole derivative, a pyrazoline derivative, a stilbene derivative, a thiophene derivative, a tetraphenylbutadiene derivative, a cyclopentadiene derivative, a bisstyrylanthracene derivative or a distyrylbenzene derivative (Japanese patent laid-open No. Hei 1-24087), a bisstyrylarylene derivative (Japanese patent laid-open No. Hei 2-247278), a diazabenzodiindene derivative, a furan derivative, a benzofuran derivative, isobenzofuran derivatives such as phenylisobenzofuran, ditrimethylphenylisobenzofuran, bis (2-methylphenyl) isobenzofuran, bis (2-trifluoromethylphenyl) isobenzofuran, and phenylisobenzofuran, dibenzofuran derivatives, coumarin derivatives such as 7-dialkylaminocoumarin derivatives, 7-piperidylcoumarin derivatives, 7-hydroxycoumarin derivatives, 7-methoxycoumarin derivatives, 7-acetoxycoumarin derivatives, 3-benzothiazylcoumarin derivatives, 3-benzimidazolylcoumarin derivatives, and 3-benzoxazolyl coumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, polymethine derivatives, cyanine derivatives, oxobenzanthracene derivatives, xanthene derivatives, rhodamine derivatives, fluorescein derivatives, pyrylium derivatives, quinolone derivatives, acridine derivatives, oxazine derivatives, phenyl ether (phenylene oxide) derivatives, quinacridone derivatives, quinazoline derivatives Derivatives, pyrrolopyridine derivatives, furopyridine derivatives, 1,2, 5-thiadiazolopyridine derivatives, pyrromethene derivatives, perinone derivatives, pyrrolopyrrole derivatives, squarylium derivatives, violanthrone derivatives, phenazine derivatives, acridone derivatives, deazaflavin derivatives, fluorene derivatives, and benzofluorene derivatives, and the like.
When each color-emitting light is exemplified, examples of the blue dopant material to the blue-green dopant material include: naphthalene, anthracene, phenanthrene, pyrene, triphenylene, perylene, fluorene, indene,
Figure BDA0003862503640001442
And aromatic hydrocarbon compounds or derivatives thereof, such as furan, pyrrole, thiophene, silole, 9-silafluorene, 9' -spirodisilylfluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyrazine, naphthyridine, quinoxaline, pyrrolopyridine, thioxanthene, and other aromatic heterocyclic compounds or derivatives thereof, distyrylbenzene derivatives, tetraphenylbutadiene derivatives, stilbene derivatives, aldazine derivatives, coumarin derivatives, imidazole, thiazole, thiadiazole, carbazole, oxazole, oxadiazole, triazole, and other azole derivatives and metal complexes thereof, and aromatic amine derivatives represented by N, N ' -diphenyl-N, N ' -bis (3-methylphenyl) -4,4' -diphenyl-1, 1' -diamine, and the like.
Examples of the green to yellow dopant materials include: coumarin derivatives, phthalimide derivatives, naphthalimide derivatives, perinone derivatives, pyrrolopyrrole derivatives, cyclopentadiene derivatives, acridone derivatives, quinacridone derivatives, tetracene derivatives such as rubrene, and the like, and further, the following compounds are preferable examples: examples of the blue-green dopant material include compounds obtained by introducing a substituent capable of increasing the wavelength of light, such as an aryl group, a heteroaryl group, an arylvinyl group, an amino group, or a cyano group, into a compound exemplified as the blue-green dopant material.
Further, the orange dopant material to the red dopant material include: naphthalimide derivatives such as bis (diisopropylphenyl) perylenetetracarboxylic acid imide, perinone derivatives, rare earth complexes such as Eu complexes in which acetylacetone or benzoylacetone and phenanthroline are used as ligands, 4- (dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran or the like, metal phthalocyanine derivatives such as magnesium phthalocyanine and aluminum phthalocyanine, rhodamine compounds, deazaflavin derivatives, coumarin derivatives, quinacridone derivatives, phenoxazine derivatives, oxazine derivatives, quinazoline derivatives, pyrrolopyridine derivatives, squarylium derivatives, violanthrone derivatives, phenazine derivatives, phenoxazinone derivatives, and thiadiazolopyridine derivatives, and the like, and further, the following compounds are exemplified as preferable examples: a compound obtained by introducing a substituent capable of increasing the wavelength of light, such as an aryl group, a heteroaryl group, an arylvinyl group, an amino group, or a cyano group, into the compounds exemplified as the blue dopant material to the cyan dopant material and the green dopant material to the yellow dopant material.
The dopant may be appropriately selected from compounds described in chemical industry, 6.2004, p.13, references cited therein, and the like.
Among the dopant materials, amines having a stilbene structure, perylene derivatives, borane derivatives, aromatic amine derivatives, coumarin derivatives, pyran derivatives, or pyrene derivatives are particularly preferable.
The amine having a stilbene structure is represented by, for example, the following formula.
[ solution 155]
Figure BDA0003862503640001441
In the formula, ar 1 Is an m-valent group derived from an aryl group having 6 to 30 carbon atoms, ar 2 And Ar 3 Are each independently an aryl group having 6 to 30 carbon atoms, ar 1 ～Ar 3 At least one of (A) has a stilbene structure, ar 1 ～Ar 3 Optionally substituted aryl, heteroaryl, alkyl, cycloalkyl, trisubstituted silyl (consisting of aryl, alkyl anda silyl group in which at least one of the cycloalkyl groups is trisubstituted) or a cyano group, and m is an integer of 1 to 4.
The amine having a stilbene structure is more preferably diaminostilbene represented by the following formula.
[ solution 156]
Figure BDA0003862503640001451
In the formula, ar 2 And Ar 3 Are each independently an aryl group having 6 to 30 carbon atoms, ar 2 And Ar 3 May be substituted with an aryl group, a heteroaryl group, an alkyl group, a cycloalkyl group, a trisubstituted silyl group (a silyl group trisubstituted by at least one of an aryl group, an alkyl group and a cycloalkyl group), or a cyano group.
Specific examples of the aryl group having 6 to 30 carbon atoms include: phenyl, naphthyl, acenaphthenyl, fluorenyl, phenalkenyl, phenanthrenyl anthryl, fluoranthryl triphenylene, pyrenyl,
Figure BDA0003862503640001452
Mesityl, tetracenyl, perylenyl, distyryl, distyrylphenyl, distyrylbiphenyl, distyrylfluorenyl, and the like.
Specific examples of the amines having a stilbene structure include: n, N, N ', N' -tetrakis (4-biphenyl) -4,4 '-diaminostilbene, N, N, N', N '-tetrakis (1-naphthyl) -4,4' -diaminostilbene, N, N, N ', N' -tetrakis (2-naphthyl) -4,4 '-diaminostilbene, N, N' -bis (2-naphthyl) -N, N '-diphenyl-4, 4' -diaminostilbene, N, N '-bis (9-phenanthryl) -N, N' -diphenyl-4, 4 '-diaminostilbene, 4' -bis [4 ″ -bis (diphenylamino) styryl ] -biphenyl, 1, 4-bis [4 '-bis (diphenylamino) styryl ] -benzene, 2, 7-bis [4' -bis (diphenylamino) styryl ] -9, 9-dimethylfluorene, 4 '-bis (9-ethyl-3-carbazolyl) -biphenyl, 4' -bis (9-phenyl-3-carbazolyl) -biphenyl, and the like.
Further, amines having a stilbene structure described in Japanese patent laid-open Nos. 2003-347056 and 2001-307884 may be used.
Examples of perylene derivatives include: 3, 10-bis (2, 6-dimethylphenyl) perylene, 3, 10-bis (2, 4, 6-trimethylphenyl) perylene, 3, 10-diphenyl perylene, 3, 4-diphenyl perylene, 2,5,8, 11-tetra-tert-butylperylene, 3,4,9, 10-tetraphenylperylene, 3- (1 ' -pyrenyl) -8, 11-di (tert-butyl) perylene, 3- (9 ' -anthryl) -8, 11-di (tert-butyl) perylene, 3' -bis (8, 11-di (tert-butyl) perylenyl), and the like.
Further, perylene derivatives described in Japanese patent laid-open No. 11-97178, japanese patent laid-open No. 2000-133457, japanese patent laid-open No. 2000-26324, japanese patent laid-open No. 2001-267079, japanese patent laid-open No. 2001-267078, japanese patent laid-open No. 2001-267076, japanese patent laid-open No. 2000-34234, japanese patent laid-open No. 2001-267075, japanese patent laid-open No. 2001-217077, and the like can also be used.
Examples of the borane derivatives include: 1, 8-diphenyl-10- (ditrimethylphenylboronyl) anthracene, 9-phenyl-10- (ditrimethylphenylboronyl) anthracene, 4- (9 ' -anthryl) ditrimethylphenylboronyl naphthalene, 4- (10 ' -phenyl-9 ' -anthryl) ditrimethylphenylboronyl naphthalene, 9- (ditrimethylphenylboronyl) anthracene, 9- (4 ' -biphenyl) -10- (ditrimethylphenylboronyl) anthracene, 9- (4 ' - (N-carbazolyl) phenyl) -10- (ditrimethylphenylboronyl) anthracene, and the like.
Further, borane derivatives described in International publication No. 2000/40586, for example, can also be used.
The aromatic amine derivative is represented by the following formula, for example.
[ chemical 157]
Figure BDA0003862503640001461
In the formula, ar 4 Is an n-valent group derived from an aryl group having 6 to 30 carbon atoms, ar 5 And Ar 6 Are each independently an aryl group having 6 to 30 carbon atoms, ar 4 ～Ar 6 May be substituted by aryl, heteroaryl, alkyl, cycloalkyl, trisubstituted silyl (silyl trisubstituted by at least one of aryl, alkyl and cycloalkyl)Or cyano, and n is an integer of 1 to 4.
In particular, the following aromatic amine derivatives are more preferable: ar (Ar) 4 Is derived from anthracene,
Figure BDA00038625036400014615
Divalent radicals of fluorene, benzofluorene or pyrene, ar 5 And Ar 6 Each independently an aryl group having 6 to 30 carbon atoms, ar 4 ～Ar 6 May be substituted with an aryl group, a heteroaryl group, an alkyl group, a cycloalkyl group, a trisubstituted silyl group (a silyl group trisubstituted by at least one of an aryl group, an alkyl group and a cycloalkyl group) or a cyano group, and n is 2.
Specific examples of the aryl group having 6 to 30 carbon atoms include: phenyl, naphthyl, acenaphthenyl, fluorenyl, phenalkenyl, phenanthrenyl anthryl, fluoranthryl triphenylene group, pyrenyl group,
Figure BDA0003862503640001463
Mesityl, tetracenyl, perylenyl, pentacenyl, and the like.
With respect to the aromatic amine derivative, as
Figure BDA0003862503640001464
Examples of the system include: n, N, N ', N' -tetraphenyl->
Figure BDA0003862503640001465
6, 12-diamine, N, N, N ', N' -tetra (p-tolyl) based on a suitable solvent for carrying out the method>
Figure BDA0003862503640001466
6, 12-diamine, N, N, N ', N' -tetra (m-tolyl) based on a suitable solvent for the replacement of the amino acid in the cell>
Figure BDA0003862503640001467
6,12-diamine, N, N, N ', N' -tetrakis (4-isopropylphenyl) & lt/EN & gt>
Figure BDA0003862503640001468
6,12-diamine, N, N, N ', N' -tetrakis (naphthalene-2-yl) & lt/EN & gt>
Figure BDA0003862503640001469
6, 12-diamine, N '-diphenyl-N, N' -di (p-tolyl) based on a physiologically acceptable medium>
Figure BDA00038625036400014610
6,12-diamine, N '-diphenyl-N, N' -bis (4-ethylphenyl) & lt/EN & gt>
Figure BDA00038625036400014611
6,12-diamine, N '-diphenyl-N, N' -bis (4-isopropylphenyl) based on>
Figure BDA00038625036400014612
6,12-diamine, N '-diphenyl-N, N' -bis (4-tert-butylphenyl) in combination with a signal-modifying agent>
Figure BDA00038625036400014613
6,12-diamine, N '-bis (4-isopropylphenyl) -N, N' -di (p-tolyl) & lt/EN & gt>
Figure BDA00038625036400014614
6,12-diamine, and the like.
Examples of pyrene-based compounds include: <xnotran> N, N, N ', N' - -1,6- , N, N, N ', N' - ( ) -1,6- , N, N, N ', N' - ( ) -1,6- , N, N, N ', N' - (4- ) -1,6- , N, N, N ', N' - (3,4- ) -1,6- , N, N '- -N, N' - ( ) -1,6- , N, N '- -N, N' - (4- ) -1,6- , N, N '- -N, N' - (4- ) -1,6- , N, N '- -N, N' - (4- ) -1,6- , N, N '- (4- ) -N, N' - ( ) -1,6- , N, N, N ', N' - (3,4- ) -3,8- -1,6- , N, N, N, N- -1,8- , N, N '- ( -4- ) -N, N' - -1,8- , </xnotran> N is a radical of 1 ,N 6 -diphenyl-N 1 ,N 6 -bis- (4-trimethylsilyl-phenyl) -1H, 8H-pyrene-1, 6-diamine, and the like.
Further, examples of anthracene series include: n, N, N, N-tetraphenylanthracene-9, 10-diamine, N, N, N ', N' -tetra (p-tolyl) anthracene-9, 10-diamine, N, N, N ', N' -tetra (m-tolyl) anthracene-9, 10-diamine, N, N, N ', N' -tetra (4-isopropylphenyl) anthracene-9, 10-diamine, N, N '-diphenyl-N, N' -di (p-tolyl) anthracene-9, 10-diamine, N, N '-diphenyl-N, N' -di (m-tolyl) anthracene-9, 10-diamine, N, N '-diphenyl-N, N' -bis (4-ethylphenyl) anthracene-9, 10-diamine, N, N '-diphenyl-N, N' -bis (4-isopropylphenyl) anthracene-9, 10-diamine, N, N '-diphenyl-N, N' -bis (4-t-butylphenyl) anthracene-9, 10-diamine, N, N '-bis (4-isopropylphenyl) -N, N' -di (p-tolyl) anthracene-9, 10-diamine, 2, 6-di-t-butyl-N, N, N ', N' -tetra (p-tolyl) anthracene-9, 10-diamine, 2, 6-di-t-butyl-N, N '-diphenyl-N, N' -bis (4-isopropylphenyl) anthracene-9, 10-diamine, a salt thereof, a base material thereof, and a binder, 2, 6-di-t-butyl-N, N '-bis (4-isopropylphenyl) -N, N' -di (p-tolyl) anthracene-9, 10-diamine, 2, 6-dicyclohexyl-N, N '-bis (4-isopropylphenyl) -N, N' -bis (4-t-butylphenyl) anthracene-9, 10-diamine, 9, 10-bis (4-diphenylamino-phenyl) anthracene, 9, 10-bis (4-di (1-naphthylamino) phenyl) anthracene, 9, 10-bis (4-di (2-naphthylamino) phenyl) anthracene, 10-di-p-tolylamino-9- (4-di-p-tolylamino-1-naphthyl) anthracene, 10-diphenylamino-9- (4-diphenylamino-1-naphthyl) anthracene, 10-diphenylamino-9- (6-diphenylamino-2-naphthyl) anthracene, and the like.
In addition, there may be mentioned: [4- (4-diphenylamino-phenyl) naphthalen-1-yl ] -diphenylamine [6- (4-diphenylamino-phenyl) naphthalen-2-yl ] -diphenylamine, 4 '-bis [ 4-diphenylaminonaphthalen-1-yl ] biphenyl 4,4' -bis [ 6-diphenylaminonaphthalene-2-yl ] biphenyl, 4 "-bis [ 4-diphenylaminonaphthalene-1-yl ] -p-terphenyl, 4" -bis [ 6-diphenylaminonaphthalene-2-yl ] -p-terphenyl, and the like.
Further, aromatic amine derivatives described in Japanese patent laid-open publication No. 2006-156888 and the like can also be used.
As the coumarin derivative, there can be mentioned: coumarin-6, coumarin-334 and the like.
Further, coumarin derivatives described in, for example, japanese patent laid-open Nos. 2004-43646, 2001-76876, and 6-298758 can also be used.
Examples of the pyran derivative include DCM and DCJTB described below.
[ solution 158]
Figure BDA0003862503640001471
Further, pyran derivatives described in Japanese patent laid-open Nos. 2005-126399, 2005-097283, 2002-234892, 2001-220577, 2001-081090, and 2001-052869 may also be used.
The material for a light-emitting layer (host material and dopant material) may be used as a polymer compound obtained by polymerizing a reactive compound having a reactive substituent substituted in the material for a light-emitting layer (host material and dopant material) as a monomer, or as a crosslinked polymer compound thereof obtained by reacting a main chain polymer with the reactive compound, or as a suspended polymer compound obtained by polymerizing a reactive compound having a reactive substituent substituted in the material for a light-emitting layer or a crosslinked polymer compound thereof. As the reactive substituent in such a case, the description of the polycyclic aromatic compound represented by the above general formula (1) can be cited.
The use of such a polymer compound and a crosslinked polymer will be described in detail later.
< Electron injection layer, electron transport layer in organic electroluminescent element >
The electron injection layer 107 functions to efficiently inject electrons transferred from the cathode 108 into the light-emitting layer 105 or the electron transport layer 106. The electron transport layer 106 functions to efficiently transport electrons injected from the cathode 108 or electrons injected from the cathode 108 through the electron injection layer 107 to the light-emitting layer 105. The electron transporting layer 106 and the electron injecting layer 107 are formed by laminating and mixing one or two or more kinds of electron transporting/injecting materials, or are formed by mixing an electron transporting/injecting material and a polymer binder.
The electron injection/transport layer is a layer that is responsible for injecting electrons from the cathode and transporting the electrons, and is preferably high in electron injection efficiency and capable of transporting the injected electrons efficiently. Therefore, a substance having a high electron affinity, a high electron mobility, and excellent stability is preferable, and impurities that become traps are less likely to be generated during production and use. However, when the balance between the transport of holes and electrons is considered, if the effect of efficiently preventing the flow of holes from the anode to the cathode side without being recombined is mainly exerted, the effect of improving the light emission efficiency is obtained as well as the effect of improving the light emission efficiency by the material having a high electron transport ability even if the electron transport ability is not so high. Therefore, the electron injection/transport layer in this embodiment mode may also include a function of a layer capable of efficiently preventing hole transfer.
The material (electron transport material) for forming the electron transport layer 106 or the electron injection layer 107 can be selected and used as desired from compounds conventionally used as electron transport compounds in photoconductive materials and conventional compounds used in electron injection layers and electron transport layers of organic EL devices. In the present invention, as the electron transporting material, a polycyclic aromatic compound represented by the general formula (1) or the general formula (2) may be used.
The material used for the electron transport layer or the electron injection layer preferably contains at least one compound selected from the following compounds: a compound containing an aromatic ring or a heteroaromatic ring containing at least one atom selected from carbon, hydrogen, oxygen, sulfur, silicon, and phosphorus; pyrrole derivatives and fused ring derivatives thereof; and a metal complex having electron-accepting nitrogen. Specifically, the following are listed: fused ring aromatic ring derivatives such as naphthalene and anthracene, styrene aromatic ring derivatives represented by 4,4' -bis (diphenylvinyl) biphenyl, perinone derivatives, coumarin derivatives, naphthalimide derivatives, quinone derivatives such as anthraquinone and diphenoquinone, phosphorus oxide derivatives, carbazole derivatives, indole derivatives, and the like. Examples of the metal complex having electron-accepting nitrogen include: and hydroxyoxazole complexes such as hydroxyphenyl oxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. These materials may be used alone or in combination with different materials.
Specific examples of the other electron transport compound include: pyridine derivatives, naphthalene derivatives, anthracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone derivatives, perylene derivatives, oxadiazole derivatives (1, 3-bis [ (4-tert-butylphenyl) 1,3, 4-oxadiazolyl ] phenylene, etc.), thiophene derivatives, triazole derivatives (N-naphthyl-2, 5-diphenyl-1, 3, 4-triazole, etc.), thiadiazole derivatives, metal complexes of 8-hydroxyquinoline (oxine) derivatives, hydroxyquinoline-based metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, indoline (benzazole) compounds, gallium complexes, pyrazole derivatives, perfluorinated phenylene derivatives, triazine derivatives, pyrazine derivatives, benzoquinoline derivatives (2, 2' -bis (benzo [ h ] quinolin-2-yl) -9,9' -spirobifluorene, etc.), imidazopyridine derivatives, borane derivatives, benzimidazole derivatives (tris (N-phenylbenzimidazol-2-yl) benzene, etc.), benzoxazole derivatives, benzothiazole derivatives, naphthoxazine derivatives, oline derivatives, benzo [ e ] quinoline-2-yl ] -9,9' -spirobifluorine derivatives, etc.), imidazopyridine derivatives, tris (4 ' -terpyridyl) -1, 6' -terpyridyl) -1, 2' -terpyridyl) derivatives, 3, 4' -terpyridyl) derivatives, etc.), etc., benzimidazole derivatives, etc, aldazine derivatives, carbazole derivatives, indole derivatives, phosphorus oxide derivatives, bisstyryl derivatives, and the like.
In addition, a metal complex having electron-accepting nitrogen may also be used, and examples thereof include: hydroxyoxazole complexes such as hydroxyquinoline metal complexes and hydroxyphenyl oxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes.
The materials can be used alone or in admixture with different materials.
Among these materials, preferred are borane derivatives, pyridine derivatives, fluoranthene derivatives, BO derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, and hydroxyquinoline metal complexes described in japanese patent laid-open No. 2021-14446.
The electron transport layer or the electron injection layer may further contain a substance capable of reducing a material forming the electron transport layer or the electron injection layer. As the reducing substance, various substances can be used as long as the substance has a certain reducing property, and for example, at least one selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, oxides of alkali metals, halides of alkali metals, oxides of alkaline earth metals, halides of alkaline earth metals, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals, and organic complexes of rare earth metals can be preferably used.
Preferable reducing substances include alkali metals such as Na (work function 2.36 eV), K (work function 2.28 eV), rb (work function 2.16 eV), and Cs (work function 1.95 eV), and alkaline earth metals such as Ca (work function 2.9 eV), sr (work function 2.0 to 2.5 eV), and Ba (work function 2.52 eV), and particularly preferable substances have a work function of 2.9eV or less. Among these, the reducing substance is more preferably K, rb or Cs as an alkali metal, further preferably Rb or Cs, and most preferably Cs. These alkali metals have particularly high reducing power, and by adding a relatively small amount of the alkali metals to a material forming the electron transporting layer or the electron injecting layer, improvement in light emission luminance or prolongation in the organic EL element can be achieved. In addition, as the reducing substance having a work function of 2.9eV or less, a combination of two or more of these alkali metals is also preferable, and a combination including Cs, for example, a combination of Cs and Na, cs and K, cs and Rb, or Cs and Na and K is particularly preferable. By including Cs, the reducing ability can be efficiently exerted, and by adding Cs to a material for forming an electron transporting layer or an electron injecting layer, improvement in light emission luminance or prolongation in life of the organic EL element can be achieved.
The material for an electron injection layer and the material for an electron transport layer may be used as a polymer compound obtained by polymerizing a reactive compound obtained by substituting a reactive substituent in the material for an electron injection layer and the material for an electron transport layer with a main chain polymer as a monomer or a crosslinked polymer thereof, or as a suspended polymer compound obtained by reacting a reactive compound with a main chain polymer or a crosslinked polymer thereof. As the reactive substituent in the above case, the description of the polycyclic aromatic compound represented by the above general formula (1) can be cited.
The use of such a polymer compound and a crosslinked polymer will be described in detail later.
< cathode in organic electroluminescent element >
The cathode 108 functions to inject electrons into the light-emitting layer 105 through the electron injection layer 107 and the electron transport layer 106.
The material forming the cathode 108 is not particularly limited as long as it can efficiently inject electrons into the organic layer, and the same material as the material forming the anode 102 can be used. Among them, metals such as tin, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, cesium, and magnesium, and alloys thereof (e.g., magnesium-silver alloys, magnesium-indium alloys, and aluminum-lithium alloys such as lithium fluoride and aluminum) are preferable. In order to improve the electron injection efficiency to improve the element characteristics, lithium, sodium, potassium, cesium, calcium, magnesium, or an alloy containing these low work function metals is effective. However, in general, these low work function metals are unstable in the atmosphere in many cases. In order to improve this, for example, a method of doping a small amount of lithium, cesium, or magnesium into an organic layer and using an electrode having high stability is known. As other dopant, inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide, and cesium oxide can also be used. However, the present invention is not limited to these examples.
Further, the following are listed as preferable examples: metals such as platinum, gold, silver, copper, iron, tin, aluminum, and indium, alloys using these metals, inorganic substances such as silicon dioxide, titanium dioxide, and silicon nitride, polyvinyl alcohol, vinyl chloride, hydrocarbon-based polymer compounds, and the like are laminated to protect the electrodes. The method of manufacturing these electrodes is not particularly limited as long as conduction can be achieved by resistance heating, electron beam evaporation, sputtering, ion plating, coating, or the like.
< Binders usable in the layers >
The materials used for the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer may be used individually for each layer, or may be dispersed in a solvent-soluble resin such as polyvinyl chloride, polycarbonate, polystyrene, poly (N-vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene ether, polybutadiene, a hydrocarbon resin, a ketone resin, a phenoxy resin, polyamide, ethyl cellulose, a vinyl acetate resin, an Acrylonitrile-Butadiene-Styrene (ABS) resin, or a polyurethane resin, or a curable resin such as a phenol resin, a xylene resin, a petroleum resin, a urea resin, a melamine resin, an unsaturated polyester resin, an alkyd resin, an epoxy resin, or a silicone resin, which is a polymer binder.
< method for manufacturing organic electroluminescent element >
Each layer constituting the organic EL element can be formed by forming a material to be each layer into a thin film by a method such as vapor deposition, resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination, printing, spin coating, casting, or coating. The film thickness of each layer formed in the above-described manner is not particularly limited, and may be appropriately set depending on the properties of the material, but is generally in the range of 2nm to 5000 nm. The film thickness can be measured by a crystal oscillation type film thickness measuring apparatus or the like. When a thin film is formed by a vapor deposition method, the vapor deposition conditions vary depending on the type of material, the target crystal structure and the association structure of the film, and the like. The deposition conditions are preferably set to +50 ℃ to +400 ℃ in a boat heating temperature and 10 degrees vacuum -6 Pa～10 -3 Pa, a deposition rate of 0.01 nm/sec to 50 nm/sec, a substrate temperature of-150 ℃ to +300 ℃, and a film thickness of 2nm to 5 μm.
When a dc voltage is applied to the organic EL element obtained as described above, the anode may be applied with a + polarity and the cathode may be applied with a-polarity, and when a voltage of about 2V to 40V is applied, light emission can be observed from the transparent or translucent electrode side (anode or cathode, or both). In addition, the organic EL element emits light even when a pulse current or an alternating current is applied thereto. In addition, the waveform of the applied alternating current may be arbitrary.
Next, as an example of a method for manufacturing an organic EL element, a method for manufacturing an organic EL element including an anode, a hole injection layer, a hole transport layer, a light-emitting layer including a host material and a dopant material, an electron transport layer, an electron injection layer, and a cathode will be described.
< vapor deposition method >
An anode is formed by forming a thin film of an anode material on an appropriate substrate by an evaporation method or the like, and then a thin film of a hole injection layer and a hole transport layer is formed on the anode. A thin film is formed on the thin film by co-evaporation of a host material and a dopant material to form a light-emitting layer, an electron-transporting layer and an electron-injecting layer are formed on the light-emitting layer, and a thin film containing a substance for a cathode is formed by an evaporation method or the like to form a cathode, thereby obtaining a target organic EL element. In the production of the organic EL element, the order of production may be reversed, and the organic EL element may be produced by using a cathode, an electron injection layer, an electron transport layer, a light-emitting layer, a hole transport layer, a hole injection layer, and an anode in this order.
< Wet film Forming method >
A low-molecular-weight compound capable of forming each organic layer of an organic EL element is prepared as a liquid composition for forming an organic layer, and a wet film-forming method is performed using the composition. In the case where an appropriate organic solvent for dissolving the low-molecular compound is not present, the composition for forming an organic layer may be prepared from a polymer compound which is polymerized together with another monomer or main chain polymer having a solubility function as a reactive compound obtained by substituting a reactive substituent in the low-molecular compound, or the like.
In general, a coating film is formed by a wet film forming method through a coating step of coating a substrate with an organic layer forming composition and a drying step of removing a solvent from the coated organic layer forming composition. In the case where the polymer compound has a crosslinkable substituent (also referred to as a crosslinkable polymer compound), the polymer compound is further crosslinked by the drying step to form a crosslinked polymer. Depending on the coating process, a method using a spin coater is called a spin coating method, a method using a slit coater is called a slit coating method, a method using a plate is called a gravure, offset, reverse offset, or flexo printing method, a method using an ink jet printer is called an ink jet method, and a method of spraying mist is called a spray method. The drying step may be carried out by air drying, heating, drying under reduced pressure, or the like. The drying step may be performed only once, or may be performed a plurality of times by using different methods or conditions. Further, for example, different methods may be used in combination as in calcination under reduced pressure.
The wet film formation method is a film formation method using a solution, and examples thereof include a partial printing method (ink jet method), a spin coating method, a casting method, and a coating method. Unlike the vacuum deposition method, the wet film formation method can form a film under atmospheric pressure without using an expensive vacuum deposition apparatus. In addition, the wet film formation method can be used for large-area production or continuous production, which leads to reduction in production cost.
On the other hand, in comparison with the vacuum deposition method, the wet film formation method may be difficult to form a laminate. In the case of producing a laminated film by a wet film formation method, it is necessary to prevent dissolution of the lower layer by the composition of the upper layer and to use a composition having controlled solubility, a crosslinking of the lower layer, an Orthogonal solvent (mutually insoluble solvent), and the like. However, even with these techniques, it is sometimes difficult to apply the wet film formation method to the coating of all the films.
Thus, the following methods can be generally employed: only a few layers were formed by a wet film formation method, and the remaining layers were formed by a vacuum deposition method, thereby producing an organic EL element.
For example, a part of the procedure for producing an organic EL element by applying a wet film formation method is described below.
(procedure 1) deposition of Anode by vacuum deposition
(procedure 2) film formation by Wet film formation method of composition for Forming hole injection layer containing Material for hole injection layer
(procedure 3) film formation of composition for hole transport layer formation containing material for hole transport layer by Wet film formation method
(procedure 4) film formation by Wet film formation method of light-emitting layer-Forming composition containing host Material and dopant Material
(program 5) film formation of Electron transport layer by vacuum deposition
(procedure 6) film formation of the Electron injection layer by vacuum deposition
(program 7) film formation of cathode by vacuum vapor deposition
By passing through the procedure, an organic EL element including an anode/a hole injection layer/a hole transport layer/a light emitting layer containing a host material and a dopant material/an electron transport layer/an electron injection layer/a cathode can be obtained.
Of course, there is a means for preventing the light-emitting layer of the underlayer from dissolving, and a means for forming a film from the cathode side contrary to the above procedure is used, so that a composition for forming a layer containing a material for an electron-transporting layer or a material for an electron-injecting layer can be prepared and the composition can be formed into a film by a wet film-forming method.
< other film formation method >
In the formation of a film of the composition for forming an organic layer, a Laser Induced Thermal Imaging (LITI) method may be used. LITI is a method of performing thermal vapor deposition of a compound attached to a substrate by using a laser, and the organic layer forming composition can be used for a material to be coated on a substrate.
< optional Process >
Before and after each step of film formation, an appropriate treatment step, cleaning step and drying step may be added as appropriate. Examples of the treatment step include: exposure treatment, plasma surface treatment, ultrasonic treatment, ozone treatment, cleaning treatment with an appropriate solvent, heat treatment, and the like. Further, a series of steps for producing the bank may be mentioned.
Photolithography techniques may be used in the fabrication of the banks. As the bank material that can be used for photolithography, a positive resist material and a negative resist material can be used. Further, a printing method capable of forming a pattern, such as an ink jet method, gravure lithography, reverse lithography, and screen printing, may be used. At this time, a permanent resist material may also be used.
Examples of the material for the banks include polysaccharides and derivatives thereof, homopolymers and copolymers of vinyl monomers having a hydroxyl group, biopolymer compounds, polyacryl compounds, polyesters, polystyrene, polyimide, polyamideimide, polyetherimide, polythioether, polysulfone, poly (phenylene), polyphenylene ether, polyurethane, epoxy (meth) acrylate, melamine (meth) acrylate, polyolefin, cyclic polyolefin, acrylonitrile-butadiene-styrene copolymer (ABS), silicone resin, polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, polyacetate, polynorbornene, synthetic rubber, fluorinated polymers such as polyvinylidene fluoride, polytetrafluoroethylene, polyhexafluoropropylene, fluorinated olefin-hydrocarbon olefin copolymers, and fluorocarbon polymers, but the present invention is not limited thereto.
< composition for forming organic layer used in Wet film Forming method >
The composition for forming an organic layer is obtained by dissolving a low-molecular compound capable of forming each organic layer of an organic EL element or a high-molecular compound obtained by polymerizing the low-molecular compound in an organic solvent. For example, the composition for forming a light-emitting layer contains a polycyclic aromatic compound (or a polymer compound thereof) as a first component, which is at least one dopant material, at least one host material as a second component, and at least one organic solvent as a third component. The first component functions as a dopant component of the light-emitting layer obtained from the composition, and the second component functions as a host component of the light-emitting layer. The third component functions as a solvent for dissolving the first component and the second component in the composition, and a smooth and uniform surface shape is obtained by a controlled evaporation rate of the third component itself at the time of coating.
< organic solvent >
The composition for forming an organic layer contains at least one organic solvent. The film forming property, the presence or absence of defects in the film, the surface roughness, and the smoothness can be controlled and improved by controlling the evaporation rate of the organic solvent during film formation. In addition, when the film formation is performed by using the ink jet method, the meniscus (meniscus) stability at the pin hole of the ink jet head can be controlled, and the ejection property can be controlled/improved. In addition, by controlling the drying rate of the film and the orientation of the derivative molecules, the electrical characteristics, light emission characteristics, efficiency, and lifetime of the organic EL element having the organic layer obtained from the composition for forming an organic layer can be improved.
(1) Physical Properties of organic solvent
The boiling point of the at least one organic solvent is 130 to 300 ℃, more preferably 140 to 270 ℃, and still more preferably 150 to 250 ℃. From the viewpoint of the ejection property of the inkjet, the boiling point is preferably higher than 130 ℃. In addition, from the viewpoint of defects, surface roughness, residual solvent and smoothness of the coating film, the boiling point is preferably less than 300 ℃. The organic solvent is more preferably a structure containing two or more organic solvents from the viewpoint of good ink jet ejection properties, film formation properties, smoothness, and a small amount of residual solvent. On the other hand, the organic layer-forming composition may be a composition which is made into a solid state by removing the solvent from the composition in consideration of the transportability and the like.
The organic solvent further contains a Good Solvent (GS) and a Poor Solvent (PS) for at least one of the solutes, and the Boiling Point (BP) of the Good Solvent (GS) is particularly preferred GS ) Lower than the Boiling Point (BP) of the Poor Solvent (PS) PS ) The structure of (1).
By adding poor solvent with high boiling point, the good solvent with low boiling point volatilizes first during film forming, the concentration of the content in the composition and the concentration of the poor solvent are increased, and the rapid film forming is promoted. As a result, a coating film having few defects, small surface roughness, and high smoothness can be obtained.
Difference in solubility (S) GS -S PS ) Preferably 1% or more, more preferably 3% or more, and still more preferably 5% or more. Difference in Boiling Point (BP) PS -BP GS ) Preferably 10 ℃ or higher, more preferably 30 ℃ or higher, and still more preferably 50 ℃ or higher.
The organic solvent is removed from the coating film by a drying step such as vacuum, reduced pressure, or heating after film formation. In the case of heating, from the viewpoint of improving coating film formability, it is preferable to perform the heating at a glass transition temperature (Tg) of at least one of the solutes) +30 ℃. From the viewpoint of reducing the residual solvent, it is preferable to heat the solvent at a glass transition temperature (Tg) of at least one solute to 30 ℃ or higher. Even if the heating temperature is lower than the boiling point of the organic solvent, the organic solvent is sufficiently removed because the film is thin. Further, the drying may be performed a plurality of times at different temperatures, or a plurality of drying methods may be used in combination.
(2) Specific examples of organic solvents
<xnotran> , , , , , , , , , , , , , , , , , , -2- , -2- , -2- , -2- , -2- , , α - (α -terpineol), β - , γ - , δ - , (), , , , , , , , , , , , , , , , , , , , , , ,2,6- ,2- - ,3- - ,2- , , ,2- -6- ,2- , ,2,3- , </xnotran> Bromobenzene, 4-fluorophenylmethyl ether, 3-trifluoromethylanisole, mesitylene, 1,2, 4-trimethylbenzene, tert-butylbenzene, 2-methylanisole, phenetole, benzodioxole (benzodioxole), 4-methylanisole, sec-butylbenzene, 3-methylanisole, 4-fluoro-3-methylanisole, isopropyltoluene (cymene), 1,2, 3-trimethylbenzene, 1, 2-dichlorobenzene, 2-fluorobenzonitrile, 4-fluoro-o-dimethoxybenzene (4-fluorodimethoxybenzene), 2, 6-dimethylanisole, n-butylbenzene, 3-fluorobenzonitrile, decalin (decalin), neopentylbenzene, 2, 5-dimethylanisole, 2, 4-dimethylanisole, benzonitrile, 2, 4-dimethylanisole, and mixtures thereof 3, 5-Dimethylanisole, diphenyl ether, 1-fluoro-3, 5-dimethoxybenzene, methyl benzoate, isopentylbenzene, 3, 4-Dimethylanisole, O-tolunitrile (o-tolonium), N-pentylbenzene, O-dimethoxybenzene (veratrole), 1,2,3, 4-Tetrahydronaphthalene, ethyl benzoate, N-hexylbenzene, propyl benzoate, cyclohexylbenzene, 1-methylnaphthalene, butyl benzoate, 2-methylbiphenyl, 3-phenoxytoluene, 2 '-Dimethylbiphenyl (2, 2' -bitolyl), dodecylbenzene, dipentylbenzene, tetramethylbenzene, trimethoxybenzene, trimethoxytoluene, 2, 3-dihydrobenzofuran, 1-methyl-4- (propoxymethyl) benzene, 1-methyl-4- (butoxymethyl) benzene, 1-methyl-4- (pentyloxymethyl) benzene, 1-methyl-4- (hexyloxymethyl) benzene, 1-methyl-4- (heptyloxymethyl) benzene, benzylbutyl ether, benzylpentyl ether, benzylhexyl ether, benzylheptyl ether, benzyloctyl ether and the like, but not limited thereto. The solvents may be used alone or in combination.
< any component >
The composition for forming an organic layer may contain any component within a range not impairing the properties thereof. Examples of the optional component include a binder and a surfactant.
(1) Adhesive agent
The organic layer-forming composition may contain a binder. As for the binder, at the time of film formation, the obtained film is joined to the substrate while forming the film. In addition, the organic layer forming composition plays a role in dissolving, dispersing, and binding other components.
Examples of the binder used in the organic layer forming composition include, but are not limited to, acrylic resins, polyethylene terephthalate, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, acrylonitrile-Ethylene-Styrene copolymer (AES) resins, ionomers, chlorinated polyethers, diallyl phthalate resins, unsaturated polyester resins, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride (polyvinylidene chloride), polystyrene, polyvinyl acetate, teflon (Teflon), acrylonitrile-butadiene-Styrene copolymer (ABS) resins, acrylonitrile-Styrene copolymer (Acrylonitrile-Styrene, AS) resins, phenol resins, epoxy resins, melamine resins, urea resins, alkyd resins, polyurethane resins, and copolymers of the above resins and polymers.
The binder used in the composition for forming an organic layer may be one kind or a mixture of two or more kinds.
(2) Surface active agent
The organic layer forming composition may contain a surfactant, for example, in order to control the film surface uniformity of the organic layer forming composition, and the solvent affinity and liquid repellency of the film surface. Surfactants are classified into ionic and nonionic surfactants according to the structure of hydrophilic groups, and further classified into alkyl surfactants, silicon surfactants, and fluorine surfactants according to the structure of hydrophobic groups. Further, the molecular structure is classified into a simple molecular system having a relatively small molecular weight and a high molecular system having a side chain or branch having a large molecular weight. Further, the compositions are classified into a single system and a mixed system in which two or more surfactants and a base material are mixed. As the surfactant that can be used in the composition for forming an organic layer, all kinds of surfactants can be used.
Examples of the surfactant include: pelizafelo (Polyflow) No.45, pelizafelo (Polyflow) KL-245, pelizafelo (Polyflow) No.75, pelizafelo (Polyflow) No.90, pelizao (Polyflow) No.95 (trade name, manufactured by Kyoeisha chemical industries, ltd.); disperbyk 161, disperbyk 162, disperbyk 163, disperbyk 164, disperbyk 166, disperbyk 170, disperbyk 180, disperbyk 181, disperbyk 182, BYK 300, BYK 306, BYK 310, BYK 320, BYK 330, BYK 342, BYK 344, BYK 346 (trade name, BYK-chemi Japan (BYK-Chemie Japan) (stock); KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (trade name, manufactured by shin-Etsu chemical industries, ltd.); safflon (Surflon) SC-101, safflon (Surflon) KH-40 (trade name, manufactured by Qingmei Chemical Co., ltd.); forgester (Ftergent) 222F, forgester (Ftergent) 251, FTX-218 (trade name, manufactured by Neos (NEOS) (Strand)); avotuo (EFTOP) EF-351, avotuo (EFTOP) EF-352, avotuo (EFTOP) EF-601, avotuo (EFTOP) EF-801, avotuo (EFTOP) EF-802 (trade name, manufactured by Mitsubishi Material, ltd.); meijia method (Megafac) F-470, meijia method (Megafac) F-471, meijia method (Megafac) F-475, meijia method (Megafac) R-08, meijia method (Megafac) F-477, meijia method (Megafac) F-479, meijia method (Megafac) F-553, meijia method (Megafac) F-554 (trade name, manufactured by Diesen (DIC) (Strand)); fluoroalkyl benzenesulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglyceryl tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethylammonium salt, fluoroalkyl sulfamate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene naphthyl ether, alkylbenzenesulfonate, and alkyldiphenyl ether disulfonate.
One kind of surfactant may be used, or two or more kinds may be used in combination.
< composition and Property of composition for Forming organic layer >
The content of each component in the composition for forming an organic layer is determined in consideration of good solubility, storage stability, and film forming property of each component in the composition for forming an organic layer, good film quality of a coating film obtained from the composition for forming an organic layer, good ejection property when an inkjet method is used, and good electrical characteristics, light emission characteristics, efficiency, and lifetime of an organic EL element having an organic layer manufactured using the composition. For example, in the case of the composition for forming a light-emitting layer, it is preferable that: the first component is 0.0001 to 2.0 wt% based on the total weight of the composition for forming a light-emitting layer, the second component is 0.0999 to 8.0 wt% based on the total weight of the composition for forming a light-emitting layer, and the third component is 90.0 to 99.9 wt% based on the total weight of the composition for forming a light-emitting layer.
More preferably: the first component is 0.005 to 1.0 wt% based on the total weight of the composition for forming a light-emitting layer, the second component is 0.095 to 4.0 wt% based on the total weight of the composition for forming a light-emitting layer, and the third component is 95.0 to 99.9 wt% based on the total weight of the composition for forming a light-emitting layer. More preferably: the first component is 0.05 to 0.5 wt% based on the total weight of the composition for forming a light-emitting layer, the second component is 0.25 to 2.5 wt% based on the total weight of the composition for forming a light-emitting layer, and the third component is 97.0 to 99.7 wt% based on the total weight of the composition for forming a light-emitting layer.
The composition for forming an organic layer can be produced by appropriately selecting the above-mentioned components by a conventional method and stirring, mixing, heating, cooling, dissolving, dispersing, or the like. After the preparation, filtration, degassing (also referred to as degassing), ion exchange treatment, inert gas replacement/encapsulation treatment, and the like may be appropriately selected and performed.
Regarding the viscosity of the organic layer forming composition, a good film forming property and a good ejection property when an inkjet method is used can be obtained in the case of a high viscosity. On the other hand, when the viscosity is low, a film is easily produced. Accordingly, the viscosity of the organic layer forming composition is preferably 0.3 to 3mPa · s, more preferably 1 to 3mPa · s, at 25 ℃. In the present invention, the viscosity is a value measured using a cone-plate type rotational viscometer (cone-plate type).
With respect to the surface tension of the organic layer forming composition, when the surface tension is low, a coating film having good film forming properties and no defects can be obtained. On the other hand, when the surface tension is high, good ink ejection properties can be obtained. Accordingly, the surface tension of the organic layer forming composition at 25 ℃ is preferably 20 to 40mN/m, and more preferably 20 to 30mN/m. In the present invention, the surface tension is a value measured using a pendant drop method.
< crosslinkable Polymer Compound: a compound represented by the general formula (XLP-1) >
Next, a case where the polymer compound has a crosslinkable substituent will be described. The crosslinkable polymer compound is, for example, a compound represented by the following general formula (XLP-1).
[ chemical 159]
Figure BDA0003862503640001551
In the formula (XLP-1),
MUx, ECx and k are defined as MU, EC and k in the formula (H3), wherein the compound represented by the formula (XLP-1) has at least one crosslinkable substituent (XLS), and preferably the content of the monovalent or divalent aromatic compound having a crosslinkable substituent is 0.1 to 80 wt% in the molecule.
The content of the monovalent or divalent aromatic compound having a crosslinkable substituent is preferably 0.5 to 50% by weight, more preferably 1 to 20% by weight.
The crosslinkable substituent (XLS) is not particularly limited as long as it is a group capable of further crosslinking the polymer compound, and is preferably a substituent having the following structure. Each structural formula indicates a bonding position.
[ 160]
Figure BDA0003862503640001561
<xnotran> L , -O-, -S-, ＞ C = O, -O-C (= O) -, 1 ～ 12 , 1 ～ 12 1 ～ 12 . </xnotran> Among the substituents, preferred is a group represented by formula (XLS-1), formula (XLS-2), formula (XLS-3), formula (XLS-9), formula (XLS-10) or formula (XLS-17), and more preferred is a group represented by formula (XLS-1), formula (XLS-3) or formula (XLS-17).
Examples of the divalent aromatic compound having a crosslinkable substituent include compounds having the following partial structures. In the following structural formula, a symbol indicates a bonding position.
[ solution 161]
Figure BDA0003862503640001562
[ chemical 162]
Figure BDA0003862503640001571
[ chemical 163]
Figure BDA0003862503640001572
[ 164]
Figure BDA0003862503640001573
< method for producing Polymer Compound and crosslinkable Polymer Compound
The production methods of the polymer compound and the crosslinkable polymer compound will be described by taking the compound represented by the above formula (H3) and the compound represented by the above formula (XLP-1) as examples. These compounds can be synthesized by appropriately combining conventional production methods.
Examples of the solvent used in the reaction include an aromatic solvent, a saturated/unsaturated hydrocarbon solvent, an alcohol solvent, and an ether solvent, and examples thereof include: dimethoxyethane, 2- (2-methoxyethoxy) ethane, 2- (2-ethoxyethoxy) ethane, and the like.
Alternatively, the reaction may be carried out in a two-phase system. In the case of carrying out the reaction in a two-phase system, a phase transfer catalyst such as quaternary ammonium salt may be added as required.
When the compound of the formula (H3) and the compound of the formula (XLP-1) are produced, they can be produced in one stage or through multiple stages. The synthesis may be carried out by an all-round polymerization method in which the reaction is started after all the raw materials are placed in the reaction vessel, by a dropping polymerization method in which the raw materials are dropped into the reaction vessel, by a precipitation polymerization method in which the product precipitates as the reaction proceeds, or by a combination of these methods as appropriate. For example, when the compound represented by formula (H3) is synthesized in one stage, the target compound is obtained by carrying out the reaction in a state where the Monomer Unit (MU) and the end-capping unit (EC) are charged into a reaction vessel. In addition, when the compound represented by the general formula (H3) is synthesized in multiple stages, the target compound is obtained by adding and reacting the end-capping unit (EC) after polymerizing the Monomer Unit (MU) to a target molecular weight. When different types of Monomer Units (MU) are added in multiple stages to carry out the reaction, a polymer having a concentration gradient with respect to the structure of the monomer units can be produced. In addition, after the precursor polymer is prepared, a polymer as a target can be obtained by a subsequent reaction.
Further, when the polymerizable group of the Monomer Unit (MU) is selected, the primary structure of the polymer can be controlled. For example, as shown in 1 to 3 of the synthesis schemes, a polymer having a random primary structure (1 of the synthesis scheme), a polymer having a regular primary structure (2 and 3 of the synthesis scheme), and the like can be synthesized, and can be used in appropriate combinations according to the target. Further, when a monomer unit having three or more polymerizable groups is used, a hyperbranched polymer or a dendrimer (dendrimer) can be synthesized.
[ solution 165]
a. b = MU or MUx
Polymerizable group = x, y (x and y bond, respectively)
1) Polymers synthesized using two monomers (x-a-y) and (x-b-y)
Figure BDA0003862503640001581
2) Polymers synthesized using two monomers (x-a-x) and (y-b-y)
Figure BDA0003862503640001582
3) Polymers synthesized using two monomers (x-a-y) and (y-b-y)
Figure BDA0003862503640001583
The monomer unit usable in the present invention can be synthesized by the methods described in Japanese patent laid-open publication No. 2010-189630, international publication No. 2012/086671, international publication No. 2013/191088, international publication No. 2002/045184, international publication No. 2011/049241, international publication No. 2013/146806, international publication No. 2005/049546, international publication No. 2015/145871, japanese patent laid-open publication No. 2010-215886, japanese patent laid-open publication No. 2008-106241, international publication No. 2016/031639, and Japanese patent laid-open publication No. 2011-174062.
Further, specific polymer synthesis procedures can be synthesized by methods described in japanese patent laid-open publication No. 2012-036388, international publication No. 2015/008851, japanese patent laid-open publication No. 2012-36381, japanese patent laid-open publication No. 2012-144722, international publication No. 2015/194448, international publication No. 2013/146806, international publication No. 2015/145871, international publication No. 2016/031639, international publication No. 2016/125560, and international publication No. 2011/049241.
< example of application of organic electroluminescent element >
In addition, the present invention is also applicable to a display device including an organic EL element, an illumination device including an organic EL element, or the like.
The display device or the lighting device including the organic EL element can be manufactured by a conventional method such as connecting the organic EL element of this embodiment to a conventional driving device, and can be driven by a conventional driving method such as direct current driving, pulse driving, or alternating current driving.
Examples of the display device include: a panel display such as a color flat panel display, a flexible display such as a flexible color organic Electroluminescence (EL) display, and the like (see, for example, japanese patent laid-open No. 10-335066, japanese patent laid-open No. 2003-321546, and japanese patent laid-open No. 2004-281086). Examples of the display mode of the display include a matrix mode and a segment mode. Further, the matrix display and the segment display may coexist in the same panel (panel).
In the matrix, pixels for display are two-dimensionally arranged in a lattice shape, a mosaic shape, or the like, and characters or images are displayed by a set of pixels. The shape or size of the pixel is determined according to the application. For example, in image and character display of a personal computer, a monitor, and a television, a rectangular pixel having a side of 300 μm or less is generally used, and in the case of a large-sized display such as a display panel, a pixel having a side of mm level is used. In the case of monochrome display, pixels of the same color may be arranged, and in the case of color display, pixels of red, green, and blue are arranged in parallel to perform display. In this case, a triangular shape and a striped shape are typical. Also, as a driving method of the matrix, any one of a line-sequential (line-sequential) driving method or an active matrix may be used. The line sequential driving has an advantage of a simple structure, but when the operation characteristics are taken into consideration, the active matrix is sometimes more excellent, and therefore the driving method needs to be used separately depending on the application.
In the segmentation method (type), a pattern is formed so as to display information determined in advance, and the determined region is caused to emit light. Examples thereof include: time and temperature display in a digital clock or a thermometer, operation state display of an audio device or an induction cooker, panel display of an automobile, and the like.
Examples of the illumination device include an illumination device such as an indoor illumination, and a backlight of a liquid crystal display device (see, for example, japanese patent laid-open nos. 2003-257621, 2003-277741, and 2004-119211). Backlights are used mainly for improving visibility of display devices that do not emit light, and are used for liquid crystal display devices, clocks, audio devices, automobile panels, display panels, signs, and the like. In particular, as a backlight for personal computer applications in which thinning is becoming a problem in a liquid crystal display device, when it is considered that thinning is difficult in the conventional system including a fluorescent lamp or a light guide plate, the backlight using the light emitting element of the present embodiment has features of being thin and lightweight.
3-2. Other organic devices
The polycyclic aromatic compound of the present invention can be used for the production of an organic field effect transistor, an organic thin film solar cell, a wavelength conversion filter, or the like, in addition to the organic electroluminescent element.
The organic field effect transistor is a transistor in which current is controlled by an electric field generated by voltage input, and includes a gate electrode in addition to an active electrode and a drain electrode. The organic field effect transistor is a transistor as follows: when a voltage is applied to the gate electrode, an electric field is generated, and the flow of electrons (or holes) flowing between the source electrode and the drain electrode can be arbitrarily blocked to control the current. A field effect transistor is easy to be miniaturized compared with a single transistor (bipolar transistor), and is often used as an element constituting an integrated circuit or the like.
In general, the organic field effect transistor may be configured such that a source electrode and a drain electrode are provided in contact with an organic semiconductor active layer formed using the polycyclic aromatic compound of the present invention, and a gate electrode is provided through an insulating layer (dielectric layer) in contact with the organic semiconductor active layer. Examples of the element structure include the following structures.
(1) Substrate, gate electrode, insulator layer, source electrode, drain electrode, and organic semiconductor active layer
(2) Substrate, gate electrode, insulator layer, organic semiconductor active layer, source electrode and drain electrode
(3) Substrate/organic semiconductor active layer/source electrode and drain electrode/insulator layer/gate electrode
(4) Substrate/source and drain electrodes/organic semiconductor active layer/insulator layer/gate electrode
The organic field effect transistor configured as described above can be suitably used as a pixel driving switching element of an active matrix driving type liquid crystal display or an organic electroluminescence display.
An organic thin-film solar cell has a structure in which an anode such as ITO, a hole transport layer, a photoelectric conversion layer, an electron transport layer, and a cathode are stacked on a transparent substrate such as glass. The photoelectric conversion layer has a p-type semiconductor layer on the anode side and an n-type semiconductor layer on the cathode side. The polycyclic aromatic compound of the present invention can be used as a material for a hole transport layer, a p-type semiconductor layer, an n-type semiconductor layer, and an electron transport layer, depending on the physical properties thereof. In the organic thin film solar cell, the polycyclic aromatic compound of the present invention can function as a hole transport material or an electron transport material. The organic thin film solar cell may suitably include a hole blocking layer, an electron injection layer, a hole injection layer, a smoothing layer, and the like, in addition to the layers. In the organic thin film solar cell, known materials used in the organic thin film solar cell may be appropriately selected and used in combination.
The application of multicolor technology based on a color conversion method to a liquid crystal display or an organic EL display, illumination, and the like is being actively studied. The color conversion is to convert the emission wavelength from the light-emitting body into light having a longer wavelength, and means, for example, converting ultraviolet light or blue light into green light or red light. The wavelength conversion material having the color conversion function is formed into a film, and for example, is combined with a blue light source, whereby three primary colors of blue, green, and red, that is, white light can be extracted from the blue light source. A full color display (full color display) can be manufactured by using a white light source in which a blue light source and a wavelength conversion filter having a color conversion function are combined as a light source unit, and combining the white light source with a liquid crystal driving section and a color filter. In addition, without a liquid crystal driving portion, the liquid crystal display device can be used as a white light source as it is, and can be applied to a white light source such as a light-emitting diode (LED) lighting. Further, a full-color organic EL display can be manufactured without using a metal mask by using a blue organic EL element as a light source and using it in combination with a wavelength conversion filter that converts blue light into green light and red light. Furthermore, a full-color micro LED display can be manufactured at low cost by using a blue micro LED as a light source in combination with a wavelength conversion filter that converts blue light into green light and red light.
The polycyclic aromatic compound of the present invention is useful as a material for use in the wavelength conversion filter. Ultraviolet light or light from a light source or a light-emitting element that generates blue light having a shorter wavelength can be converted into blue light or green light having high color purity and suitable for use in a display device (a display device or a liquid crystal display device using an organic EL element) using a wavelength conversion filter containing the polycyclic aromatic compound of the present invention. The color to be converted can be adjusted by appropriately selecting the substituent of the polycyclic aromatic compound of the present invention, a binder resin used in a wavelength converting composition described later, and the like. The wavelength converting material may be prepared as a wavelength converting composition containing the polycyclic aromatic compound of the present invention. In addition, a wavelength conversion filter can also be formed using the wavelength conversion composition.
The wavelength conversion composition may further contain a binder resin, other additives, and a solvent in addition to the polycyclic aromatic compound of the present invention. Examples of the binder resin include resins described in paragraphs 0173 to 0176 of International publication No. 2016/190283. As other additives, compounds described in paragraphs 0177 to 0181 of International publication No. 2016/190283 can be used. As the solvent, the description of the solvent contained in the composition for forming a light-emitting layer can be referred to.
The wavelength conversion filter includes a wavelength conversion layer formed by curing a wavelength conversion composition. As a method for producing a wavelength conversion layer from the wavelength conversion composition, a conventional film formation method can be referred to. The wavelength conversion filter may include only a wavelength conversion layer formed of the composition including the polycyclic aromatic compound of the present invention, and may also include other wavelength conversion layers (for example, a wavelength conversion layer converting blue light into green light or red light, and a wavelength conversion layer converting blue light or green light into red light). Further, the wavelength conversion filter may include a base material layer or a barrier layer for preventing the color conversion layer from being deteriorated by oxygen, moisture, or heat.
[ examples ]
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples. First, a synthesis example of the polycyclic aromatic compound will be described below.
Synthesis example (1): synthesis of Compound (1-1)
[ solution 166]
Figure BDA0003862503640001611
To a flask containing intermediate (X-1) (20.0 g), iron (46.5 mg) and chloroform (100 ml) was added bromine (6.43 ml) under a nitrogen atmosphere. After stirring at room temperature for 18 hours, it was cooled to 0 ℃ and an aqueous solution of sodium thiosulfate (10 wt%,200 ml) was added. Thereafter, heptane was added and stirred, and then the organic layer was separated and washed with water. Thereafter, the crude product obtained by concentrating the organic layer was purified by means of a silica gel short path column (eluent: heptane), whereby intermediate (X-2) (26.2 g) was obtained.
[ 167]
Figure BDA0003862503640001612
To a flask, under a nitrogen atmosphere, intermediate (X-2) (10.0 g), intermediate (X-3) (14.0 g), 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl (SPhos, 1.93 g), palladium acetate (0.35 g) as a palladium catalyst, sodium tert-butoxide (tBuONa, 4.51 g) and toluene (500 ml) were added, and the mixture was heated at 110 ℃ for 3 hours. After the reaction, water and ethyl acetate were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. After that, the crude product obtained by concentrating the organic layer was purified by means of a silica gel short path column (eluent: toluene/heptane =1/4 (volume ratio)), whereby intermediate (X-4) (12.4 g) was obtained.
[ solution 168]
Figure BDA0003862503640001621
To a flask, under a nitrogen atmosphere, intermediate (X-4) (12.4 g), 3,4, 5-trichlorotert-butylbenzene (4.0 g), dichlorobis [ di-tert-butyl (4-dimethylaminophenyl) phosphino ] palladium (II) (Pd-132, 0.6 g) as a palladium catalyst, tBuONa (2.43 g) and toluene (300 ml) were added, and the mixture was heated at 120 ℃ for 5 hours. After the reaction, water and ethyl acetate were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. After that, the crude product obtained by concentrating the organic layer was purified by means of a silica gel short path column (eluent: toluene/heptane =1/4 (volume ratio)), whereby intermediate (X-5) (7.5 g) was obtained.
[ solution 169]
Figure BDA0003862503640001622
To a flask, under a nitrogen atmosphere, intermediate (X-5) (7.5 g), intermediate (X-6) (4.3 g), pd-132 (0.33 g) as a palladium catalyst, tBuONa (1.3 g) and toluene (300 ml) were added, and the mixture was heated at 120 ℃ for 6 hours. After the reaction, water and ethyl acetate were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Thereafter, the crude product obtained by concentrating the organic layer was purified by a silica gel short-path column (eluent: toluene/heptane =1/5 (volume ratio)), thereby obtaining an intermediate (X-7) (7.9 g).
[ solution 170]
Figure BDA0003862503640001623
A1.60M solution (8.5 ml) of t-butyllithium pentane was added to a flask into which intermediate (X-7) (7.9 g) and t-butylbenzene (100 ml) were charged under a nitrogen atmosphere at 0 ℃. After the completion of the dropwise addition, the temperature was raised to 70 ℃ and the mixture was stirred for 0.5 hour, and then components having a boiling point lower than that of tert-butylbenzene were distilled off under reduced pressure. Boron tribromide (3.4 g) was added after cooling to-50 ℃ and the mixture was warmed to room temperature and stirred for 0.5 hour. Then, the mixture was cooled again to 0 ℃ and N, N-diisopropylethylamine (1.8 g) was added thereto, and the mixture was stirred at room temperature until heat generation was completed, and then heated to 100 ℃ and stirred for 1 hour. The reaction solution was cooled to room temperature, and then an aqueous sodium acetate solution cooled in an ice bath was added thereto, followed by adding ethyl acetate to separate the solution. The organic layer was concentrated and purified by silica gel short path column chromatography (eluent: chlorobenzene). The obtained crude product was recrystallized using toluene, whereby compound (1-1) (2.3 g) was obtained.
[ solution 171]
Figure BDA0003862503640001631
The structure of the obtained compound was confirmed by Nuclear Magnetic Resonance (NMR) measurement.
1 H-NMR(500MHz,CDCl 3 )：δ＝0.90(s,6H),0.95(s,9H),1.09(s,6H),1.18-1.27(m,8H),1.32(s,18H),1.37-1.46(m,16H),1.48-1.52(m,4H),1.66-1.83(m,10H),2.17-2.22(m,1H),5.93(d,1H),6.11(d,1H),6.47(d,1H),6.61(s,1H),6.88(dd,1H),6.98-7.04(m,4H),7.06(dd,1H),7.15(d,2H),7.18-7.23(m,4H),7.28(d,1H),7.43(d,2H),7.58(d,1H),8.68(d,1H),8.75(s,1H).
Synthesis example (2): synthesis of Compound (1-7)
Compound (1-7) was obtained from intermediate (Int-1-7) in the same manner as in Synthesis example (1).
[ chemical 172]
Figure BDA0003862503640001632
The target was M/z (M + H) =1162.81 as confirmed by Matrix-assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF-MS).
Synthesis example (3): synthesis of Compound (1-13)
Compound (1-13) was obtained from intermediate (Int-1-13) in the same manner as in Synthesis example (1).
[ chemical 173]
Figure BDA0003862503640001641
It was confirmed by MALDI-TOF-MS that M/z (M + H) =983.74 of the target.
Synthesis example (4): synthesis of Compound (1-14)
Compound (1-14) was obtained from intermediate (Int-1-14) in the same manner as in Synthesis example (1).
[ 174]
Figure BDA0003862503640001642
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1103.83 as the target.
Synthesis example (5): synthesis of Compound (1-15)
Compound (1-15) was obtained from intermediate (Int-1-15) in the same manner as in Synthesis example (1).
[ chemical 175]
Figure BDA0003862503640001643
The target was confirmed to be M/z (M + H) =1047.77 by MALDI-TOF-MS.
Synthesis example (6): synthesis of Compound (1-16)
Compound (1-16) was obtained from intermediate (Int-1-16) in the same manner as in Synthesis example (1).
[ solution 176]
Figure BDA0003862503640001651
The target was confirmed to be M/z (M + H) =1019.74 by MALDI-TOF-MS.
Synthesis example (7): synthesis of Compound (1-17)
Compound (1-17) was obtained from intermediate (Int-1-17) in the same manner as in Synthesis example (1).
[ solution 177]
Figure BDA0003862503640001652
The target was confirmed to be M/z (M + H) =1061.78 by MALDI-TOF-MS.
Synthesis example (8): synthesis of Compound (1-18)
Compound (1-18) was obtained from intermediate (Int-1-18) in the same manner as in Synthesis example (1).
[ solution 178]
Figure BDA0003862503640001653
The target was confirmed to be M/z (M + H) =1038.69 by MALDI-TOF-MS.
Synthesis example (9): synthesis of Compound (1-32)
Compound (1-32) was obtained from intermediate (Int-1-32) in the same manner as in Synthesis example (1).
[ chemical 179]
Figure BDA0003862503640001661
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1207.88 as a target.
Synthesis example (10): synthesis of Compound (1-44)
Compound (1-44) was obtained from intermediate (Int-1-44) in the same manner as in Synthesis example (1).
[ solution 180]
Figure BDA0003862503640001662
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1168.75 as the target.
Synthesis example (11): synthesis of Compound (1-45)
Compound (1-45) was obtained from intermediate (Int-1-45) in the same manner as in Synthesis example (1).
[ solution 181]
Figure BDA0003862503640001663
The target was confirmed to be M/z (M + H) =1113.80 by MALDI-TOF-MS.
Synthesis example (12): synthesis of Compound (1-46)
Compound (1-46) was obtained from intermediate (Int-1-46) in the same manner as in Synthesis example (1).
[ solution 182]
Figure BDA0003862503640001671
The target was confirmed to be M/z (M + H) =1023.68 by MALDI-TOF-MS.
Synthesis example (13): synthesis of Compound (1-47)
Compound (1-47) was obtained from intermediate (Int-1-47) in the same manner as in Synthesis example (1).
[ solution 183]
Figure BDA0003862503640001672
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1027.69 as an object.
Synthesis example (14): synthesis of Compound (1-48)
Compound (1-48) was obtained from intermediate (Int-1-48) in the same manner as in Synthesis example (1).
[ solution 184]
Figure BDA0003862503640001673
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1188.75 as the target.
Synthesis example (15): synthesis of Compound (1-49)
Compound (1-49) was obtained from intermediate (Int-1-49) in the same manner as in Synthesis example (1).
[ solution 185]
Figure BDA0003862503640001681
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1073.71 as the target.
Synthesis example (16): synthesis of Compound (1-50)
Compound (1-50) was obtained from intermediate (Int-1-50) in the same manner as in Synthesis example (1).
[ solution 186]
Figure BDA0003862503640001682
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1341.90 as the target.
The structure of the obtained compound was confirmed by NMR measurement.
1 H-NMR(500MHz,CDCl 3 )：δ＝0.90-1.00(m,32H),1.08(s,3H),1.23(d,6H),1.27-1.34(m,27H),1.38(s,3H),1.44-1.55(m,4H),1.58-1.80(m,9H),1.93-1.97(m,2H),2.15(s,3H),2.26-2.31(m,1H),5.95(s,1H),5.98(s,1H),6.26(s,1H),6.43(d,1H),6.82(dd,1H),6.90-6.97(m,6H),7.02(t,1H),7.15-7.20(m,5H),7.30-7.47(m,3H),7.71(d,2H),7.81(s,1H),8.44(d,1H).
Synthesis example (17): synthesis of Compound (1-56)
Compound (1-56) was obtained from intermediate (Int-1-56) in the same manner as in Synthesis example (1).
[ chemical formula 187]
Figure BDA0003862503640001683
The target was confirmed to be M/z (M + H) =1193.79 by MALDI-TOF-MS.
The structure of the obtained compound was confirmed by NMR measurement.
1 H-NMR(500MHz,CDCl 3 )：δ＝0.90-0.94(m,30H),1.19(s,9H),1.22-1.29(m,5H),1.30(s,3H),1.32(s,6H),1.41-1.50(m,10H),1.57-1.68(m,8H),1.78-1.87(m,6H),2.23-2.26(m,4H),6.15(s,1H),6.28(s,1H),6.35(s,1H),6.57(d,1H),6.95(d,2H),6.98(t,1H),7.20(d,1H),7.31(s,1H),7.48(d,1H),7.54(d,2H),7.59(d,1H),7.65(s,1H),7.70(dd,2H),7.85(s,1H),7.94(dd,2H),8.53(d,1H).
Synthesis example (18): synthesis of Compound (1-59)
Compound (1-59) was obtained from intermediate (Int-1-59) in the same manner as in Synthesis example (1).
[ solution 188]
Figure BDA0003862503640001691
The target was confirmed to be M/z (M + H) =1241.75 by MALDI-TOF-MS.
Synthesis example (19): synthesis of Compound (1-62)
Compound (1-62) was obtained from intermediate (Int-1-62) in the same manner as in Synthesis example (1).
[ formulation 189]
Figure BDA0003862503640001692
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1286.85 as the target.
Synthesis example (20): synthesis of Compound (1-68)
Compound (1-68) was obtained from intermediate (Int-1-68) in the same manner as in Synthesis example (1).
[ solution 190]
Figure BDA0003862503640001701
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1123.67 of the target.
Synthesis example (21): synthesis of Compound (1-69)
Compound (1-69) was obtained from intermediate (Int-1-69) in the same manner as in Synthesis example (1).
[ solution 191]
Figure BDA0003862503640001702
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1214.92 was the target.
Synthesis example (22): synthesis of Compound (1-71)
Compound (1-71) was obtained from intermediate (Int-1-71) in the same manner as in Synthesis example (1).
[ solution 192]
Figure BDA0003862503640001703
The target was confirmed to be M/z (M + H) =1235.83 by MALDI-TOF-MS.
Synthesis example (23): synthesis of Compound (1-72)
Compound (1-72) was obtained from intermediate (Int-1-72) in the same manner as in Synthesis example (1).
[ solution 193]
Figure BDA0003862503640001711
The target was confirmed to be M/z (M + H) =1159.80 by MALDI-TOF-MS.
Synthesis example (24): synthesis of Compound (1-75)
Compound (1-75) was obtained from intermediate (Int-1-75) in the same manner as in Synthesis example (1).
[ solution 194]
Figure BDA0003862503640001712
The target was confirmed to be M/z (M + H) =1187.74 by MALDI-TOF-MS.
Synthesis example (25): synthesis of Compound (1-76)
Compound (1-76) was obtained from intermediate (Int-1-76) in the same manner as in Synthesis example (1).
[ solution 195]
Figure BDA0003862503640001713
The target was confirmed to be M/z (M + H) =1249.85 by MALDI-TOF-MS.
Synthesis example (26): synthesis of Compound (1-78)
Compound (1-78) was obtained from intermediate (Int-1-78) in the same manner as in Synthesis example (1).
[ solution 196]
Figure BDA0003862503640001721
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The target was confirmed to be M/z (M + H) =1301.86 by MALDI-TOF-MS.
Synthesis example (27): synthesis of Compound (1-79)
Compound (1-79) was obtained from intermediate (Int-1-79) in the same manner as in Synthesis example (1).
[ solution 197]
Figure BDA0003862503640001722
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1137.69 as the target.
Synthesis example (28): synthesis of Compound (1-80)
Compound (1-80) was obtained from intermediate (Int-1-80) in the same manner as in Synthesis example (1).
[ chemical formula 198]
Figure BDA0003862503640001723
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1170.67 was the target.
Synthesis example (29): synthesis of Compound (1-85)
Compound (1-85) was obtained from intermediate (Int-1-85) in the same manner as in Synthesis example (1).
[ 199]
Figure BDA0003862503640001731
The target was confirmed to be M/z (M + H) =1055.63 by MALDI-TOF-MS.
Synthesis example (30): synthesis of Compound (1-88)
Compound (1-88) was obtained from intermediate (Int-1-88) in the same manner as in Synthesis example (1).
[ solution 200]
Figure BDA0003862503640001732
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1337.85 as the target.
Synthesis example (31): synthesis of Compound (1-92)
Compound (1-92) was obtained from intermediate (Int-1-92) in the same manner as in Synthesis example (1).
[ solution 201]
Figure BDA0003862503640001733
The target was confirmed to be M/z (M + H) =1221.80 by MALDI-TOF-MS.
Synthesis example (32): synthesis of Compound (1-95)
Compound (1-95) was obtained from intermediate (Int-1-95) in the same manner as in Synthesis example (1).
[ solution 202]
Figure BDA0003862503640001741
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1133.67 of the target was present.
Synthesis example (33): synthesis of Compound (1-96)
Compound (1-96) was obtained from intermediate (Int-1-96) in the same manner as in Synthesis example (1).
[ formula 203]
Figure BDA0003862503640001742
The target was confirmed to be M/z (M + H) =1095.71 by MALDI-TOF-MS.
Synthesis example (34): synthesis of Compound (1-101)
Compound (1-101) was obtained from intermediate (Int-1-101) in the same manner as in Synthesis example (1).
[ chemical 204]
Figure BDA0003862503640001743
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1239.79 of the target.
Synthesis example (35): synthesis of Compound (1-102)
Compound (1-102) was obtained from intermediate (Int-1-102) in the same manner as in Synthesis example (1).
[ formulation 205]
Figure BDA0003862503640001751
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1151.66 target.
Synthesis example (36): synthesis of Compound (1-103)
Compound (1-103) was obtained from intermediate (Int-1-103) in the same manner as in Synthesis example (1).
[ solution 206]
Figure BDA0003862503640001752
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1261.77 as the target.
Synthesis example (37): synthesis of Compound (1-104)
Compound (1-104) was obtained from intermediate (Int-1-104) in the same manner as in Synthesis example (1).
[ solution 207]
Figure BDA0003862503640001753
The target was confirmed to be M/z (M + H) =1206.82 by MALDI-TOF-MS.
Synthesis example (38): synthesis of Compound (1-105)
Compound (1-105) was obtained from intermediate (Int-1-105) in the same manner as in Synthesis example (1).
[ solution 208]
Figure BDA0003862503640001761
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1109.75 as a target.
Synthesis example (39): synthesis of Compound (1-106)
Compound (1-106) was obtained from intermediate (Int-1-106) in the same manner as in Synthesis example (1).
[ solution 209]
Figure BDA0003862503640001762
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1110.78 as the target.
Synthesis example (40): synthesis of Compound (1-110)
Compound (1-110) was obtained from intermediate (Int-1-110) in the same manner as in Synthesis example (1).
[ solution 210]
Figure BDA0003862503640001763
The target was confirmed to be M/z (M + H) =1311.87 by MALDI-TOF-MS.
The structure of the obtained compound was confirmed by NMR measurement.
1 H-NMR(500MHz,CD 2 Cl 2 )：δ＝0.90-2.21(m,87H),6.50(td,3H),6.70-6.81(m,2H),6.90(d,1H),7.01-7.12(m,3H),7.31(m,1H),7.40(dd,2H),7.57-7.70(m,6H),7.79(d,2H),8.00(dd,1H),8.04(d,2H),8.52(t,1H).
Synthesis example (41): synthesis of Compound (1-116)
Compound (1-116) was obtained from intermediate (Int-1-116) in the same manner as in Synthesis example (1).
[ solution 211]
Figure BDA0003862503640001771
The target was confirmed to be M/z (M + H) =1256.81 by MALDI-TOF-MS.
Synthesis example (42): synthesis of Compound (1-120)
Compound (1-120) was obtained from intermediate (Int-1-120) in the same manner as in Synthesis example (1).
[ solution 212]
Figure BDA0003862503640001772
The target was confirmed to be M/z (M + H) =1340.89 by MALDI-TOF-MS.
Synthesis example (43): synthesis of Compound (1-128)
Compounds (1-128) were obtained from intermediates (Int-1-128) in the same manner as in Synthesis example (1).
[ solution 213]
Figure BDA0003862503640001773
The target was confirmed to be M/z (M + H) =1394.94 by MALDI-TOF-MS.
Synthesis example (44): synthesis of Compound (1-134)
Compound (1-134) was obtained from intermediate (Int-1-134) in the same manner as in Synthesis example (1).
[ solution 214]
Figure BDA0003862503640001781
The target was confirmed to be M/z (M + H) =1373.09 by MALDI-TOF-MS.
Synthesis example (45): synthesis of Compound (1-135)
Compound (1-135) was obtained from intermediate (Int-1-135) in the same manner as in Synthesis example (1).
[ solution 215]
Figure BDA0003862503640001782
The target was confirmed to be M/z (M + H) =1427.14 by MALDI-TOF-MS.
Synthesis example (46): synthesis of Compound (1-140)
Compound (1-140) was obtained from intermediate (Int-1-140) in the same manner as in Synthesis example (1).
[ solution 216]
Figure BDA0003862503640001783
The target was confirmed to be M/z (M + H) =1039.71 by MALDI-TOF-MS.
Synthesis example (47): synthesis of Compound (1-142)
Compound (1-142) was obtained from intermediate (Int-1-142) in the same manner as in Synthesis example (1).
[ chemical formula 217]
Figure BDA0003862503640001791
The structure of the obtained compound was confirmed by NMR measurement.
1 H-NMR(500MHz,CDCl 3 )：δ＝0.90(s,9H),0.96(s,6H),1.10(s,9H),1.14(s,9H),1.26-1.33(m,11H),1.46-1.53(m,4H),1.63-1.75(m,4H),1.91(s,2H),2.27-2.30(m,1H),5.97(s,1H),6.16-6.28(m,2H),6.52-6.63(m,5H),6.79-6.80(m,1H),6.91-7.10(m,8H),7.38-7.51(m,8H),7.72(d,2H),7.86(d,1H),7.90(d,1H),7.97(d,1H),8.45(d,1H).
Synthesis example (48): synthesis of Compound (1-144)
Compound (1-144) was obtained from intermediate (Int-1-144) in the same manner as in Synthesis example (1).
[ solution 218]
Figure BDA0003862503640001792
The target was confirmed to be M/z (M + H) =1207.80 by MALDI-TOF-MS.
Synthesis example (49): synthesis of Compound (1-145)
Compound (1-145) was obtained from intermediate (Int-1-145) in the same manner as in Synthesis example (1).
[ solution 219]
Figure BDA0003862503640001801
The target was confirmed to be M/z (M + H) =1207.80 by MALDI-TOF-MS.
Synthesis example (50): synthesis of Compound (1-148)
Compound (1-148) was obtained from intermediate (Int-1-148) in the same manner as in Synthesis example (1).
[ chemical 220]
Figure BDA0003862503640001802
The structure of the obtained compound was confirmed by NMR measurement.
1 H-NMR(500MHz,CDCl 3 )：δ＝0.89(s,18H),0.93-0.94(m,12H),1.03(s,9H),1.21-1.32(m,5H),1.33(s,9H),1.40-1.52(m,18H),1.56-1.68(m,9H),1.75-1.86(m,6H),2.22-2.27(m,1H),6.24(d,1H),6.33(d,1H),6.41(s,1H),6.80(d,1H),6.87(d,2H),6.94(t,1H),7.36(s,1H),7.43-7.64(m,6H),7.71(d,2H),7.88(s,1H),7.94(d,2H),8.58(d,1H).
Synthesis example (51): synthesis of Compound (1-150)
Compounds (1-150) were obtained from intermediates (Int-1-150) in the same manner as in Synthesis example (1).
[ solution 221]
Figure BDA0003862503640001803
The structure of the obtained compound was confirmed by NMR measurement.
1 H-NMR(500MHz,CDCl 3 )：δ＝0.87(s,18H),0.93(s,6H),1.06(s,9H),1.20-1.35(m,8H),1.40-1.50(m,19H),1.57-1.68(m,4H),1.78-1.86(m,6H),2.22-2.27(m,1H),6.34(t,2H),6.52(d,1H),6.75(d,1H),6.81(d,2H),6.91(t,1H),7.33(t,1H),7.37-7.42(m,2H),7.46-7.64(m,6H),7.66(d,2H),7.86-7.94(m,3H),8.64(d,1H).
Synthesis example (52): synthesis of Compound (1-151)
Compound (1-151) was obtained from intermediate (Int-1-151) in the same manner as in Synthesis example (1).
[ solution 222]
Figure BDA0003862503640001811
The structure of the obtained compound was confirmed by NMR measurement.
1 H-NMR(500MHz,CDCl 3 )：δ＝0.92(s,6H),1.02(s,9H),1.06(s,9H),1.13(s,9H),1.20(s,9H),1.22-1.29(m,1H),1.30-1.53(m,15H),1.57-1.66(m,4H),1.84(d,2H),2.23-2.26(m,1H),6.29-6.41(m,2H),6.57(s,1H),6.68-6.75(m,1H),7.03(d,2H),7.14(d,2H),7.20(d,1H),7.37(dd,1H),7.53(d,2H),7.57-7.67(m,3H),7.69-7.72(m,3H),7.86(d,1H),7.93(d,2H),8.59(d,1H).
Synthesis example (53): synthesis of Compound (1-153)
Compound (1-153) was obtained from intermediate (Int-1-153) in the same manner as in Synthesis example (1).
[ solution 223]
Figure BDA0003862503640001812
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1289.88 as the target.
Synthesis example (54): synthesis of Compound (1-154)
Compound (1-154) was obtained from intermediate (Int-1-154) in the same manner as in Synthesis example (1).
[ 224]
Figure BDA0003862503640001821
The structure of the obtained compound was confirmed by NMR measurement.
1 H-NMR(500MHz,CDCl 3 )：δ＝0.86-0.93(m,24H),0.95-1.04(m,15H),1.20-1.38(m,14H),1.39-1.51(m,18H),1.55-1.72(m,9H),1.74-1.89(m,6H),2.21-2.27(m,1H),6.11-6.16(m,1H),6.29-6.34(m,1H),6.54-6.59(m,1H),6.75-6.82(m,1H),6.90-7.00(m,3H),7.08-7.24(m,1H),7.35-7.56(m,5H),8.59(d,1H),8.02(d,2H),7.86-7.91(m,2H),7.94-7.98(m,1H),8.58-8.61(m,1H).
Synthesis example (55): synthesis of Compound (1-155)
Compound (1-155) was obtained from intermediate (Int-1-155) in the same manner as in Synthesis example (1).
[ solution 225]
Figure BDA0003862503640001822
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1097.69 as the target.
Synthesis example (56): synthesis of Compound (1-156)
Compound (1-156) was obtained from intermediate (Int-1-156) in the same manner as in Synthesis example (1).
[ chemical 226]
Figure BDA0003862503640001823
The structure of the obtained compound was confirmed by NMR measurement.
1 H-NMR(500MHz,CDCl 3 )：δ＝0.74-0.80(m,20H),0.89-0.93(m,7H),1.02-1.08(m,13H),1.12(s,2H),1.19-1.29(m,2H),1.32-1.37(m,6H),1.42-1.50(m,14H),1.54-1.56(m,9H),1.57-1.72(m,7H),1.83(s,2H),1.22-1.25(m,1H),6.63-6.64(m,4H),6.89-6.90(m,1H),7.39-7.42(m,2H),7.52(d,2H),7.59(d,1H),7.72-7.81(m,5H),7.91(d,2H),8.62(s,1H).
Synthesis example (57): synthesis of Compound (1-157)
Compound (1-157) was obtained from intermediate (Int-1-157) in the same manner as in Synthesis example (1).
[ formulation 227]
Figure BDA0003862503640001831
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1071.68 as the target.
Synthesis example (58): synthesis of Compound (1-158)
Compound (1-158) was obtained from intermediate (Int-1-158) in the same manner as in Synthesis example (1).
[ solution 228]
Figure BDA0003862503640001832
The structure of the obtained compound was confirmed by NMR measurement.
1 H-NMR(500MHz,CD 2 Cl 2 )：δ＝0.84(s,18H),0.91(s,6H),1.03(s,3H),1.10(s,15H),1.22-2.21(m,52H),6.17(s,1H),6.51(s,1H),6.59(d,2H),6.79(s,2H),7.00-7.28(m,3H),7.57-8.01(m,9H),8.53(s,1H).
Synthesis example (59): synthesis of Compound (1-167)
Compound (1-167) was obtained from intermediate (Int-1-167) in the same manner as in Synthesis example (1).
[ solution 229]
Figure BDA0003862503640001841
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1362.88 as the target.
Synthesis example (60): synthesis of Compound (1-173)
Compound (1-173) was obtained from intermediate (Int-1-173) in the same manner as in Synthesis example (1).
[ solution 230]
Figure BDA0003862503640001842
The target was confirmed to be M/z (M + H) =1424.89 by MALDI-TOF-MS.
Synthesis example (61): synthesis of Compound (1-177)
Compound (1-177) was obtained from intermediate (Int-1-177) in the same manner as in Synthesis example (1).
[ solution 231]
Figure BDA0003862503640001843
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1189.74 of the target.
Synthesis example (62): synthesis of Compound (1-180)
Compound (1-180) was obtained from intermediate (Int-1-180) in the same manner as in Synthesis example (1).
[ Hua 232]
Figure BDA0003862503640001851
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1147.86 as the target.
Synthesis example (63): synthesis of Compound (1-181)
Compound (1-181) was obtained from intermediate (Int-1-181) in the same manner as in Synthesis example (1).
[ 233]
Figure BDA0003862503640001852
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1202.92 of the target.
Synthesis example (64): synthesis of Compound (1-182)
Compound (1-182) was obtained from intermediate (Int-1-182) in the same manner as in Synthesis example (1).
[ solution 234]
Figure BDA0003862503640001853
It was confirmed by MALDI-TOF-MS that M/z (M + H) = 1309.00.
Synthesis example (65): synthesis of Compound (1-183)
Compound (1-183) was obtained from intermediate (Int-1-183) in the same manner as in Synthesis example (1).
[ solution 235]
Figure BDA0003862503640001861
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1459.11 of the target.
Synthesis example (66): synthesis of Compound (1-166)
Compound (1-166) was obtained from intermediate (Int-1-166) in the same manner as in Synthesis example (1).
[ solution 236]
Figure BDA0003862503640001862
The target was confirmed to be M/z (M + H) =1139.74 by MALDI-TOF-MS.
The structure of the obtained compound was confirmed by NMR measurement.
1 H-NMR(500MHz,CD 2 Cl 2 )：δ＝0.78(s,18H),0.91(s,6H),1.04(s,9H),1.09-1.47(m,16H),1.51(s,9H),1.56-1.86(m,15H),2.19-2.23(m,1H),6.19(s,1H),6.50(d,1H),6.58-6.61(m,3H),6.64(d,1H),6.86(t,1H),7.21-7.23(m,1H),7.28-7.40(m,2H),7.52(d,2H),7.58(d,1H),7.72-7.77(m,5H),7.94(d,2H),8.49(d,1H).
Synthesis example (67): synthesis of Compound (1-184)
Compound (1-184) was obtained from intermediate (Int-1-184) in the same manner as in Synthesis example (1).
[ solution 237]
Figure BDA0003862503640001863
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1181.79 of the target.
The structure of the obtained compound was confirmed by NMR measurement.
1 H-NMR(500MHz,CD 2 Cl 2 )：δ＝0.79(s,18H),0.91(s,6H),1.04(s,9H),1.07(s,6H),1.15(s,9H),1.18-1.28(m,2H),1.36-1.45(m,2H),1.49(s,6H),1.51(s,9H),1.53-1.82(m,12H),2.22-2.24(m,1H),6.14-6.16(m,1H),6.37-6.38(m,1H),6.53-6.56(m,1H),6.71(d,2H),6.84-6.85(m,1H),6.92(t,1H),7.28-7.40(m,3H),7.52-7.55(m,3H),7.72-7.74(m,2H),7.77(d,2H),7.82(d,1H),7.94(d,2H),8.56(s,1H).
Synthesis example (68): synthesis of Compound (1-185)
Compound (1-185) was obtained from intermediate (Int-1-185) in the same manner as in Synthesis example (1).
[ solution 238]
Figure BDA0003862503640001871
/>
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1125.73 as a target.
The structure of the obtained compound was confirmed by NMR measurement.
1 H-NMR(500MHz,CD 2 Cl 2 )：δ＝0.92(s,6H),0.95-1.02(m,15H),1.12(s,9H),1.19-1.30(m,2H),1.34-1.54(m,28H),1.57-1.74(m,8H),1.80-1.85(m,2H),2.20-2.26(m,1H),6.14(d,1H),6.30(d,1H),6.67(d,1H),6.70(s,1H),6.99(d,2H),7.09(d,2H),7.33-7.46(m,4H),7.51(d,2H),7.65(dd,1H),7.71(d,2H),7.82(d,1H),7.88-7.92(m,3H),8.74(d,1H).
Synthesis example (69): synthesis of Compound (1-186)
Compounds (1-186) were obtained from intermediates (Int-1-186) in the same manner as in Synthesis example (1).
[ chemical 239]
Figure BDA0003862503640001872
It was confirmed by MALDI-TOF-MS that M/z (M + H) = 1095.77.
Synthesis example (70): synthesis of Compound (1-192)
Compound (1-192) was obtained from intermediate (Int-1-192) in the same manner as in Synthesis example (1).
[ solution 240]
Figure BDA0003862503640001881
The target was confirmed to be M/z (M + H) =1062.56 by MALDI-TOF-MS.
Synthesis example (71): synthesis of Compound (1-198)
Compound (1-198) was obtained from intermediate (Int-1-198) in the same manner as in Synthesis example (1).
[ solution 241]
Figure BDA0003862503640001882
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1084.54 target.
Synthesis example (72): synthesis of Compound (1-219)
Compound (1-219) was obtained from intermediate (Int-1-219) in the same manner as in Synthesis example (1).
[ solution 242]
Figure BDA0003862503640001883
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1122.61 of the target.
Synthesis example (73): synthesis of Compound (1-245)
Compound (1-245) was obtained from intermediate (Int-1-245) in the same manner as in Synthesis example (1).
[ solution 243]
Figure BDA0003862503640001891
The target was confirmed to be M/z (M + H) =1033.72 by MALDI-TOF-MS.
Synthesis example (74): synthesis of Compound (1-255)
Compound (1-255) was obtained from intermediate (Int-1-255) in the same manner as in Synthesis example (1).
[ chemical 244]
Figure BDA0003862503640001892
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1165.81 as the target.
Synthesis example (75): synthesis of Compound (1-256)
Compound (1-256) was obtained from intermediate (Int-1-256) in the same manner as in Synthesis example (1).
[ chemical 245]
Figure BDA0003862503640001893
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1107.73 as the target.
Synthesis example (76): synthesis of Compound (1-270)
Compound (1-270) was obtained from intermediate (Int-1-270) in the same manner as in Synthesis example (1).
[ solution 246]
Figure BDA0003862503640001901
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1124.76 as the target.
Synthesis example (77): synthesis of Compound (1-295)
Compound (1-295) was obtained from intermediate (Int-1-295) in the same manner as in Synthesis example (1).
[ formulation 247]
Figure BDA0003862503640001902
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1161.78 as the target.
Synthesis example (78): synthesis of Compound (1-334)
Compound (1-334) was obtained from intermediate (Int-1-334) in the same manner as in Synthesis example (1).
[ chemical 248]
Figure BDA0003862503640001903
The target was confirmed to be M/z (M + H) =1116.74 by MALDI-TOF-MS.
Synthesis example (79): synthesis of Compound (1-336)
Compound (1-336) was obtained from intermediate (Int-1-336) in the same manner as in Synthesis example (1).
[ Hua 249]
Figure BDA0003862503640001911
The target was confirmed to be M/z (M + H) =1169.90 by MALDI-TOF-MS.
Synthesis example (80): synthesis of Compound (1-337)
Compound (1-337) was obtained from intermediate (Int-1-337) in the same manner as in Synthesis example (1).
[ solution 250]
Figure BDA0003862503640001912
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1202.92 of the target.
Synthesis example (81): synthesis of Compound (1-340)
Compound (1-340) was obtained from intermediate (Int-1-340) in the same manner as in Synthesis example (1).
[ chemical 251]
Figure BDA0003862503640001921
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1163.79 as the target.
Synthesis example (82): synthesis of Compound (1-343)
Compound (1-343) was obtained from intermediate (Int-1-343) in the same manner as in Synthesis example (1).
[ solution 252]
Figure BDA0003862503640001922
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1111.76 as the target.
Synthesis example (83): synthesis of Compound (1-347)
Compound (1-347) was obtained from intermediate (Int-1-347) in the same manner as in Synthesis example (1).
[ solution 253]
Figure BDA0003862503640001923
The target was confirmed to be M/z (M + H) =1165.81 by MALDI-TOF-MS.
Synthesis example (84): synthesis of Compound (1-350)
Compound (1-350) was obtained from intermediate (Int-1-350) in the same manner as in Synthesis example (1).
[ chemical 254]
Figure BDA0003862503640001931
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1235.83 as the target.
Synthesis example (85): synthesis of Compound (1-351)
Compound (1-351) was obtained from intermediate (Int-1-351) in the same manner as in Synthesis example (1).
[ solution 255]
Figure BDA0003862503640001932
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1179.77 as the target.
Synthesis example (86): synthesis of Compound (1-352)
Compound (1-352) was obtained from intermediate (Int-1-352) in the same manner as in Synthesis example (1).
[ chemical 256]
Figure BDA0003862503640001933
/>
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1181.79 of the target.
Synthesis example (87): synthesis of Compound (1-367)
Compound (1-367) was obtained from intermediate (Int-1-367) in the same manner as in Synthesis example (1).
[ solution 257]
Figure BDA0003862503640001941
It was confirmed by MALDI-TOF-MS that M/z (M + H) =973.53 as the target.
Synthesis example (88): synthesis of Compound (1-370)
Compound (1-370) was obtained from intermediate (Int-1-370) in the same manner as in Synthesis example (1).
[ Hua 258]
Figure BDA0003862503640001942
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1105.75 as the target.
Synthesis example (89): synthesis of Compound (1-386)
Compound (1-386) was obtained from intermediate (Int-1-386) in the same manner as in Synthesis example (1).
[ solution 259]
Figure BDA0003862503640001943
The target was confirmed to be M/z (M + H) =1105.75 by MALDI-TOF-MS.
Synthesis example (90): synthesis of Compound (1-391)
Compound (1-391) was obtained from intermediate (Int-1-391) in the same manner as in Synthesis example (1).
[ chemical 260]
Figure BDA0003862503640001951
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1087.76 of the target.
Synthesis example (91): synthesis of Compound (1-411)
Compound (1-411) was obtained from intermediate (Int-1-411) in the same manner as in Synthesis example (1).
[ solution 261]
Figure BDA0003862503640001952
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1115.74 as the target.
Synthesis example (92): synthesis of Compound (1-412)
Compound (1-412) was obtained from intermediate (Int-1-412) in the same manner as in Synthesis example (1).
[ solution 262]
Figure BDA0003862503640001953
The target was confirmed to be M/z (M + H) =1023.73 by MALDI-TOF-MS.
Synthesis example (93): synthesis of Compound (1-418)
Compound (1-418) was obtained from intermediate (Int-1-418) in the same manner as in Synthesis example (1).
[ solution 263]
Figure BDA0003862503640001961
/>
The target was confirmed to be M/z (M + H) =969.72 by MALDI-TOF-MS.
Synthesis example (94): synthesis of Compound (1-419)
Compound (1-419) was obtained from intermediate (Int-1-419) in the same manner as in Synthesis example (1).
[ chemical 264]
Figure BDA0003862503640001962
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1045.75 of the target.
Synthesis example (95): synthesis of Compound (1-426)
Compound (1-426) was obtained from intermediate (Int-1-426) in the same manner as in Synthesis example (1).
[ solution 265]
Figure BDA0003862503640001963
The target was confirmed to be M/z (M + H) =1313.88 by MALDI-TOF-MS.
Synthesis example (96): synthesis of Compound (1-427)
Compound (1-427) was obtained from intermediate (Int-1-427) in the same manner as in Synthesis example (1).
[ solution 266]
Figure BDA0003862503640001971
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1269.87 as the target.
Synthesis example (97): synthesis of Compound (1-430)
Compound (1-430) was obtained from intermediate (Int-1-430) in the same manner as in Synthesis example (1).
[ solution 267]
Figure BDA0003862503640001972
The target was confirmed to be M/z (M + H) =1237.85 by MALDI-TOF-MS.
Synthesis example (98): synthesis of Compound (1-432)
Compound (1-432) was obtained from intermediate (Int-1-432) in the same manner as in Synthesis example (1).
[ chemical 268]
Figure BDA0003862503640001973
The target was confirmed to be M/z (M + H) =1367.93 by MALDI-TOF-MS.
Synthesis example (99): synthesis of Compound (1-441)
Compound (1-441) was obtained from intermediate (Int-1-441) in the same manner as in Synthesis example (1).
[ 269]
Figure BDA0003862503640001981
The target was confirmed to be M/z (M + H) =1297.90 by MALDI-TOF-MS.
Synthesis example (100): synthesis of Compound (1-442)
Compound (1-442) was obtained from intermediate (Int-1-442) in the same manner as in Synthesis example (1).
[ solution 270]
Figure BDA0003862503640001982
The target was confirmed to be M/z (M + H) =1313.88 by MALDI-TOF-MS.
Synthesis example (101): synthesis of Compound (1-448)
Compound (1-448) was obtained from intermediate (Int-1-448) in the same manner as in Synthesis example (1).
[ 271]
Figure BDA0003862503640001983
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1237.85 as the target.
Synthesis example (102): synthesis of Compound (1-450)
Compound (1-450) was obtained from intermediate (Int-1-450) in the same manner as in Synthesis example (1).
[ solution 272]
Figure BDA0003862503640001991
The target was confirmed to be M/z (M + H) =1051.78 by MALDI-TOF-MS.
Synthesis example (103): synthesis of Compound (1-456)
Compound (1-456) was obtained from intermediate (Int-1-456) in the same manner as in Synthesis example (1).
[ 273]
Figure BDA0003862503640001992
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1191.86 as the target.
Synthesis example (104): synthesis of Compound (1-457)
Compound (1-457) was obtained from intermediate (Int-1-457) in the same manner as in Synthesis example (1).
[ solution 274]
Figure BDA0003862503640001993
It was confirmed by MALDI-TOF-MS that M/z (M + H) =1115.83 as the target.
Synthesis example (105): synthesis of Compound (1-458)
Compound (1-458) was obtained from intermediate (Int-1-458) in the same manner as in Synthesis example (1).
[ design 275]
Figure BDA0003862503640002001
The target was confirmed to be M/z (M + H) =1093.71 by MALDI-TOF-MS.
The other compounds of the present invention can be synthesized by the method according to the synthesis example by appropriately changing the compound as a raw material.
Next, the production and evaluation of an organic EL device using the compound of the present invention will be described. The application of the compound of the present invention is not limited to the examples shown below, and the film thickness and the structural material of each layer may be appropriately changed according to the basic properties of the compound of the present invention.
< A. Evaluation of basic physical Properties >
< preparation of sample >
When the absorption characteristics and the light emission characteristics (fluorescence and phosphorescence) of a compound to be evaluated are evaluated, there are a case where the compound to be evaluated is dissolved in a solvent and evaluated in the solvent, and a case where the compound to be evaluated is evaluated in a thin film state. Further, when the evaluation is performed in a thin film state, there are a case where only the compound to be evaluated is made thin and evaluated, and a case where the compound to be evaluated is dispersed in an appropriate matrix material and made thin and evaluated, depending on the use form of the compound to be evaluated in the organic EL device. Here, a thin film obtained by vapor deposition of only the compound to be evaluated is referred to as "single film", and a thin film obtained by applying and drying a coating liquid containing the compound to be evaluated and a matrix material is referred to as "coating film".
As the matrix material, commercially available polymethyl methacrylate (PMMA) or the like can be used. In this example, a thin film sample was prepared by dissolving PMMA and a compound to be evaluated in toluene and then forming a thin film on a quartz transparent support substrate (10 mm × 10 mm) by a spin coating method.
Further, a film sample in the case where the host material is the host compound was prepared as follows. A quartz transparent support substrate (10 mm. Times.10 mm. Times.1.0 m) was usedm) was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by the Changzhou industry), a molybdenum vapor deposition boat containing a host compound and a molybdenum vapor deposition boat containing a dopant compound were set, and then the vacuum vessel was depressurized to 5X 10 -4 Until Pa. Next, the evaporation boat containing the host compound and the evaporation boat containing the dopant compound were heated at the same time, and the host compound and the dopant compound were co-evaporated to have an appropriate film thickness, thereby forming a mixed thin film (sample) of the host compound and the dopant compound. Here, the deposition rate is controlled according to a set mass ratio of the host compound to the dopant compound.
< evaluation of absorption Property and luminescence Property >
The absorption spectrum of the sample was measured using an ultraviolet-visible near-infrared spectrophotometer (Shimadzu corporation, UV-2600). The fluorescence spectrum or phosphorescence spectrum of the sample was measured using a spectrofluorometer (Hitachi High-Tech (manufactured by Hitachi High-Tech Co., ltd., F-7000)).
For measurement of fluorescence spectrum, photoluminescence was measured by excitation at an appropriate excitation wavelength at room temperature. For the measurement of the phosphorescence spectrum, the measurement was performed in a state where the sample was immersed in liquid nitrogen (temperature 77K) using an attached cooling unit. In order to observe the phosphorescence spectrum, a chopper was used to adjust the delay time from the irradiation of the excitation light until the start of measurement. With respect to the sample, photoluminescence was measured by excitation at an appropriate excitation wavelength.
Further, the fluorescence quantum yield (PLQY) was measured using a Photoluminescence (PL) quantum yield measuring device (manufactured by hamamatsu photonics (inc., ltd., C9920-02G)).
< evaluation of fluorescence lifetime (delayed fluorescence) >
The fluorescence lifetime was measured at 300K using a fluorescence lifetime measuring apparatus (manufactured by Hamamatsu photonics (Strand), C11367-01). Specifically, a light-emitting component having a fast fluorescence lifetime and a light-emitting component having a slow fluorescence lifetime at a maximum light-emitting wavelength measured at an appropriate excitation wavelength are observed. In a fluorescence lifetime measurement at room temperature of a general organic EL material emitting fluorescence, a triplet component is deactivated by heat, and thus a slow light emitting component in which a triplet component derived from phosphorescence participates is hardly observed. In the case where a slow light-emitting component is observed in a compound to be evaluated, it is observed that triplet energy having a long excitation lifetime is transferred to singlet energy by thermal activation and delayed fluorescence is observed.
< calculation of energy gap (Eg) >)
From the long wavelength end a (nm) of the absorption spectrum obtained by the method, it was calculated by Eg = 1240/a.
< measurement of ionization potential (Ip) >
A transparent supporting substrate (28 mm. Times.26 mm. Times.0.7 mm) on which ITO (indium tin oxide) was vapor-deposited was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by the Changzhou industry), a molybdenum vapor deposition boat containing a target compound was placed, and then the pressure in a vacuum chamber was reduced to 5X 10 -4 Until Pa. Next, the evaporation boat is heated to evaporate the target compound, thereby forming a single film (undoped (Neat) film) of the target compound.
The ionization potential of the target compound was measured using a photoelectron spectrometer (PYS-201, sumitomo heavy machinery industry co., ltd) using the obtained individual film as a sample.
< calculation of Electron affinity (Ea) >
The electron affinity can be estimated from the difference between the ionization potential measured by the method and the energy gap calculated by the method.
< calculation of E (S, sh), E (T, sh) and Δ E (ST) >)
Singlet excitation level E (S, sh) is determined by wavelength B at the intersection of the tangent line passing through the inflection point on the short wavelength side of the peak of the fluorescence spectrum and the base line Sh (nm) by using E (S, sh) =1240/B Sh To calculate. In addition, the triplet excitation level E (T, sh) is determined by the wavelength C at the intersection of the tangent line passing through the inflection point on the short wavelength side of the peak of the phosphorescence spectrum and the baseline Sh (nm) by using E (T, sh) =1240/C Sh To calculate.
Δ E (ST) is defined by the energy difference between E (S, sh) and E (T, sh), i.e., Δ E (ST) = E (S, sh) -E (T, sh). In addition, Δ E (ST) can also be calculated by using, for example, a method described in "pure organic electroluminescent material (100% conversion from electroluminescence to light) that realizes 100% photoelectric conversion", h.pass, h.bell wood, t.foro, k.zhijin, k.gming, s.jubao, t.smallfurden, h.macrorock, f.bellwood, a. Jugong, y.village, c.ander (h.kaji, h.suzuki, t.fukushima, k.shizu, k.katsuaki, s.kubo, t.kominoo, h.oiwa, f.suzuki, a.wakamiya, y.mura, c.adachi, and com.natu.8476, 8476, which is incorporated by reference.
< possibility of application in organic EL element >
The compound of the present invention is expected to have an appropriate energy gap (Eg) and high triplet excitation energy (E) T ) And a small Δ EST, and therefore, for example, application to a light-emitting layer and a charge-transporting layer, particularly to a light-emitting layer, is expected.
< B evaluation of vapor deposition type organic EL element >
Next, the production and evaluation of an organic EL device using the polycyclic aromatic compound of the present invention will be described.
< Structure of organic EL element >
The material structures of the respective layers in the organic EL devices of examples B1 to B41, B42 to B65, B66 to B79, B80 to B105, and B1 to B7 are shown in tables B-1, B-2, B-3, B-4, B-5, B-6, and B-7 below.
[ Table B-1]
Figure BDA0003862503640002021
[ Table B-2]
Figure BDA0003862503640002031
[ Table B-3]
Figure BDA0003862503640002041
[ Table B-4]
Figure BDA0003862503640002051
[ Table B-5]
Figure BDA0003862503640002061
[ Table B-6]
Figure BDA0003862503640002071
[ Table B-7]
Figure BDA0003862503640002072
The chemical structures of "HI", "HAT-CN", "HT-1", "HT-2", "BH", "ET-1", "ET-2", "Liq", "comparative compound (1)", "comparative compound (2)", "comparative compound (3)", "comparative compound (4)", "comparative compound (5)", "comparative compound (6)", and "comparative compound (7)" in tables B-1, B-2, B-3, and B-7 are shown below.
[ 276]
Figure BDA0003862503640002081
[ Hua 277]
Figure BDA0003862503640002082
< elements of embodiment B1 >
A glass substrate (manufactured by optoscience) of 26mm × 28mm × 0.7mm, which is prepared by polishing ITO having a thickness of 180nm deposited by sputtering to 150nm, was used as a transparent support substrate. The transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa vacuum deposition (Strand)), and a molybdenum vapor deposition boat and an aluminum nitride vapor deposition boat were respectively charged with HI, HAT-CN, HT-1, HT-2, BH, the compounds (1-1), ET-1, and ET-2, and with Liq, liF, and aluminum.
The following layers are sequentially formed on the ITO film of the transparent support substrate. The vacuum vessel was depressurized to 5X 10 -4 Pa, HI was heated and vapor deposition was performed so that the film thickness became 40nm, HAT-CN was heated and vapor deposition was performed so that the film thickness became 5nm, HT-1 was heated and vapor deposition was performed so that the film thickness became 45nm, HT-2 was heated and vapor deposition was performed so that the film thickness became 10nm, and a hole layer including four layers was formed. Then, BH and the compound (1-1) were heated at the same time, and vapor deposition was performed so that the film thickness became 25nm to form a light-emitting layer. The deposition rate was adjusted so that the mass ratio of BH to the compound (1-1) became about 97 to 3. Further, ET-1 was heated and vapor-deposited so that the film thickness became 5nm, and then ET-2 was simultaneously heated with Liq and vapor-deposited so that the film thickness became 25nm, thereby forming an electron layer including two layers. The deposition rate was adjusted so that the mass ratio of ET-2 to Liq became about 50 to 50. The deposition rate of each layer is 0.01 nm/sec to 1 nm/sec. Then, liF was heated and vapor-deposited at a vapor deposition rate of 0.01 nm/second to 0.1 nm/second so that the film thickness became 1nm, and aluminum was heated and vapor-deposited so that the film thickness became 100nm to form a cathode, thereby obtaining an organic EL element.
< elements of example B2 to example B41, example B42 to example B65, example B66 to example B79, example B80 to example B105, and comparative example B1 to comparative example B7 >
Organic EL elements of examples B2 to B41, B42 to B65, B66 to B79, B80 to B105, and B1 to B7 were obtained in the same manner as in example B1 except that the dopant materials described in tables B-1, B-2, B-3, B-4, B-5, B-6, and B-7 were used in place of compound (1-1).
< evaluation of organic EL characteristics >
In the organic EL devices of examples B1 to B41, B42 to B65, B66 to B79, B80 to B105, and B1 to B7, dc voltage was applied to ITO electrode as anode and LiF/aluminum electrode as cathode, and 1000cd/m was measured 2 Driving voltage at the time of light emission, external quantum efficiency, and device lifetime. In addition, the component lifetime is 1000cd/m 2 The voltage during light emission is continuously driven for a period of time in which the luminance is maintained at 95% or more of the initial luminance. The results are shown in tables B-8, B-9, B-10 and B-11.
The quantum efficiency of a light-emitting element includes an internal quantum efficiency and an external quantum efficiency, and the internal quantum efficiency indicates a ratio of external energy injected as electrons (or holes) into a light-emitting layer of the light-emitting element to be converted into photons. On the other hand, the external quantum efficiency is calculated based on the amount of photons emitted to the outside of the light-emitting element, and since a part of the photons generated in the light-emitting layer is absorbed or continuously reflected by the inside of the light-emitting element without being emitted to the outside of the light-emitting element, the external quantum efficiency is lower than the internal quantum efficiency.
The method for measuring the external quantum efficiency is as follows. The luminance of the applied element reached 1000cd/m using a voltage/current generator R6144 manufactured by Edwaten test (Advantest) 2 The element is caused to emit light. The spectral radiance in the visible light region was measured from the direction perpendicular to the light-emitting surface using a spectral radiance meter SR-3AR manufactured by Topycon (TOPCON). Assuming that the light-emitting surface is a perfect diffusion surface, the number obtained by dividing the value of the measured spectral radiance of each wavelength component by the wavelength energy and multiplying by pi is the number of photons at each wavelength. Then, the number of photons is accumulated in the observed full wavelength region, And is set to the total number of photons released from the element. The number of carriers (carriers) injected into the device is defined as a value obtained by dividing the applied current value by the elementary charge (elementary charge), and the number of total photons emitted from the device is defined as the external quantum efficiency by dividing the number of carriers injected into the device.
[ Table B-8]
Figure BDA0003862503640002101
[ Table B-9]
Figure BDA0003862503640002111
[ Table B-10]
Figure BDA0003862503640002121
[ Table B-11]
Figure BDA0003862503640002122
< C. evaluation of coated organic EL element
Next, an organic EL device obtained by forming an organic layer by coating will be described.
< macromolecular host compound: synthesis of SPH-101
SPH-101 was synthesized according to the method described in International publication No. 2015/008851. A copolymer in which M2 or M3 is bonded to the adjacent site of M1 is obtained, and each unit is estimated to be 50:26:24 (molar ratio).
[ 278]
Figure BDA0003862503640002131
< high molecular hole transport compound: synthesis of XLP-101
XLP-101 was synthesized according to the method described in Japanese patent laid-open publication No. 2018-61028. A copolymer in which M5 or M6 is bonded to a portion adjacent to M4 is obtained, and each unit is estimated to be 40:10:50 (molar ratio).
[ chemical No. 279]
Figure BDA0003862503640002141
< examples C1 to C9 >
A coating solution of the material forming each layer was prepared to prepare a coating type organic EL device.
< production of organic EL element in embodiments C1 to C3 >
The material structure of each layer in the organic EL device is shown in table C-1.
[ Table C-1]
Figure BDA0003862503640002142
The chemical structure of "ET1" in Table C-1 is shown below.
[ solution 280]
Figure BDA0003862503640002151
< preparation of composition (1) for Forming light-emitting layer >
The following components were stirred until a uniform solution was obtained, thereby preparing a composition (1) for forming a light-emitting layer. The prepared composition for forming a light-emitting layer was spin-coated on a glass substrate, and dried by heating under reduced pressure, thereby obtaining a coating film free from film defects and excellent in smoothness.
Figure BDA0003862503640002152
The compound (X) is a polycyclic aromatic compound represented by the general formula (1) (for example, a compound of the formula (1-1)) or a multimer thereof, a polymer compound obtained by polymerizing the polycyclic aromatic compound as a monomer (that is, the monomer has a reactive substituent), a crosslinked polymer obtained by further crosslinking the polymer compound, a pendant polymer obtained by substituting the monomer in a main chain polymer, or a pendant polymer obtained by further crosslinking the pendant polymer. The polymer compound or the pendant polymer compound used for obtaining the crosslinked polymer or the pendant polymer has a crosslinkable substituent.
< PEDOT: PSS solution >
Commercially available PEDOT was used: PSS solution (Clevios (TM) P VP AI4083, PEDOT: aqueous dispersion of PSS, manufactured by Heraeus Holdings).
[ Hua 281]
Figure BDA0003862503640002153
Preparation of OTPD solution
OTPD (LT-N159, manufactured by luminology Technology Corp) and IK-2 (photo cation polymerization initiator, manufactured by Sanapro) were dissolved in toluene to prepare an OTPD solution having an OTPD concentration of 0.7 wt% and an IK-2 concentration of 0.007 wt%.
[ solution 282]
Figure BDA0003862503640002161
< preparation of XLP-101 solution >
A 0.7 wt% XLP-101 solution was prepared by dissolving XLP-101 in xylene at a concentration of 0.6 wt%.
< preparation of PCz solution >
PCz (polyvinylcarbazole) was dissolved in dichlorobenzene to prepare a 0.7 wt% PCz solution.
[ 283] chemical reaction
Figure BDA0003862503640002162
< example C1 >
On a glass substrate on which ITO with a thickness of 150nm was evaporated, PEDOT: PSS solution, calcined on a hot plate at 200 ℃ for 1 hour, thus producing PEDOT: PSS film (hole injection layer). Then, the OTPD solution was spin-coated, dried on a hot plate at 80 ℃ for 10 minutes, and then exposed to light at an exposure intensity of 100mJ/cm using an exposure machine 2 The film was exposed to light and calcined on a hot plate at 100 ℃ for 1 hour, whereby an OTPD film (hole transport layer) having a film thickness of 30nm, which was insoluble in the solution, was formed. Subsequently, the composition (1) for forming a light-emitting layer was spin-coated and calcined on a hot plate at 120 ℃ for 1 hour, thereby forming a light-emitting layer having a thickness of 20 nm.
The multilayer film thus produced was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by showa vacuum (jet)), and a molybdenum vapor deposition boat containing ET1, a molybdenum vapor deposition boat containing LiF, and a tungsten vapor deposition boat containing aluminum were installed therein. The vacuum vessel was depressurized to 5X 10 -4 Pa, ET1 was heated and vapor-deposited so that the film thickness became 30nm, thereby forming an electron transport layer. The deposition rate in forming the electron transport layer was set to 1 nm/sec. Then, liF is heated and vapor deposition is performed at a vapor deposition rate of 0.01 nm/sec to 0.1 nm/sec so that the film thickness becomes 1 nm. Subsequently, aluminum was heated and vapor-deposited to a film thickness of 100nm to form a cathode. Thus, an organic EL element was obtained.
< example C2 >
An organic EL element was obtained by the same method as in example C1. Further, as for the hole transport layer, an XLP-101 solution was spin-coated and calcined on a hot plate at 200 ℃ for 1 hour, thereby preparing a film having a film thickness of 30 nm.
< example C3 >
An organic EL element was obtained by the same method as in example C1. Further, as for the hole transport layer, a PCz solution was spin-coated and calcined on a hot plate at 120 ℃ for 1 hour, thereby preparing a film having a film thickness of 30 nm.
< production of organic EL elements in embodiments C4 to C6 >
The material structure of each layer in the organic EL device is shown in table C-2.
[ Table C-2]
Figure BDA0003862503640002171
< preparation of composition (2) for Forming light-emitting layer to preparation of composition (4) for Forming light-emitting layer >
The following components were stirred until a uniform solution was obtained, thereby preparing a composition (2) for forming a light-emitting layer.
mCBP 1.98 wt.%
Compound (X) 0.02% by weight
98.00% by weight of toluene
The following components were stirred until a uniform solution was obtained, thereby preparing a composition (3) for forming a light-emitting layer.
SPH-101.98% by weight
Compound (X) 0.02% by weight
98.00% by weight of xylene
The following components were stirred until a uniform solution was obtained, thereby preparing a composition (4) for forming a light-emitting layer.
DOBNA 1.98% by weight
Compound (X) 0.02% by weight
98.00% by weight of toluene
In Table C-2, "mCBP" is 3,3 '-bis (N-carbazolyl) -1,1' -biphenyl, "DOBNA" is 3, 11-di-o-tolyl-5, 9-dioxa-13 b-boranaphtho [3,2,1-de ] anthracene, and "TSPO1" is diphenyl [4- (triphenylsilyl) phenyl ] phosphine oxide. The chemical structure is shown below.
[ CHEMICAL 284]
Figure BDA0003862503640002181
< example C4 >
An ND-3202 (manufactured by Nissan chemical industries) solution was spin-coated on a glass substrate on which ITO was formed to a thickness of 45nm, and then the substrate was heated at 50 ℃ for 3 minutes and 230 ℃ for 15 minutes in an atmospheric environment, thereby forming an ND-3202 film (hole injection layer) having a thickness of 50 nm. Subsequently, an XLP-101 solution was spin-coated, and heated on a hot plate at 200 ℃ for 30 minutes under a nitrogen gas atmosphere, thereby forming an XLP-101 film (hole transport layer) having a film thickness of 20 nm. Subsequently, the composition (2) for forming a light-emitting layer was spin-coated and heated at 130 ℃ for 10 minutes in a nitrogen gas atmosphere, thereby forming a light-emitting layer of 20 nm.
The multilayer film thus produced was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by showa vacuum (stock)), and a molybdenum vapor deposition boat containing TSPO1, a molybdenum vapor deposition boat containing LiF, and a tungsten vapor deposition boat containing aluminum were installed therein. The vacuum vessel was depressurized to 5X 10 -4 Pa, TSPO1 was heated and vapor-deposited to a film thickness of 30nm, thereby forming an electron transport layer. The deposition rate in forming the electron transport layer was set to 1 nm/sec. Then, liF is heated and vapor deposition is performed at a vapor deposition rate of 0.01 nm/second to 0.1 nm/second so that the film thickness becomes 1 nm. Subsequently, aluminum was heated and vapor-deposited to a film thickness of 100nm to form a cathode. Thus, an organic EL element was obtained.
< example C5 and example C6 >
An organic EL device was obtained in the same manner as in example C4, using the composition (3) for forming a light-emitting layer or the composition (4) for forming a light-emitting layer.
< production of organic EL element in embodiments C7 to C9 >
The material structure of each layer in the organic EL device is shown in table C-3.
[ Table C-3]
Figure BDA0003862503640002182
< preparation of composition (5) for Forming light-emitting layer to composition (7) for Forming light-emitting layer >
The following components were stirred until a uniform solution was obtained, thereby preparing a composition (5) for forming a light-emitting layer.
Figure BDA0003862503640002183
The following components were stirred until a uniform solution was obtained, thereby preparing a composition (6) for forming a light-emitting layer.
Figure BDA0003862503640002191
The following components were stirred until a uniform solution was obtained, thereby preparing a composition (7) for forming a light-emitting layer.
Figure BDA0003862503640002192
In Table C-3, "2PXZ-TAZ" is 10,10' - ((4-phenyl-4H-1, 2, 4-triazole-3, 5-diyl) bis (4, 1-phenyl)) bis (10H-phenoxazine). The chemical structure is shown below.
[ solution 285]
Figure BDA0003862503640002193
< example C7 >
An ND-3202 (manufactured by Nissan chemical industries) solution was spin-coated on a glass substrate on which ITO was formed to a thickness of 45nm, and then the substrate was heated at 50 ℃ for 3 minutes and 230 ℃ for 15 minutes in an atmospheric environment, thereby forming an ND-3202 film (hole injection layer) having a thickness of 50 nm. Subsequently, an XLP-101 solution was spin-coated, and heated on a hot plate at 200 ℃ for 30 minutes under a nitrogen gas atmosphere, thereby forming an XLP-101 film (hole transport layer) having a film thickness of 20 nm. Subsequently, the composition (5) for forming a light-emitting layer was spin-coated and heated at 130 ℃ for 10 minutes in a nitrogen gas atmosphere, thereby forming a light-emitting layer of 20 nm.
The produced multilayer film was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by showa vacuum (stock)), and a boat for vapor deposition made of molybdenum in which TSPO1 was placed, a boat for vapor deposition made of molybdenum in which LiF was placed, and a boat for vapor deposition made of tungsten in which aluminum was placed were installed. The vacuum vessel was depressurized to 5X 10 -4 Pa, TSPO1 was heated and vapor-deposited to a film thickness of 30nm, thereby forming an electron transport layer. The deposition rate in forming the electron transport layer was set to 1 nm/sec. Then, liF is heated and vapor deposition is performed at a vapor deposition rate of 0.01 nm/sec to 0.1 nm/sec so that the film thickness becomes 1 nm. Subsequently, aluminum was heated and vapor-deposited to a film thickness of 100nm to form a cathode. Thus, an organic EL element was obtained.
< example C8 and example C9 >
An organic EL device was obtained in the same manner as in example C7, using the composition (6) for forming a light-emitting layer or the composition (7) for forming a light-emitting layer.
As described above, although some of the compounds of the present invention have been evaluated as excellent materials for organic EL devices, other compounds not evaluated also have the same basic skeleton and have similar structures as a whole, and those skilled in the art can similarly understand that the compounds are excellent materials for organic EL devices.
[ industrial applicability ]
The polycyclic aromatic compound of the present invention is useful as a material for an organic device, particularly a material for a light-emitting layer for forming a light-emitting layer of an organic electroluminescent element. By using the polycyclic aromatic compound of the present invention as a dopant for a light-emitting layer, an organic electroluminescent element which has a long lifetime, a low driving voltage, and high efficiency of light emission, particularly, which has a long lifetime and high efficiency of light emission can be obtained.

Claims (18)

1. A polycyclic aromatic compound represented by the following general formula (1), or a polymer of the polycyclic aromatic compound having a plurality of unit structures represented by the following general formula (1),
Figure FDA0003862503630000011
in the formula (1), the reaction mixture is,
ring A, ring B, and ring C are each independently an aryl or heteroaryl ring, at least one hydrogen in these rings may be substituted,
Y 1 is > B-, > P (= O) -, > P (= S) -, > Al-, > Ga-, > As-, > Si (-R) -, or > Ge (-R) -, wherein R of "> Si (-R) -" and R of "> Ge (-R) -" are independently aryl which may be substituted, heteroaryl which may be substituted, alkyl which may be substituted, or cycloalkyl which may be substituted,
X 1 and X 2 Are each independently > N-R, > O, > S, > C (-R) 2 、＞Si(-R) 2 Or > Se, said "> R of N-R" > C (-R) 2 "R, and" > Si (-R) 2 R of "are each independently hydrogen, aryl which may be substituted, heteroaryl which may be substituted, alkyl which may be substituted, or cycloalkyl which may be substituted,
in addition, as X 1 And X 2 Said "> C (-R) 2 "two R of each other and" > Si (-R) 2 "two R's may be independently bonded to each other via a linking group,
in addition, as X 1 And X 2 The "> R of N-R" > C (-R) 2 "R, and" > Si (-R) 2 R of "" may be independently bonded to at least one of the A ring, the B ring, and the C ring via a linking group, respectively,
at least one hydrogen in the compound or unit structure represented by the formula (1) is substituted with a group represented by the formula (G),
in the formula (G), the reaction mixture is,
rg are each independently hydrogen or a substituent, wherein not all Rg are hydrogen,
* Is a bonding position with the compound or unit structure represented by the formula (1),
at least one of the A ring, B ring, C ring, aryl group, and heteroaryl group in the compound or unit structure represented by the formula (1) may be condensed with at least one cycloalkane, at least one hydrogen in the cycloalkane may be substituted, and at least one of the cycloalkanes — -CH 2 - "may be substituted by" -O- ", and,
at least one hydrogen in the compound or unit structure represented by the formula (1) may be substituted with deuterium, cyano, or halogen.
2. The polycyclic aromatic compound or the multimer thereof according to claim 1, wherein in the formula (1),
the A ring, the B ring, and the C ring are each independently an aryl ring or a heteroaryl ring, at least one hydrogen in these rings may each be independently substituted with a substitutable aryl group, a substitutable heteroaryl group, a substitutable diarylamino group, a substitutable diheteroarylamino group, a substitutable arylheteroarylamino group, a substitutable diarylboron group, a substitutable alkyl group, a substitutable cycloalkyl group, a substitutable alkenyl group, a substitutable alkoxy group, a substitutable aryloxy group, a substitutable arylthio group, or a substituted silyl group, two aryl groups of the diarylamino group may be bonded via a linking group, two heteroaryl groups of the diarylamino group may be bonded via a linking group, an aryl group and a heteroaryl group of the arylheteroarylamino group may be bonded via a linking group, two aryl groups of the diarylboron group may be bonded via a linking group,
Y 1 is > B-, > P (= O) -, > P (= S) -, > Al-, > Ga-, > As-, > Si (-R) -, or > Ge (-R) -, R of said "> Si (-R) -" and R of said "> Ge (-R) -" are independently aryl, heteroaryl, alkyl, or cycloalkyl, respectively, at least one hydrogen of said R may be independently substituted with alkyl or cycloalkyl, respectively,
X 1 And X 2 Are respectively provided withIndependently > N-R, > O, > S, > C (-R) 2 、＞Si(-R) 2 Or > Se, said "> R of N-R" > C (-R) 2 "R, and" > Si (-R) 2 R of "are each independently hydrogen, aryl, heteroaryl, alkyl, or cycloalkyl, at least one of which may each independently be substituted with aryl, alkyl, or cycloalkyl which may be substituted with alkyl or cycloalkyl,
in addition, as X 1 And X 2 Said "> C (-R) 2 "two R of each other and" > Si (-R) 2 "two R' S may each independently of one another be bound via a single bond, -CH = CH-," C-CR = CR-, -C ≡ C-, -N (-R) -, -O-, -S-, -C (-R) 2 -、-Si(-R) 2 a-or-Se-bond, R of the "-CR = CR-", "-N (-R) -", and "-C (-R) 2 R of- "and" -Si (-R) 2 - "R's are each independently hydrogen, aryl, heteroaryl, alkyl, alkenyl, alkynyl, or cycloalkyl, at least one of which may be independently substituted with alkyl or cycloalkyl, and two adjacent R's may be bonded to each other to each independently form a cycloalkylene ring, an arylene ring, or a heteroarylene ring,
in addition, as X 1 And X 2 The "> R of N-R" > C (-R) 2 "R, and" > Si (-R) 2 R of "may each independently be via a single bond, -CH = CH-, -CR = CR-, -C.ident.C-, -N (-R) -, -O-, -S-, -C (-R) 2 -、-Si(-R) 2 -, or-Se-bonded to at least one of the A ring, the B ring, and the C ring, R of the "-CR = CR-", "-R of the" -N (-R) - "," -C (-R) 2 - "R, and" -Si (-R) 2 - "R's are each independently hydrogen, aryl, heteroaryl, alkyl, alkenyl, alkynyl, or cycloalkyl, at least one of which may be independently substituted with alkyl or cycloalkyl, and two adjacent R's may be bonded to each other to each independently form a cycloalkylene ring, an arylene ring, or a heteroarylene ring,
at least one hydrogen in the compound or unit structure represented by the formula (1) is substituted with a group represented by the formula (G),
in the formula (G), the compound represented by the formula (G),
rg are each independently hydrogen, an aryl group which may be substituted, a heteroaryl group which may be substituted, a diarylamino group which may be substituted, a diheteroarylamino group which may be substituted, an arylheteroarylamino group which may be substituted, a diarylboron group which may be substituted, an alkyl group which may be substituted, a cycloalkyl group which may be substituted, an alkenyl group which may be substituted, an alkoxy group which may be substituted, an aryloxy group which may be substituted, an arylthio group which may be substituted, a silyl group which may be substituted, or a halogen, two aryl groups of the diarylamino group may be bonded via a linking group, two heteroaryl groups of the diarylamino group may be bonded via a linking group, an aryl group and a heteroaryl group of the arylheteroarylamino group may be bonded via a linking group, two aryl groups of the diarylboron group may be bonded via a linking group, wherein Rg is not all hydrogen,
* Is a bonding position with the compound or unit structure represented by the formula (1),
at least one of the A ring, B ring, C ring, aryl group, and heteroaryl group in the compound or unit structure represented by the formula (1) may be condensed with at least one cycloalkane, at least one hydrogen in the cycloalkane may be independently substituted with an aryl group, a heteroaryl group, an alkyl group, or a cycloalkyl group, respectively, and at least one "-CH-in the cycloalkane 2 - "may be substituted by" -O- ", and,
at least one hydrogen in the compound or unit structure represented by the formula (1) may be substituted with deuterium, cyano, or halogen.
3. The polycyclic aromatic compound or the multimer thereof according to claim 1, wherein the general formula (1) is represented by the following general formula (2),
Figure FDA0003862503630000031
/>
in the formula (2), the reaction mixture is,
R 1 ～R 11 each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboron, alkyl, cycloalkylAlkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, or alkylbicycloalkylsilyl, R 1 ～R 11 At least one hydrogen in the diarylamino group can be independently substituted with an aryl group, a heteroaryl group, an alkyl group, or a cycloalkyl group, two aryl groups of the diarylamino group can be bonded via a linking group, two heteroaryl groups of the diheteroarylamino group can be bonded via a linking group, an aryl group and a heteroaryl group of the arylheteroarylamino group can be bonded via a linking group, two aryl groups of the diarylboron group can be bonded via a linking group,
In addition, R 1 ～R 3 、R 4 ～R 7 And R 8 ～R 11 Wherein adjacent groups in (a) may be bonded to each other and form an aryl ring or a heteroaryl ring together with the a-ring, the b-ring, and the c-ring, respectively, at least one hydrogen in the formed ring may be independently substituted with an aryl group, a heteroaryl group, a diarylamino group, a diheteroarylamino group, a diarylboron group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group, an arylthio group, a triarylsilyl group, a trialkylsilyl group, a tricycloalkylsilyl group, a dialkylcycloalkylsilyl group, or an alkylbicycloalkylsilyl group, at least one of these substituents may be independently substituted with an aryl group, a heteroaryl group, an alkyl group, or a cycloalkyl group, two aryl groups of the diarylamino group may be bonded via a linking group, two heteroaryl groups of the diheteroarylamino group may be bonded via a linking group, an aryl group and a heteroaryl group of the arylheteroarylamino group may be bonded via a linking group, two aryl groups of the diarylboron group may be bonded via a linking group,
any of the rings a, b, and C may be substituted with "-N =" where R is R, and the "C (-R) =" may be substituted with "N = 1 ～R 11 Any "-C (-R) = C (-R) -" may be substituted with "-N (-R) -", "-O-", "-S-", "-C (-R) 2 -”、“-Si(-R) 2 - ", or" -Se- ", wherein R of the" -C (-R) = C (-R) - "is R 1 ～R 11 R of the "-N (-R) -", "-C (-R) 2 R of- ", and" -Si-R) 2 - "R are each independently hydrogen, aryl, heteroaryl, alkyl, or cycloalkyl, at least one of said R hydrogens may each be independently substituted with alkyl or cycloalkyl, and said" -C (-R) 2 Two R of- "are each other and" -Si (-R) 2 Two R of-can each independently be via a single bond, -CH = CH-) -CR = CR-, -C ≡ C-, -N (-R) -, -O-, -S-, -C (-R) 2 -、-Si(-R) 2 -, or-Se-is bonded, R of the "-CR = CR-", "-N (-R) -", and "-C (-R) 2 R of- "and" -Si (-R) 2 - "R's are each independently hydrogen, aryl, heteroaryl, alkyl, alkenyl, alkynyl, or cycloalkyl, at least one of which may be independently substituted with alkyl or cycloalkyl, and two adjacent R's may be bonded to each other to each independently form a cycloalkylene ring, an arylene ring, or a heteroarylene ring,
Y 1 is > B-, > P (= O) -, or > P (= S) -,
X 1 and X 2 Each independently > N-R, > O, > S, or > C (-R) 2 R of "> N-R" and "> C (-R) 2 R of "are each independently hydrogen, aryl, heteroaryl, alkyl, or cycloalkyl, at least one of which may each independently be substituted with aryl, alkyl, or cycloalkyl which may be substituted with alkyl or cycloalkyl,
In addition, as X 1 And X 2 Said "> C (-R) 2 "two R' S may be linked to each other via a single bond, -CH = CH-, -CR = CR-, -C.ident.C-, -N (-R) -, -O-, -S-, -C (-R) 2 -、-Si(-R) 2 -, or-Se-is bonded, R of the "-CR = CR-", "-N (-R) -", and "-C (-R) 2 R of- "and" -Si (-R) 2 R of- "are each independently hydrogen, aryl, heteroaryl, alkyl, alkenyl, alkynyl, or cycloalkyl, at least one of which may be independently substituted with alkyl or cycloalkyl, and two adjacent R's may be bonded to each other to form cycloalkylene, arylene, or heteroarylene rings, respectively,
in addition, as X 1 And X 2 R of "> N-R" and "> C (-R) 2 R of "may each independently be via a single bond, -CH = CH-, -CR = CR-, -C ≡ C-, -N (-R) -, -O-, -S-, -C (-R) 2 -、-Si(-R) 2 -, or-Se-bonded to at least one of the rings a, b, and C, R of the "-CR = CR-", "-R of the" -N (-R) - "," -C (-R) 2 - "R, and" -Si (-R) 2 R of- "are each independently hydrogen, aryl, heteroaryl, alkyl, alkenyl, alkynyl, or cycloalkyl, at least one of which may be independently substituted with alkyl or cycloalkyl, and two adjacent R's may be bonded to each other to form cycloalkylene, arylene, or heteroarylene rings, respectively,
At least one hydrogen in the compound or unit structure represented by the formula (2) is substituted with a group represented by the formula (G),
in the formula (G), the compound represented by the formula (G),
rg are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboron, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, alkylbicycloalkylsilyl, or halogen, at least one of Rg is each independently substituted with aryl, heteroaryl, alkyl, or cycloalkyl, two aryl groups of the diarylamino can be bonded via a linking group, two heteroaryl groups of the diheteroarylamino can be bonded via a linking group, aryl and heteroaryl groups of the arylheteroarylamino can be bonded via a linking group, two aryl groups of the diarylboron can be bonded via a linking group, rg, wherein not all are hydrogen,
* Is a bonding position with the compound or unit structure represented by the formula (2),
at least one of the a-ring, b-ring, c-ring, formed ring, aryl group, and heteroaryl group in the compound or unit structure represented by the formula (2) may be condensed with at least one cycloalkane, at least one of hydrogens in the cycloalkane may be independently substituted with an aryl group, a heteroaryl group, an alkyl group, or a cycloalkyl group, respectively, and at least one of the cycloalkanes "-CH 2 - "passable" -O- "and, furthermore,
at least one hydrogen in the compound or unit structure represented by the formula (2) may be substituted with deuterium, cyano, or halogen.
4. The polycyclic aromatic compound or the multimer thereof according to claim 3, wherein in the formula (2),
R 1 ～R 11 each independently represents hydrogen, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a diarylamino group, a diheteroarylamino group, an arylheteroarylamino group, a diarylboron group, an alkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms, an alkenyl group having 1 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an arylthio group having 6 to 30 carbon atoms, a triarylsilyl group, a trialkylsilyl group, a tricycloalkylsilyl group, a dialkylcycloalkylsilyl group, or an alkylbicycloalkylsilyl group, an aryl group in the diarylamino group is an aryl group having 6 to 12 carbon atoms, and a heteroaryl group in the diheteroarylamino group is a heteroaryl group having 2 to 15 carbon atoms, the aryl group in the arylheteroarylamino group is an aryl group having 6 to 12 carbon atoms, the heteroaryl group is a heteroaryl group having 2 to 15 carbon atoms, the aryl group in the diarylboron group is an aryl group having 6 to 12 carbon atoms, the aryl group in the triarylsilyl group is an aryl group having 6 to 12 carbon atoms, the alkyl group in the trialkylsilyl group is an alkyl group having 1 to 12 carbon atoms, the cycloalkyl group in the tricycloalkylsilyl group is a cycloalkyl group having 3 to 12 carbon atoms, the alkyl group in the dialkylcycloalkylsilyl group is an alkyl group having 1 to 12 carbon atoms, the cycloalkyl group is a cycloalkyl group having 3 to 12 carbon atoms, the alkyl group in the alkylbicycloalkylsilyl group is an alkyl group having 1 to 12 carbon atoms, the cycloalkyl group is a cycloalkyl group having 3 to 12 carbon atoms, R is a cycloalkyl group having 3 to 12 carbon atoms, and R is an alkyl group having 2 to 15 carbon atoms 1 ～R 11 Wherein at least one hydrogen in the alkyl group is independently substituted by an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 14 carbon atoms,
in addition, R 1 ～R 3 、R 4 ～R 7 And R 8 ～R 11 Wherein adjacent groups in (a) may be bonded to each other, and form an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms together with the a-ring, the b-ring, and the c-ring, respectivelyWherein at least one hydrogen atom is independently substituted by an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a diarylamino group, a diheteroarylamino group, an arylheteroarylamino group, a diarylboron group, an alkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms, an alkenyl group having 1 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an arylthio group having 6 to 30 carbon atoms, a triarylsilyl group, a trialkylsilyl group, a tricycloalkylsilyl group, a dialkylcycloalkylsilyl group, or an alkylbicycloalkylsilyl group, the aryl group in the diarylamino group is an aryl group having 6 to 12 carbon atoms, the heteroaryl group in the diheteroarylamino group is a heteroaryl group having 2 to 15 carbon atoms, and the aryl group in the arylheteroarylamino group is an aryl group having 6 to 12 carbon atoms, the heteroaryl group is a heteroaryl group having 2 to 15 carbon atoms, the aryl group in the diarylboron group is an aryl group having 6 to 12 carbon atoms, the aryl group in the triarylsilyl group is an aryl group having 6 to 12 carbon atoms, the alkyl group in the trialkylsilyl group is an alkyl group having 1 to 12 carbon atoms, the cycloalkyl group in the tricycloalkylsilyl group is a cycloalkyl group having 3 to 12 carbon atoms, the alkyl group in the dialkylcycloalkylsilyl group is an alkyl group having 1 to 12 carbon atoms, the cycloalkyl group is a cycloalkyl group having 3 to 12 carbon atoms, the alkyl group in the alkylbicycloalkylsilyl group is an alkyl group having 1 to 12 carbon atoms, and the cycloalkyl group is a cycloalkyl group having 3 to 12 carbon atoms, and at least one hydrogen of these substituents may be independently substituted by an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 14 carbon atoms,
any of the rings a, b, and C may be substituted with "-N =" where R is R, and the "C (-R) =" may be substituted with "N = 1 ～R 11 Any "-C (-R) = C (-R) -" may be substituted with "-N (-R) -", "-O-", "-S-", "-C (-R) 2 -”、“-Si(-R) 2 - ", or" -Se- ", wherein R of the" -C (-R) = C (-R) - "is R 1 ～R 11 R of the "-N (-R) -", "-C (-R) 2 - "R, and" -Si (-R) 2 - "R is independently hydrogen, aryl having 6 to 12 carbon atoms, heteroaryl having 2 to 15 carbon atoms, alkyl having 1 to 6 carbon atoms, or cycloalkyl having 3 to 14 carbon atoms, and at least one hydrogen in R is independently hydrogen atom or a C1 to C6 alkyl group or C3 to C14 cycloalkyl groupSubstituted radical, the said "-C (-R) 2 - "two R of each other and" -Si (-R) 2 Two R of-can each independently be via a single bond, -CH = CH-) -CR = CR-, -C ≡ C-, -N (-R) -, -O-, -S-, -C (-R) 2 -、-Si(-R) 2 -, or-Se-is bonded, R of the "-CR = CR-", "-N (-R) -", and "-C (-R) 2 - "R, and" -Si (-R) 2 - "wherein R is each independently hydrogen, an aryl group having 6 to 10 carbon atoms, a heteroaryl group having 2 to 10 carbon atoms, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, an alkynyl group having 1 to 5 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms, at least one hydrogen in the R may be each independently substituted by an alkyl group having 1 to 5 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms, and two adjacent R's may be bonded to each other to form a cycloalkylene ring having 3 to 14 carbon atoms, an arylene ring having 6 to 12 carbon atoms, or a heteroarylene ring having 2 to 15 carbon atoms,
Y 1 Is > B-, > P (= O) -, or > P (= S) -,
X 1 and X 2 Each independently > N-R, > O, > S, or > C (-R) 2 R of "> N-R" and "> C (-R) 2 "R is independently hydrogen, aryl having 6 to 18 carbon atoms, heteroaryl having 2 to 15 carbon atoms, alkyl having 1 to 6 carbon atoms, or cycloalkyl having 3 to 14 carbon atoms, wherein at least one hydrogen in R is independently substituted by aryl having 6 to 18 carbon atoms, alkyl having 1 to 6 carbon atoms, or cycloalkyl having 3 to 14 carbon atoms which may be substituted by alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms,
in addition, as X 1 And X 2 Said "> C (-R) 2 "two R' S may be linked to each other via a single bond, -CH = CH-, -CR = CR-, -C ≡ C-, -N (-R) -, -O-, -S-, -C (-R) 2 -、-Si(-R) 2 -, or-Se-is bonded, R of the "-CR = CR-", "-N (-R) -", and "-C (-R) 2 - "R, and" -Si (-R) 2 R of the formula- "is each independently hydrogen, aryl having 6 to 12 carbon atoms, heteroaryl having 2 to 15 carbon atoms, alkyl having 1 to 6 carbon atoms, alkenyl having 1 to 6 carbon atoms, alkynyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms, and at least one hydrogen in the formula R may be independently an alkyl having 1 to 6 carbon atoms or an alkyl having 3 to 14 carbon atomsWherein adjacent two R's may be bonded to each other to form independently a cycloalkylene ring having 3 to 14 carbon atoms, an arylene ring having 6 to 12 carbon atoms, or a heteroarylene ring having 2 to 15 carbon atoms,
In addition, as X 1 And X 2 R of "> N-R" and "> C (-R) 2 R of "may each independently be via a single bond, -CH = CH-, -CR = CR-, -C ≡ C-, -N (-R) -, -O-, -S-, -C (-R) 2 -、-Si(-R) 2 -, or-Se-bonded to at least one of the rings a, b, and C, R of the "-CR = CR-", "-R of the" -N (-R) - "," -C (-R) 2 - "R, and" -Si (-R) 2 R in the formula- "is independently hydrogen, aryl having 6 to 12 carbon atoms, heteroaryl having 2 to 15 carbon atoms, alkyl having 1 to 6 carbon atoms, alkenyl having 1 to 6 carbon atoms, alkynyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms, at least one of the hydrogens in the R may be independently substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms, and two adjacent Rs may be bonded to each other to independently form cycloalkylene having 3 to 14 carbon atoms, arylene having 6 to 12 carbon atoms or heteroarylene having 2 to 15 carbon atoms,
at least one hydrogen in the compound or unit structure represented by the formula (2) is substituted with a group represented by the formula (G),
in the formula (G), the compound represented by the formula (G),
rg is independently hydrogen, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a diarylamino group, a diheteroarylamino group, an arylheteroarylamino group, a diarylboron group, an alkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms, an alkenyl group having 1 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an arylthio group having 6 to 30 carbon atoms, a triarylsilyl group, a trialkylsilyl group, a tricycloalkylsilyl group, a dialkylcycloalkylsilyl group, or an alkylbicycloalkylsilyl group, or a halogen, the aryl group in the diarylamino group is an aryl group having 6 to 12 carbon atoms, the heteroaryl group in the diheteroarylamino group is a heteroaryl group having 2 to 15 carbon atoms, the aryl group in the arylheteroarylsilyl group is an aryl group having 6 to 12 carbon atoms, the aryl group in the triarylsilyl group is an aryl group having 6 to 12 carbon atoms, the alkyl group in the trialkylsilyl group is an alkyl group having 1 to 12 carbon atoms, the cycloalkyl group in the triarylsilyl group is an alkyl group having 6 to 12 carbon atoms, the cycloalkyl group having 3 to 12 carbon atoms, the cycloalkyl group is a hydrogen, the cycloalkyl group is substituted by at least one of the cycloalkyl group having 3 to 12 carbon atoms, the cycloalkyl group in the cycloalkyl group, the cycloalkyl group having 3 to 12 carbon atoms, the cycloalkyl group is not a hydrogen, and the cycloalkyl group having 3 to 12 carbon atoms,
* Is a bonding position with the compound or unit structure represented by the formula (2),
at least one of the a-ring, b-ring, c-ring, formed ring, aryl group and heteroaryl group in the compound or unit structure represented by the formula (2) may be condensed with at least one cycloalkane having 3 to 24 carbon atoms, at least one hydrogen in the cycloalkane may be independently substituted with an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 16 carbon atoms, and at least one ″ -CH in the cycloalkane may be 2 - "may be substituted by" -O- ",
in the case of multimers, dimers or trimers having two or three unit structures represented by formula (2), and,
at least one hydrogen in the compound or unit structure represented by the formula (2) may be substituted with deuterium, cyano, or halogen.
5. The polycyclic aromatic compound or the multimer thereof according to claim 3, wherein in the formula (2),
R 1 ～R 11 independently represents hydrogen, aryl group having 6 to 30 carbon atoms, heteroaryl group having 2 to 30 carbon atoms, diarylamino group, diheteroarylamino group, alkyl group having 1 to 24 carbon atoms, cycloalkyl group having 3 to 24 carbon atoms, alkoxy group having 1 to 24 carbon atoms, aryloxy group having 6 to 30 carbon atoms or arylthio group having 6 to 30 carbon atoms, wherein aryl group in diarylamino group is aryl group having 6 to 12 carbon atoms, and heteroaryl group in diheteroarylamino group is aryl group having 6 to 12 carbon atoms Heteroaryl having 2 to 15 carbon atoms, excluding adamantyl in the cycloalkyl having 3 to 24 carbon atoms, R 1 ～R 11 Wherein at least one hydrogen in the above-mentioned group is independently substituted by an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 14 carbon atoms, with the exception of an adamantyl group in the cycloalkyl group having 3 to 14 carbon atoms,
in addition, R 1 ～R 3 、R 4 ～R 7 And R 8 ～R 11 Wherein adjacent groups in (b) are each optionally bonded to each other and form an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms together with the a ring, the b ring and the c ring, at least one hydrogen in the formed rings is independently substituted with an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a diarylamino group, an alkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, an aryloxy group having 6 to 30 carbon atoms or an arylthio group having 6 to 30 carbon atoms, the aryl group in the diarylamino group is an aryl group having 6 to 12 carbon atoms, the heteroaryl group in the diarylamino group is a heteroaryl group having 2 to 15 carbon atoms, the hydrogen in the cycloalkyl group having 3 to 24 carbon atoms is excluded, at least one of these substituents is independently substituted with an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, or an adamantyl group having 3 to 14 carbon atoms,
any of the rings a, b, and C may be substituted with "-N =" where R is R, and the "C (-R) =" may be substituted with "N = 1 ～R 11 Any "-C (-R) = C (-R) -" may be substituted with "-N (-R) -", "-O-", or "-S-", where R of the "-C (-R) = C (-R) -" is R 1 ～R 11 Wherein R of the "-N (-R) -" is independently hydrogen, aryl having 6 to 12 carbon atoms, heteroaryl having 2 to 15 carbon atoms, alkyl having 1 to 6 carbon atoms, or cycloalkyl having 3 to 14 carbon atoms, with the exception of adamantyl group in the cycloalkyl having 3 to 14 carbon atoms,
Y 1 is > B-, > P (= O) -, or > P (= S) -,
X 1 and X 2 Each independently > N-R, > O, or > S, said "> N-R" RIndependently represents hydrogen, aryl having 6 to 18 carbon atoms, heteroaryl having 2 to 15 carbon atoms, alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms, with the exception of adamantyl in the cycloalkyl having 3 to 14 carbon atoms, wherein at least one hydrogen in R is independently substituted by aryl having 6 to 18 carbon atoms, alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms which may be substituted by alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms, with the exception of adamantyl in the cycloalkyl having 3 to 14 carbon atoms,
in addition, as X 1 And X 2 R of said "> N-R" may each independently be via a single bond, -CH = CH-) -CR = CR-, -C ≡ C-, -N (-R) -, -O-, -S-, -C (-R) 2 -、-Si(-R) 2 -, or-Se-bonded to at least one of the a ring, the b ring, and the C ring, R of the "-CR = CR-", "-N (-R) -", and "-C (-R) 2 - "R, and" -Si (-R) 2 R of the formula- "is independently hydrogen, aryl group having 6 to 12 carbon atoms, heteroaryl group having 2 to 15 carbon atoms, alkyl group having 1 to 6 carbon atoms, alkenyl group having 1 to 6 carbon atoms, alkynyl group having 1 to 6 carbon atoms or cycloalkyl group having 3 to 14 carbon atoms, with the exception of adamantyl group in the cycloalkyl group having 3 to 14 carbon atoms,
at least one hydrogen in the compound or unit structure represented by the formula (2) is substituted with a group represented by the formula (G),
in the formula (G), the compound represented by the formula (G),
rg is independently hydrogen, aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, diarylamino, diheteroarylamino, alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, alkoxy having 1 to 24 carbon atoms, aryloxy having 6 to 30 carbon atoms, arylthio having 6 to 30 carbon atoms, or halogen, aryl in diarylamino is aryl having 6 to 12 carbon atoms, heteroaryl in diarylamino is heteroaryl having 2 to 15 carbon atoms, adamantyl in cycloalkyl having 3 to 24 carbon atoms is excluded, at least one hydrogen in Rg is independently substituted by aryl having 6 to 12 carbon atoms, heteroaryl having 2 to 15 carbon atoms, alkyl having 1 to 6 carbon atoms, or cycloalkyl having 3 to 14 carbon atoms, with the exception of adamantyl in cycloalkyl having 3 to 14 carbon atoms, wherein not all of Rg are hydrogen,
* Is a bonding position with the compound or unit structure represented by the formula (2),
at least one of the a-ring, b-ring, c-ring, ring formed, aryl group and heteroaryl group in the compound or unit structure represented by the formula (2) may be condensed with at least one cycloalkane having 3 to 24 carbon atoms, wherein at least one hydrogen in the cycloalkane may be independently substituted with an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 16 carbon atoms,
in the case of multimers, dimers or trimers having two or three unit structures represented by formula (2), and,
at least one hydrogen in the compound or unit structure represented by the formula (2) may be substituted with deuterium, cyano, or halogen.
6. The polycyclic aromatic compound or the multimer thereof according to any one of claims 1 to 5, wherein the X 1 And X 2 Is > N-R, X 1 And X 2 R or X of > N-R 1 And X 2 Two of R > N-R, i.e., at least one hydrogen of "aryl" or "heteroaryl", is substituted with a group represented by the formula (G).
7. The polycyclic aromatic compound or the multimer thereof of claim 6, wherein said B-and C-rings, or said B-and C-rings, are condensed with cycloalkanes, at least one hydrogen in said cycloalkane being substituted, at least one "-CH in said cycloalkane 2 - "may be substituted by" -O- ".
8. The polycyclic aromatic compound or the multimer thereof according to claim 6 or 7, wherein the X 1 And X 2 Wherein one R > N-R, i.e., at least one hydrogen of "aryl" or "heteroaryl", is substituted with a group represented by the formula (G) and the other R > N-R, is a group represented by the following formula (A) or formula (B),
Figure FDA0003862503630000081
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in the formula (A) and the formula (B),
x is > N-R, > O, > S, > C (-R) 2 、＞Si(-R) 2 Or > Se, said "> R of N-R" > C (-R) 2 "R, and" > Si (-R) 2 R of "are each independently hydrogen, aryl which may be substituted, heteroaryl which may be substituted, alkyl which may be substituted, or cycloalkyl which may be substituted,
further, the "> C (-R) as X 2 "two R of each other and" > Si (-R) 2 "two R's may be independently bonded to each other via a linking group,
R a and R b Each independently is hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, or alkylbicycloalkylsilyl, R a And R b At least one hydrogen in the diarylamino group can be independently substituted with an aryl group, a heteroaryl group, an alkyl group, or a cycloalkyl group, two aryl groups of the diarylamino group can be bonded via a linking group, two heteroaryl groups of the diheteroarylamino group can be bonded via a linking group, an aryl group and a heteroaryl group of the arylheteroarylamino group can be bonded via a linking group, two aryl groups of the diarylboron group can be bonded via a linking group,
in addition, R a Or R b May be bonded to each other and form, together with the a1 ring and the b1 ring, an aryl ring or a heteroaryl ring, respectively, at least one hydrogen in the formed ring may be independently substituted by an aryl group, a heteroaryl group, a diarylamino group, a diheteroarylamino group, an arylheteroarylamino group, a diarylboron group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group, an arylthio group, a triarylsilyl group, a trialkylsilyl group, a tricycloalkylsilyl group, a dialkylcycloalkylsilyl group, or an alkylbicycloalkylsilyl group, respectively, and at least one hydrogen in these substituents may be independently substituted by an aryl group, a heteroaryl group, a diarylamino group, or an alkylbicycloalkylsilyl group, respectivelyAryl, heteroaryl, alkyl, or cycloalkyl, two aryl groups of the diarylamino group may be bonded via a linking group, two heteroaryl groups of the diheteroarylamino group may be bonded via a linking group, an aryl and heteroaryl group of the arylheteroarylamino group may be bonded via a linking group, two aryl groups of the diarylboron group may be bonded via a linking group,
any of the "C (-R) s in the a1 Ring a ) = ", or any of" -C (-R) in b1 ring b ) = "may be substituted for" -N = ", and,
the group represented by the formula (A) is represented by R or any R > N-R as X a Is a position of 1 Or X 2 With an N-bond > N-R, the radical of formula (B) being any R b Is a position of (A) and is X 1 Or X 2 N-R.
9. The polycyclic aromatic compound or the multimer thereof of claim 8, wherein at least one of the B-and C-rings, or at least one of the B-and C-rings, is a heteroaryl ring.
10. The polycyclic aromatic compound according to claim 1, represented by any one of the following structural formulae,
Figure FDA0003862503630000091
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Figure FDA0003862503630000101
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Figure FDA0003862503630000111
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Figure FDA0003862503630000121
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Figure FDA0003862503630000131
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Figure FDA0003862503630000141
/>
Figure FDA0003862503630000151
/>
Figure FDA0003862503630000161
/>
Figure FDA0003862503630000171
/>
Figure FDA0003862503630000181
wherein Me represents a methyl group, tBu represents a tert-butyl group, and D represents deuterium.
11. A material for organic devices, comprising the polycyclic aromatic compound according to any one of claims 1 to 10 or a multimer thereof.
12. The material for organic devices according to claim 11, which is a material for organic electroluminescent elements, a material for organic field effect transistors, a material for organic thin-film solar cells, or a material for wavelength conversion filters.
13. The material for organic devices according to claim 12, wherein the material for organic electroluminescent elements is a material for light-emitting layers.
14. An organic electroluminescent element comprising: a pair of electrodes including an anode and a cathode; and an organic layer disposed between the pair of electrodes, the organic layer containing the polycyclic aromatic compound according to any one of claims 1 to 10 or a multimer thereof.
15. The organic electroluminescent element according to claim 14, wherein the organic layer is a light-emitting layer.
16. A display device comprising the organic electroluminescent element as claimed in claim 14 or 15.
17. A lighting device comprising the organic electroluminescent element as claimed in claim 14 or 15.
18. A wavelength conversion filter comprising the material for organic devices according to claim 12 as a material for wavelength conversion filters.
CN202211168536.5A 2021-09-29 2022-09-20 Polycyclic aromatic compound, multimer thereof, material for organic device, organic electroluminescent element, and application thereof Pending CN115894535A (en)

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