CN112236435A - Polycyclic aromatic compound and multimer thereof - Google Patents

Polycyclic aromatic compound and multimer thereof Download PDF

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CN112236435A
CN112236435A CN201980037310.1A CN201980037310A CN112236435A CN 112236435 A CN112236435 A CN 112236435A CN 201980037310 A CN201980037310 A CN 201980037310A CN 112236435 A CN112236435 A CN 112236435A
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畠山琢次
近藤靖宏
笹田康幸
小林孝弘
王国防
梁井元树
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Kwansei Gakuin Educational Foundation
SK Materials JNC Co Ltd
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JNC Corp
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Abstract

The present invention provides a novel polycyclic aromatic compound in which a plurality of aromatic rings are connected by a boron atom, a nitrogen atom, or the like, thereby increasing the number of options for materials for organic EL devices. Further, by using a novel polycyclic aromatic compound as a material for an organic electroluminescent element, an excellent organic EL element is provided.

Description

Polycyclic aromatic compound and multimer thereof
Technical Field
The present invention relates to a polycyclic aromatic compound and a multimer thereof (hereinafter, these are also collectively referred to simply as "polycyclic aromatic compound"), and an organic device such as an organic electroluminescent element, an organic field effect transistor, and an organic thin-film solar cell, a display device, and a lighting device using the same.
Background
Conventionally, display devices using light-emitting elements that perform electroluminescence have been studied in various ways because they can achieve power saving and reduction in thickness, and further, organic electroluminescence elements including organic materials have been studied actively because they are easy to reduce the weight and increase the size. In particular, active studies have been made to develop organic materials having light-emitting characteristics such as blue, which is one of the three primary colors of light, and to develop organic materials having charge transport capabilities (having the possibility of becoming semiconductors or superconductors) such as holes and electrons, regardless of high-molecular compounds and low-molecular compounds.
An organic Electroluminescence (EL) element has a structure including: the organic light-emitting device includes 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 these layers have been developed.
As a material for the light-emitting layer, for example, a benzofluorene compound has been developed (international publication No. 2004/061047). Further, as the hole transporting material, for example, triphenylamine compounds and the like have been developed (Japanese patent laid-open No. 2001-172232). Further, as an electron transport material, for example, an anthracene compound has been developed (Japanese patent laid-open No. 2005-170911).
In recent years, as a material used for an organic EL device or an organic thin film solar cell, a material in which a triphenylamine derivative is improved has also been reported (international publication No. 2012/118164). The material is characterized by comprising the following components in parts by weight: referring to N, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine (triphenyldiamine, TPD), which has been put to practical use, the planarity of the aromatic rings constituting triphenylamine is improved by linking the aromatic rings to each other. In the above-mentioned document, for example, the charge transport properties of the NO-linked compound (compound 1 on page 63) are evaluated, but there is NO description of a method for producing a material other than the NO-linked compound, and the properties obtained from 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. Examples of such compounds are also found elsewhere (International publication No. 2011/107186). For example, a compound having a conjugated structure with a large triplet exciton energy (T1) can emit phosphorescence with a shorter wavelength, and is therefore useful as a material for a blue light-emitting layer. Further, as an electron-transporting material or a hole-transporting material which sandwiches the light-emitting layer, a compound having a novel conjugated structure with a large T1 is also demanded.
The host (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. The reason for this is that: by linking a plurality of aromatic rings having a relatively small conjugated system, a large Highest Occupied Molecular Orbital (HOMO) -Lowest Unoccupied Molecular Orbital (LUMO) gap (band gap Eg of the thin film) required for the host material can be ensured. Furthermore, a host material of an organic EL element using a phosphorescent material or a Thermally Active Delayed Fluorescence (TADF) material also requires high triplet excitation energy (E)T) By linking an aromatic ring or substituent of donor or acceptor to the molecule, the Single Occupied Molecular Orbital (SOMO) 1 and SOMO2 of triplet excited state (T1) are localized, and the exchange interaction between the two orbitals is reduced, whereby the triplet excitation energy (E) can be increasedT). However, the oxidation-reduction stability of an aromatic ring having a small conjugated system is not sufficient, and the life of an element using a molecule in which conventional aromatic rings are linked as a host material is not sufficient. On the other hand, a polycyclic aromatic compound having an extended pi-conjugated system is generally excellent in redox stability, but has a HOMO-LUMO gap (band gap Eg of thin film) or triplet excitation energy (E) T) Low and therefore not considered suitable as host material.
In recent years, compounds obtained by condensing a plurality of aromatic rings with boron or the like as a central atom have also been reported (international publication No. 2015/102118). In the above-mentioned document, evaluation of an organic EL element using a compound obtained by condensing the above-mentioned plurality of aromatic rings as a dopant material of a light-emitting layer has been carried out, and it is advantageous to study a compound having excellent organic EL characteristics, particularly light-emitting characteristics, among these compounds, which is disclosed in a very large number of compounds. As the light emission characteristics, a narrow half-value width of the emission spectrum, a high fluorescence quantum yield, and a small retardation are basically requiredFluorescence lifetime, large energy gap Eg and small Δ ESTAnd the like, and preferably one or more of these are excellent in properties, and when they have all of the excellent properties, they are expected to be used as a thermally activated delayed fluorescence material.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2004/061047
Patent document 2: japanese patent laid-open No. 2001-172232
Patent document 3: japanese patent laid-open No. 2005-170911
Patent document 4: international publication No. 2012/118164
Patent document 5: international publication No. 2011/107186
Patent document 6: international publication No. 2015/102118
Disclosure of Invention
Problems to be solved by the invention
As described above, various materials have been developed as materials used in organic EL devices, but in order to further improve organic EL characteristics such as light emitting characteristics or to increase options for organic EL materials such as materials for light emitting layers, it is desired to develop compounds which have not been specifically known before.
Means for solving the problems
As a result of diligent research directed toward solving the above problems, the present inventors have found that a polycyclic aromatic compound in which a plurality of aromatic rings are connected by a boron atom, a nitrogen atom, an oxygen atom, or the like has a condensed structure at a specific position and expands the plane formed by the molecules, and that a substituent is further introduced at a specific position in the compound to deform the plane formed by the molecules, thereby obtaining an excellent organic EL device, and have completed the present invention. That is, the present invention provides the following polycyclic aromatic compound, and further provides an organic device material and the like containing the following polycyclic aromatic compound.
In the present specification, the number of carbon atoms in the chemical structure or the substituent may be represented by the number of carbon atoms, and the number of carbon atoms in the chemical structure or the substituent when the chemical structure is substituted with a substituent or when the substituent is substituted with a substituent does not mean the number of carbon atoms in the chemical structure or the substituent in total or the number of carbon atoms in the substituent and the substituent in total. 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.
A polycyclic aromatic compound represented by the following general formula (1) or a polymer of a polycyclic aromatic compound having a plurality of structures represented by the following general formula (1).
[ solution 20]
Figure BDA0002815937380000031
(in the above-mentioned formula (1),
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13and R14Each independently hydrogen, aryl, heteroaryl, diarylamino, diarylboron (two aryl groups may be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, or aryloxy, at least one of which may be further substituted with aryl, heteroaryl, alkyl, or cycloalkyl, and R1～R3、R4～R7、R8～R10And R11～R14Wherein adjacent groups may be bonded to each other and form an aryl or heteroaryl ring together with at least one of the a, b, c and d ringsAt least one hydrogen may be substituted by an aryl, heteroaryl, diarylamino, diarylboron (two aryl groups may be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, or aryloxy group, at least one of which may in turn be substituted by an aryl, heteroaryl, alkyl, or cycloalkyl group,
x is > O, > N-R, > S or > Se, R > N-R being aryl, heteroaryl, alkyl or cycloalkyl, at least one of which may be substituted by aryl, heteroaryl, alkyl or cycloalkyl,
L is a single bond, > C (-R)2O, > S and > N-R, said > C (-R)2And R in N-R are each independently hydrogen, aryl, heteroaryl, diarylamino, diarylboryl (two aryl groups may be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, or aryloxy, at least one of which hydrogen may be further substituted by aryl, heteroaryl, alkyl, or cycloalkyl,
wherein, when X is > N-R, L is not > O,
in the case of multimers, R in the following formula (1)2Is hydrogen and, furthermore,
at least one hydrogen in the compound and structure represented by the general formula (1) may be substituted by cyano, halogen or deuterium
Item 2.
The polycyclic aromatic compound or multimer thereof according to item 1, wherein
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13And R14Independently represents hydrogen, aryl group having 6 to 30 carbon atoms, heteroaryl group having 2 to 30 carbon atoms, diarylamino group (wherein each aryl group is aryl group having 6 to 12 carbon atoms), diarylboron group (wherein each aryl group is aryl group having 6 to 12 carbon atoms, and two aryl groups may be bonded via a single bond or a linking group), alkyl group having 1 to 12 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms, alkoxy group having 1 to 12 carbon atoms, or aryloxy group having 6 to 30 carbon atoms, and at least one hydrogen of these groups may further be substituted by aryl group having 6 to 30 carbon atoms, heteroaryl group having 2 to 30 carbon atoms, or aryloxy group having 1 carbon atom 12 alkyl or C5-10 cycloalkyl, and R1～R3、R4～R7、R8～R10And R11～R14Wherein adjacent groups are 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 at least one of the a, b, c and d rings, at least one hydrogen in the formed 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 each aryl group is an aryl group having 6 to 12 carbon atoms), a diarylboron group (wherein each aryl group is an aryl group having 6 to 12 carbon atoms and both aryl groups may be bonded via a single bond or a linking group), an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or an aryloxy group having 6 to 30 carbon atoms, and at least one hydrogen in these groups is further substituted by an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms,
x is > O, > N-R, > S or > Se, wherein R > N-R is aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, alkyl having 1 to 12 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, and at least one hydrogen of these groups may be substituted by aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, alkyl having 1 to 12 carbon atoms or cycloalkyl having 5 to 10 carbon atoms,
L is a single bond, > C (-R)2O, > S and > N-R, said > C (-R)2And R in the > N-R independently represents hydrogen, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a diarylamino group (wherein each aryl group is an aryl group having 6 to 12 carbon atoms), a diarylboron group (wherein each aryl group is an aryl group having 6 to 12 carbon atoms and both aryl groups may be bonded via a single bond or a linking group), an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or an aryloxy group having 6 to 30 carbon atoms, at least one hydrogen of these groups being further substituted by an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms,
wherein, when X is > N-R, L is not > O,
in the case of multimers, R in the following formula (1)2Is hydrogen and, furthermore,
at least one hydrogen in the compound and the structure represented by the general formula (1) may be substituted by cyano, halogen or deuterium.
Item 3.
The polycyclic aromatic compound or the multimer thereof according to item 1 or item 2, wherein R4～R7Wherein the adjacent groups are bonded to each other and form an aryl ring or heteroaryl ring together with the b ring, selected from the group consisting of a naphthalene ring, a phenanthrene ring, an anthracene ring, a dibenzofuran ring, a carbazole ring, a dibenzothiophene ring, a silafluorene ring, a fluorene ring, and a ring in which benzene rings are condensed on these rings.
Item 4.
The polycyclic aromatic compound or the multimer thereof according to item 3, wherein R4～R7Wherein the aryl ring or heteroaryl ring, which is formed together with the b ring and to which adjacent groups are bonded, is a ring represented by the following partial structural formula (1a), formula (1b) or formula (1 c).
[ solution 21]
Figure BDA0002815937380000041
In the following formulas, the first and second groups,
R4、R5、R7、R1b、R2b、R3b、R4b、R5band R6bIndependently of one another, hydrogen, aryl, heteroaryl, diarylamino, diarylboron (two aryl groups may be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, or aryloxy, at least one of which hydrogen may in turn be substituted by aryl, heteroaryl, alkyl, or cycloalkyl,
x is > O, > N-R, > S or > Se, R > N-R being aryl, heteroaryl, alkyl or cycloalkyl, at least one of which may be substituted by aryl, heteroaryl, alkyl or cycloalkyl,
z is > O, > N-R, > S, > Si (-R)2And > C (-R)2The > N-R, > Si (-R)2And > C (-R)2Wherein R is independently hydrogen, aryl, heteroaryl, diarylamino, diarylboron (both)An aryl group may be bonded via a single bond or a linking group), an alkyl group, a cycloalkyl group, an alkoxy group, or an aryloxy group, at least one hydrogen of which may in turn be substituted by an aryl group, a heteroaryl group, an alkyl group, or a cycloalkyl group.
Item 5.
The polycyclic aromatic compound or the multimer thereof according to any one of items 1 to 4, wherein R > N-R as the X is an aryl or heteroaryl group, at least one hydrogen of which is substituted with fluorine.
Item 6.
The polycyclic aromatic compound or the multimer thereof according to any one of items 1 to 4, wherein R > N-R as the X is an aryl or heteroaryl group, at least one hydrogen in the ortho position with respect to the N in the aryl or heteroaryl group being substituted with fluorine.
Item 7.
The polycyclic aromatic compound or the multimer thereof according to any one of items 1 to 6, wherein L is a single bond, > O, or > N-R.
Item 8.
The polycyclic aromatic compound or the multimer thereof according to any one of items 1 to 6, wherein L is a single bond.
Item 9.
The polycyclic aromatic compound or the multimer thereof according to any one of items 1 to 4, wherein X is > O and L is a single bond.
Item 10.
The polycyclic aromatic compound or the multimer thereof according to any one of items 1 to 6, wherein X is > N-R, and L is a single bond.
Item 11.
The polycyclic aromatic compound or the multimer thereof according to any one of items 1 to 10, wherein R7And R8One of them is halogen, alkyl group having 1 to 6 carbon atoms, cycloalkyl group having 3 to 14 carbon atoms, aryl group having 6 to 10 carbon atoms or heteroaryl group having 2 to 10 carbon atoms, and the other is hydrogen, alkyl group having 1 to 6 carbon atoms, cycloalkyl group having 3 to 14 carbon atoms, aryl group having 6 to 10 carbon atoms or heteroaryl group having 2 to 10 carbon atoms.
Item 12.
Any one of item 1 to item 10The polycyclic aromatic compound or the multimer thereof, wherein R7And R8Wherein one is halogen, alkyl group having 1 to 4 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms or phenyl group, and the other is hydrogen, alkyl group having 1 to 4 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms or phenyl group.
Item 13.
The polycyclic aromatic compound or the multimer thereof according to any one of items 1 to 10, wherein R7And R8One is methyl, tert-butyl or phenyl and the other is hydrogen, methyl, tert-butyl or phenyl.
Item 14.
The polycyclic aromatic compound or the multimer thereof according to any one of items 1 to 10, wherein R7And R8One is methyl or tert-butyl and the other is hydrogen or methyl.
Item 15.
The polycyclic aromatic compound or the multimer thereof according to any one of items 1 to 10, wherein R7And R8Wherein one is methyl and the other is hydrogen, and when X is > N-R, R > N-R is phenyl, and at least one hydrogen in the phenyl is substituted by aryl having 6 to 12 carbon atoms, heteroaryl having 2 to 10 carbon atoms, alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 14 carbon atoms, or fluorine.
Item 16.
The polycyclic aromatic compound or multimer thereof according to claim 1, which is represented by any one of the following formulae.
[ solution 22]
Figure BDA0002815937380000061
[ solution 23]
Figure BDA0002815937380000062
[ solution 24]
Figure BDA0002815937380000071
[ solution 25]
Figure BDA0002815937380000072
[ solution 26]
Figure BDA0002815937380000073
[ solution 27]
Figure BDA0002815937380000081
(in the formulae, "Me" is methyl and "tBu" is tert-butyl)
Item 17.
The polycyclic aromatic compound according to claim 1, which is represented by any one of the following formulae.
[ solution 28]
Figure BDA0002815937380000082
[ solution 29]
Figure BDA0002815937380000083
[ solution 30]
Figure BDA0002815937380000091
[ solution 31]
Figure BDA0002815937380000092
[ solution 32]
Figure BDA0002815937380000101
[ solution 33]
Figure BDA0002815937380000102
(in the formulae, "Me" is methyl and "tBu" is tert-butyl)
Item 18.
The polycyclic aromatic compound according to claim 1, which is represented by any one of the following formulae.
[ chemical 34]
Figure BDA0002815937380000111
[ solution 35]
Figure BDA0002815937380000112
[ solution 36]
Figure BDA0002815937380000113
(in the formulae, "Me" is methyl and "tBu" is tert-butyl)
Item 19.
A material for organic devices, which contains the polycyclic aromatic compound according to any one of items 1 to 18 or a multimer thereof.
Item 20.
The material for an organic device according to item 19, wherein the material for an organic device is a material for an organic electroluminescent element, a material for an organic field-effect transistor, or a material for an organic thin-film solar cell.
Item 21.
The material for an organic device according to item 20, wherein the material for an organic electroluminescent element is a material for a light-emitting layer.
Item 22.
An organic electroluminescent element comprising: a pair of electrodes including an anode and a cathode; and a light-emitting layer which is arranged between the pair of electrodes and contains the material for a light-emitting layer according to item 21.
Item 23.
The organic electroluminescent element according to item 22, wherein the light-emitting layer further contains a compound represented by the following general formula (3) and/or a compound represented by the following general formula (4).
[ solution 37]
Figure BDA0002815937380000121
(in the general formula (3), L1Is an arylene group having 6 to 30 carbon atoms or a heteroarylene group having 2 to 30 carbon atoms,
in the general formula (4), L2And L3Each independently an aryl group having 6 to 30 carbon atoms or a heteroaryl group having 2 to 30 carbon atoms,
at least one hydrogen in the compound represented by the above formula may be substituted by 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
Item 24.
The organic electroluminescent element according to item 22 or item 23, wherein the light-emitting layer further contains a compound represented by the following general formula (5).
[ solution 38]
Figure BDA0002815937380000131
(in the general formula (5) mentioned above,
R1～R11independently of one another, hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboron (two aryl groups may be bonded via a single bond or a linking group), alkyl or cycloalkyl, at least one hydrogen of which may in turn be replaced by aryl, heteroaryl, diarylamino, diarylboronA group (two aryl groups may be bonded via a single bond or a linking group), an alkyl group or a cycloalkyl group,
R1～R11Wherein adjacent groups may be bonded to each other and form, together with the a-, b-or c-ring, an aryl or heteroaryl ring, at least one hydrogen in the ring formed may be substituted by an aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboron (two aryl groups may be bonded via a single bond or a linking group), an alkyl or a cycloalkyl group, at least one hydrogen of which may in turn be substituted by an aryl, heteroaryl, diarylamino, diarylboron (two aryl groups may be bonded via a single bond or a linking group), an alkyl or a cycloalkyl group,
at least one hydrogen in the compound represented by the general formula (5) may be independently substituted with halogen or deuterium, respectively)
Item 25.
The organic electroluminescent element according to any one of items 22 to 24, which has an electron transport layer and/or an electron injection layer disposed between the cathode and the light-emitting layer, and at least one of the electron transport layer and the electron injection layer contains at least one selected from the group consisting of a borane derivative, a pyridine derivative, a fluoranthene derivative, a BO-based derivative, an anthracene derivative, a benzofluorene derivative, a phosphine oxide derivative, a pyrimidine derivative, a carbazole derivative, a triazine derivative, a benzimidazole derivative, a phenanthroline derivative, and a hydroxyquinoline-based metal complex.
Item 26.
The organic electroluminescent element according to claim 25, wherein the electron transport layer and/or the electron injection layer further contains 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.
Item 27.
A display device or a lighting device, comprising the organic electroluminescent element according to any one of items 22 to 26.
ADVANTAGEOUS EFFECTS OF INVENTION
According to a preferred embodiment of the present invention, the polycyclic aromatic compound represented by the general formula (1) which has not been specifically known can further improve organic EL characteristics such as light-emitting characteristics, or increase the number of options for organic EL materials such as materials for a light-emitting layer. Specific examples of the emission characteristics include a half-value width of an emission spectrum, a fluorescence quantum yield, a delayed fluorescence lifetime, and energy gaps Eg and Δ ESTIn the preferred embodiment of the present invention, the above-described effects are obtained in any one or more of the above-described properties, and the present invention is expected to be used as a thermally activated delayed fluorescence material when the material has the overall excellent properties.
Drawings
Fig. 1 is a schematic sectional view showing an organic EL element according to the present embodiment.
FIG. 2 shows fluorescence spectra of compound (BNpCz-0230), compound (BNpCz-0230/0611-1), and compound (BNpCz-0230/0611/0911S-F26-1) in solution.
Detailed Description
1. Polycyclic aromatic compound represented by general formula (1) and multimer thereof
The present invention is a polycyclic aromatic compound represented by the following general formula (1) or a polymer of a polycyclic aromatic compound having a plurality of structures represented by the following general formula (1).
[ solution 39]
Figure BDA0002815937380000141
For example, three kinds of materials, i.e., a fluorescent material, a phosphorescent material, and a Thermally Activated Delayed Fluorescence (TADF) material, are used as light-emitting materials for organic EL displays, and the light-emitting efficiency of the fluorescent material is low, about 25% to 62.5%. On the other hand, although the emission efficiencies of the phosphorescent material and the TADF material may reach 100%, both have a problem of low color purity (wide emission spectrum width). In a display, various colors are expressed by mixing light emissions of three primary colors of light, i.e., red, green, and blue, but if the color purity of each color is low, a color that cannot be reproduced is generated, and the image quality of the display is greatly reduced. Therefore, in a commercially available display, an unnecessary color is removed from the emission spectrum by an optical filter, and the display is used after improving the color purity (after narrowing the spectral width). Therefore, if the original spectral width is wide, the ratio of removal increases, and therefore, even when the light emission efficiency is high, the substantial efficiency is greatly reduced. For example, the half-value width of the blue emission spectrum of a commercially available smartphone is about 20nm to 25nm, but the half-value width of a general fluorescent material is about 40nm to 60nm, a phosphorescent material is about 60nm to 90nm, and a TADF material is about 70nm to 100 nm. In the case of using a fluorescent material, the half-value width is relatively narrow, and therefore, it is sufficient to remove only a part of the unnecessary color, but in the case of using a phosphorescent material or a TADF material, it is necessary to remove more than half. Under such circumstances, development of a light-emitting material having both light-emitting efficiency and color purity is desired.
Generally, a TADF material is designed to localize HOMO and LUMO in a molecule using an electron donating substituent called a donor and an electron accepting substituent called an acceptor to generate efficient intersystem crossing (reverse intercross crossing), but when a donor or an acceptor is used, structural relaxation in an excited state becomes large (in a certain molecule, a stable structure is different between a ground state and an excited state, and therefore, when a transition from the ground state to the excited state occurs by an external stimulus, the structure thereafter changes to a stable structure in the excited state), thereby providing a broad emission spectrum with low color purity.
Therefore, patent document 6 (international publication No. 2015/102118) proposes a novel molecular design for dramatically improving the color purity of a TADF material. In the compounds (1-401) disclosed in the documents, for example, HOMO is successfully localized on 3 carbons (black circles) on a benzene ring containing 6 carbons and LUMO is localized on the remaining 3 carbons (white circles) by utilizing a multiple resonance effect of boron (electron withdrawing property) and nitrogen (electron donating property). By the efficient intersystem crossing, the luminous efficiency of the compound reaches 100% at the maximum. Further, boron and nitrogen in the compound (1-401) not only localize HOMO and LUMO, but also serve to suppress structural relaxation in an excited state by maintaining a strong planar structure by contracting 3 benzene rings, and as a result, an emission spectrum having a small Stokes shift (Stokes shift) of absorption and emission peaks and high color purity is successfully obtained. The half-value width of the emission spectrum was 28nm, and color purity also exceeded the level of a fluorescent material with high color purity put to practical use. In addition, in the dimer compound (1-422), 2 boron and 2 nitrogen bonds to the central benzene ring, thereby further enhancing the multiple resonance effect on the central benzene ring, and as a result, light emission having an extremely narrow emission peak width can be realized.
[ solution 40]
Figure BDA0002815937380000151
On the other hand, the energy difference Δ E between the excited singlet energy and the excited triplet energy is observed in the compounds (1-401)STHowever, since the organic electroluminescent element has a relatively small size, has a high planarity and a small Spin-Orbit interaction (Spin-Orbit Coupling (SOC)), and thus has a long delayed fluorescence lifetime (tau (delay)), there are problems that the efficiency is low and roll-off (roll-off) is large when the organic electroluminescent element is used as a light-emitting material of an organic electroluminescent element using Thermally Active Delayed Fluorescence (TADF).
Further, in the dimer compound (1-422), since the molecular planarity is high and the resonance is broadened, the emission wavelength becomes long and is far from the practical blue wavelength, and further, since the intermolecular stacking is induced due to the high planarity, there is also a problem that the efficiency of the light-emitting element is not sufficiently satisfied.
Accordingly, the present inventors have made extensive studies and, as a result, have realized adjustment of the emission wavelength and the half-value width of the emission spectrum, high emission efficiency and short delayed fluorescence lifetime in a compound and realized appropriate emission wavelength and the half-value width of the emission spectrum, high device efficiency and small roll-off in a device by appropriately combining three methods (i) introduction of an element for adjusting the multiple resonance effect to an appropriate position, (ii) crosslinking of an aromatic ring for increasing the planarity of a molecule, and (iii) introduction of a substituent at an appropriate position for deforming a molecule and reducing the planarity.
With respect to the (i), specifically, the polycyclic aromatic compound represented by the general formula (1) of the present invention has > O, > N-R, > S or > Se as X1And X2But is introduced into X1And X2The electronegativity of the element(s) in (1) and the multiple resonance effect of the molecule(s) are affected. For example, if at X1And/or X2When > O is introduced, the emission wavelength is generally shorter and the half-value width of the emission spectrum is wider than when > N-R is introduced.
Specifically, the polycyclic aromatic compound represented by the general formula (1) of the present invention has a linking group L connecting the c-ring and the d-ring. By introducing L, conjugation and extension are performed, and the planarity of the molecule is increased. This increases the overlap between the orbitals of the ground state and the excited state, increases the transition probability, and improves the light emission efficiency. On the other hand, the conjugate extension causes a longer emission wavelength. Further, a condensed ring including the c-ring, the d-ring, and the linking group L changes in planarity and flexibility depending on the type of L, and when the planarity is high, improvement of light emission efficiency is expected, whereas when the flexibility is high, intermolecular stacking (stacking) is reduced, and on the other hand, the half-value width of the light emission spectrum is widened.
With respect to (iii), specifically, R is adjusted7Or R8A substituent of (1). The molecule is deformed by introducing a specific substituent, and accompanying this, the singlet and triplet orbitals are also deformed. The deformation of the orbitals brings about greater spin-orbit interactions, which are more likely to produce TADF. The transition from the triplet state to the singlet state (or from the singlet state to the triplet state) is accompanied by the inversion of the electron spin, and according to the law of conservation of energy and the law of conservation of angular momentum, the electron spin is required between the orbitals where the transition is madeThe same orbital angular momentum. The deformation of the molecule and the orbit induced by the substituents causes the generation of greater orbital angular momentum upon transition, thereby inducing a greater magnetic moment, resulting in greater spin-orbit interaction (also known as spin-orbit coupling). In addition, the planarity is reduced due to large deformation of molecules, and thus the stacking between molecules is also reduced.
As a result of combining the methods (i) to (iii), the emission wavelength and the half-value width of the emission spectrum are adjusted in the compound, and high emission efficiency and short delayed fluorescence lifetime are realized, and the half-value width of the emission wavelength and the emission spectrum, high element efficiency, and small roll off are realized appropriately in the element. However, the effect of the polycyclic aromatic compound of the present invention is not limited to the above principle.
In the general formula (1) described above,
R1～R14(hereinafter also referred to as "R")1Etc.) are each independently hydrogen, aryl, heteroaryl, diarylamino, diarylboron (two aryl groups may also be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, or aryloxy (the foregoing being first substituents), at least one hydrogen of which may in turn be substituted by aryl, heteroaryl, alkyl, or cycloalkyl (the foregoing being second substituents), and R is1～R3、R4～R7、R8～R10And R11～R14Wherein adjacent groups may also be bonded to each other and form an aryl or heteroaryl ring together with at least one of the a, b, c and d rings, at least one hydrogen in the formed ring may also be substituted by aryl, heteroaryl, diarylamino, diarylboron (two aryl groups may also be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy or aryloxy (above the first substituent), at least one hydrogen in these may in turn be substituted by aryl, heteroaryl, alkyl or cycloalkyl (above the second substituent),
x is > O, > N-R, > S or > Se, R > N-R being aryl, heteroaryl, alkyl or cycloalkyl (above a first substituent), at least one hydrogen of which may also be substituted by aryl, heteroaryl, alkyl or cycloalkyl (above a second substituent),
L is a single bond, > C (-R)2O, > S and > N-R, said > C (-R)2And R in N-R are each independently hydrogen, aryl, heteroaryl, diarylamino, diarylboron (two aryl groups may also be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, or aryloxy (above the first substituent), at least one hydrogen of which may in turn be substituted by aryl, heteroaryl, alkyl, or cycloalkyl (above the second substituent),
wherein, when X is > N-R, L is not > O,
in the case of multimers, R in the following formula (1)2Is hydrogen and, furthermore,
at least one hydrogen in the compound and the structure represented by the general formula (1) may be substituted by cyano, halogen or deuterium.
R1The "aryl group" (first substituent) is, for example, an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 16 carbon atoms, further preferably an aryl group having 6 to 12 carbon atoms, and particularly preferably an aryl group having 6 to 10 carbon atoms.
Specific examples of the aryl group include: phenyl as a monocyclic system; biphenyl as a bicyclic ring system; naphthyl as the condensed bicyclic system; terphenyl (m-terphenyl, o-terphenyl, p-terphenyl) as a tricyclic system; acenaphthenyl, fluorenyl, phenalkenyl, phenanthrenyl as condensed tricyclic systems; triphenylene, pyrenyl, and tetracenyl groups as condensed quaternary ring systems; perylene groups and pentacene groups as condensed five-ring systems, and the like.
R1The "heteroaryl group" (first substituent) is, for example, 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, further preferably a heteroaryl group having 2 to 15 carbon atoms, and particularly preferably a heteroaryl group having 2 to 10 carbon atoms. The heteroaryl group is, for example, a heterocyclic ring containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen as ring-constituting atoms in addition to carbon, or the like.
Specific examples of the heteroaryl group 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, indolizinyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, furazanyl, thianthrenyl, indolocarbazolyl, benzindolocarbazolyl, benzindolizolocarbazolyl, tetrazolyl, cinnolinyl, carbazolyl, Naphthobenzofuranyl, and the like.
As R1The "aryl group" in the "diarylamino group" (first substituent) and the "aryl group" in the "aryloxy group" (first substituent) of the above, the description of the aryl group can be cited.
R1The "alkyl group" (first substituent) may be either a straight chain or branched chain, 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), more preferably an alkyl group having 1 to 12 carbon atoms (branched chain alkyl group having 3 to 12 carbon atoms), still more preferably an alkyl group having 1 to 6 carbon atoms (branched chain alkyl group having 3 to 6 carbon atoms), and particularly preferably an alkyl group having 1 to 4 carbon atoms (branched chain alkyl group having 3 to 4 carbon atoms).
Specific examples of the alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 2, 6-dimethyl-4-heptyl, 3,5, 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.
R1The "cycloalkyl group" (first substituent) may be any of a cycloalkyl group having 1 ring, a cycloalkyl group having a plurality of rings, a cycloalkyl group having an unconjugated double bond in a ring, and a cycloalkyl group having a branch outside a ring, and examples thereof include a cycloalkyl group having 3 to 24 carbon atoms, 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, and a cycloalkyl group having 5 carbon atoms. Preferably a C5-10 cycloalkyl group, more preferably a C6-10 cycloalkyl group.
As specific cycloalkyl groups, there may be mentioned: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and substituents of these groups having 1 to 4 carbon atoms of an alkyl group (particularly methyl), norbornenyl, bicyclo [1.0.1] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.0.1] pentyl, bicyclo [1.2.1] hexyl, bicyclo [3.0.1] hexyl, bicyclo [2.1.2] heptyl, bicyclo [2.2.2] octyl, adamantyl, diamantanyl, decahydronaphthyl (decahydronaphthyl), decahydroazulenyl (decahydroazulenyl), and the like.
R1The "alkoxy group" (first substituent) is, for example, a linear alkoxy group having 1 to 24 carbon atoms or a branched alkoxy group having 3 to 24 carbon atoms. The alkoxy group is preferably an alkoxy group having 1 to 18 carbon atoms (an alkoxy group having 3 to 18 carbon atoms in a branched chain), more preferably an alkoxy group having 1 to 12 carbon atoms (an alkoxy group having 3 to 12 carbon atoms in a branched chain), yet more preferably an alkoxy group having 1 to 6 carbon atoms (an alkoxy group having 3 to 6 carbon atoms in a branched chain), and particularly preferably an alkoxy group having 1 to 4 carbon atoms (an alkoxy group having 3 to 4 carbon atoms in a branched chain).
Specific examples of the alkoxy group include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and the like.
R1The "boron group" in the "diarylboron group" (first substituent) of the same or like may refer to the description of the aryl group. In addition, the two aryl groups may also be mono-or viaA bond or linking group (e.g., > C (-R)2O, > S or > N-R). Here, > C (-R)2And R > N-R is aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy (the above is the first substituent), which may be further substituted on at least one hydrogen in the first substituent with aryl, heteroaryl, alkyl or cycloalkyl (the above is the second substituent), and as specific examples of these groups, mention may be made of the above-mentioned R1And (c) aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy, or aryloxy of (a first substituent).
As at R1Etc. (first substituent) may be further substituted with an aryl, heteroaryl, alkyl or cycloalkyl group (the above is the second substituent), and a description of the aryl, heteroaryl, alkyl or cycloalkyl group as the first substituent may be cited.
In particular, can be represented by R1The structure of the (first substituent) is preferably a group represented by the following structural formula, more preferably methyl, tert-butyl, phenyl, o-tolyl, p-tolyl, 2, 4-xylyl, 2, 5-xylyl, 2, 6-xylyl, 2,4, 6-mesityl, diphenylamino, di-p-tolylamino, bis (p-tert-butyl) phenyl) amino, carbazolyl, 3, 6-dimethylcarbazolyl, 3, 6-di-tert-butylcarbazolyl, phenoxy, further preferably methyl, tert-butyl, phenyl, o-tolyl, 2, 6-xylyl, 2,4, 6-mesityl, diphenylamino, di-p-tolylamino, bis (p-tert-butyl) phenyl) amino, Carbazolyl, 3, 6-dimethylcarbazolyl, and 3, 6-di-tert-butylcarbazolyl. From the viewpoint of ease of synthesis, those having large steric hindrance are preferable for selective synthesis, and specifically, t-butyl, o-tolyl, p-tolyl, 2, 4-xylyl, 2, 5-xylyl, 2, 6-xylyl, 2,4, 6-mesitylyl, di-p-tolylamino, bis (p- (t-butyl) phenyl) amino, 3, 6-dimethylcarbazolyl, and 3, 6-di-t-butylcarbazolyl are preferable.
In the following structural formula, "Me" represents a methyl group and "tBu" represents a tert-butyl group.
[ solution 41]
Figure BDA0002815937380000181
[ solution 42]
Figure BDA0002815937380000191
[ solution 43]
Figure BDA0002815937380000192
[ solution 44]
Figure BDA0002815937380000201
[ solution 45]
Figure BDA0002815937380000202
R of the general formula (1)1～R3、R4～R7、R8～R10And R11～R14In the formula (1), the ring structure of the compound may be changed as shown in the following general formulae (1-1), (1-2) and (1-3) depending on the bonding form of the substituents in the a ring, the b ring, the c ring and the d ring. The symbols in each formula are as defined in the general formula (1).
[ solution 46]
Figure BDA0002815937380000211
The a ', b', c 'and d' rings in the formulae (1-1) to (1-3)Represents a substituent R1Substituent R3A substituent R4Substituent R7A substituent R8Substituent R10And a substituent R11Substituent R14Wherein adjacent groups are bonded to each other and each form an aryl ring or a heteroaryl ring together with at least one of the a-ring, the b-ring, the c-ring and the d-ring (may be referred to as a fused ring in which other ring structures are condensed on the a-ring, the b-ring, the c-ring or the d-ring). Although not shown by the formula, other combinations may exist in which all of the a-, b-, c-and d-rings are changed to a 'ring, b' -ring, c '-ring and d' -ring. Further, as can be seen from the formulae (1-1) to (1-3), for example, R of the a ring 3R with ring b4R of ring b7R with ring c8R of ring c10R with ring d11R of ring d14R with ring a1Etc. do not correspond to "adjacent groups to each other", these are not bonded. That is, the term "adjacent groups" refers to groups adjacent to each other on the same ring.
The "aryl ring" (a 'ring, b' ring, c 'ring, or d' ring) or "heteroaryl ring" (a 'ring, b' ring, c 'ring, or d' ring) formed is an invalidity ring to the aryl or heteroaryl group as the first substituent. However, since the a-ring (b-ring, c-ring, or d-ring) constituting a part of the a '-ring (b-ring, c-ring, or d' -ring) is already a benzene ring having 6 carbon atoms, the total number of carbon atoms 9 of condensed rings in which 5-membered rings are condensed on the benzene ring becomes the lower limit of carbon atoms in the "aryl ring", and the total number of carbon atoms 6 of condensed rings in which 5-membered rings are condensed on the benzene ring becomes the lower limit of carbon atoms in the "heteroaryl ring".
The compounds represented by the formulae (1-1) to (1-3) are, for example, compounds having an a 'ring (b', c ', or d' ring) formed by condensing, for example, a benzene ring, an indole ring, a pyrrole ring, a benzofuran ring, or a benzothiophene ring with respect to a benzene ring as the a ring (b, c, or d ring), and the fused rings a '(fused ring b', fused ring c ', or fused ring d') formed are a naphthalene ring, a carbazole ring, an indole ring, a dibenzofuran ring, or a dibenzothiophene ring, respectively.
As aryl substituted on at least one hydrogen of the aryl or heteroaryl ring formed,Heteroaryl, diarylamino, diarylboryl (two aryl groups may also be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, or aryloxy (above the first substituent), and aryl, heteroaryl, alkyl, or cycloalkyl (above the second substituent) further substituted on at least one hydrogen of the first substituent, may be cited as the R1And (c) aryl, heteroaryl, diarylamino, diarylboron, alkyl, cycloalkyl, alkoxy, or aryloxy groups of the same (first substituent).
X in the general formula (1) is > O, > N-R, > S or > Se, preferably > O and > N-R.
As said R, there may be cited as R an aryl, heteroaryl, alkyl or cycloalkyl group (above the first substituent) as R > N-R, and an aryl, heteroaryl, alkyl or cycloalkyl group (above the second substituent) further substituted on at least one hydrogen of said first substituent1Etc. (first substituent) are described.
L in the general formula (1) is a single bond, > C (-R)2And > O, > S and > N-R, preferably a single bond, > O or > N-R, more preferably a single bond.
With respect to as > C (-R)2And aryl, heteroaryl, diarylamino, diarylboryl (two aryl groups may also be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, or aryloxy (above the first substituent), and aryl, heteroaryl, alkyl, or cycloalkyl (above the second substituent) substituted on at least one hydrogen of the first substituent for R > N-R, which may be cited as the R1And (c) aryl, heteroaryl, diarylamino, diarylboron, alkyl, cycloalkyl, alkoxy, or aryloxy groups of the same (first substituent).
Furthermore, compounds in which X is > N-R and L is > O are not included in the compounds of the invention of the present application.
The present invention also provides a polymer of a polycyclic aromatic compound having a plurality of unit structures represented by general formula (1). The multimer is preferably a dimer to a hexamer, more preferably a dimer to a trimer, and particularly preferably a dimer. The polymer may be in the form of a single compound having a plurality of the unit structures, and may be in the form of a single bond, a linkage group such as alkylene having 1 to 3 carbon atoms (e.g., methylene), phenylene, or naphthylene, or in the form of a linkage group in which a plurality of the unit structures are bonded to each other so that any ring (a ring, b ring, c ring, or d ring) included in the unit structure is shared by the plurality of unit structures (a ring-shared polymer), or in the form of a linkage group in which any ring (a ring, b ring, c ring, or d ring) included in the unit structure is condensed to each other (ring-shared polymer).
Examples of such a polymer include those represented by the following general formula (1-4), formula (1-5-1), formula (1-5-2), formula (1-6-1) and formula (1-6-2). When the general formula (1) is used for explanation, the multimer represented by the following formula (1-4) is a multimer (ring-shared multimer) having a plurality of unit structures represented by the general formula (1) (two in the following structural formula) in one compound so as to share a benzene ring as an a-ring. In addition, the general formula (1) is described, the polymer represented by the following formula (1-5-1) or formula (1-5-2) is a polymer having a plurality of (two in the following structural formula) unit structures represented by the general formula (1) (ring-shared polymer) in one compound so that benzene rings as b rings are shared. Further, when the general formula (1) is described, the multimer represented by the following formula (1-6-1) or formula (1-6-2) is a multimer (ring condensation-type multimer) having a plurality of unit structures represented by the general formula (1) (two in the following structural formula) in one compound, such that, for example, a benzene ring of the a-ring (b-ring, c-ring, or d-ring) as a certain unit structure is condensed with a benzene ring of the a-ring (b-ring, c-ring, or d-ring) as a certain unit structure. R in the following formulae 2Is hydrogen.
[ solution 47]
Figure BDA0002815937380000231
[ solution 48]
Figure BDA0002815937380000232
[ solution 49]
Figure BDA0002815937380000233
The polymer may be a polymer obtained by combining the multimerization pattern represented by formula (1-4) with the multimerization pattern represented by formula (1-5-1) or formula (1-5-2), or may be a polymer obtained by combining the multimerization pattern represented by formula (1-4), formula (1-5-1) or formula (1-5-2) with the multimerization pattern represented by formula (1-6-1) or formula (1-6-2).
In addition, all or a part of hydrogen in the chemical structure of the polycyclic aromatic compound represented by the general formula (1) and the multimer thereof may be substituted with cyano, halogen or deuterium. For example, in the general formula (1), the a ring, the b ring, the C ring, the d ring, and the substituents for these rings, and when X is > N — R, R (═ aryl, heteroaryl, alkyl, cycloalkyl), L is > C (-R)2And hydrogen in R (> N-R) (aryl, heteroaryl, diarylamino, diarylboryl, alkyl, cycloalkyl, alkoxy, or aryloxy) may be substituted with cyano, halogen, or deuterium. Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine.
In the general formula (1), it is preferable that: r7And R8One of them is halogen, alkyl group having 1 to 6 carbon atoms, cycloalkyl group having 3 to 14 carbon atoms, aryl group having 6 to 10 carbon atoms or heteroaryl group having 2 to 10 carbon atoms, and the other is hydrogen, alkyl group having 1 to 6 carbon atoms, cycloalkyl group having 3 to 14 carbon atoms, aryl group having 6 to 10 carbon atoms or heteroaryl group having 2 to 10 carbon atoms. In addition, in the above case, R of the b ring 7And R of ring c8Are not bonded to adjacent groups, nor form part of the aryl or heteroaryl ring formed. In addition, it is preferable that one of the above-mentioned groups is R7The "other" is R8. With respect to the R7And R8The characteristics of (A) are also described in detail below as substituent group Z.
R7And R8The halogen of (a) is fluorine, chlorine, bromine, or iodine. From the viewpoint of increasing the spin-orbit interaction due to the heavy atom effect, a halogen having a large molecular weight is preferable, and chlorine, bromine, and iodine are preferable, chlorine and bromine are more preferable, and iodine is even more preferable. From the viewpoint of deepening the HOMO/LUMO orbital by introducing an element having a high electronegativity, elements having a high electronegativity are preferable, fluorine, chlorine, and bromine are preferable, fluorine and chlorine are more preferable, and fluorine is even more preferable.
R7And R8The alkyl group having 1 to 6 carbon atoms may be either a straight chain or branched chain, and is preferably an alkyl group having 1 to 4 carbon atoms (branched chain alkyl group having 3 to 4 carbon atoms). Specifically, the alkyl group includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, and 2-ethylbutyl, more preferably methyl or tert-butyl, and still more preferably methyl.
R7And R8The cycloalkyl group having 3 to 14 carbon atoms is preferably 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, a cycloalkyl group having 5 carbon atoms or the like. More specifically, preferred examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and C1-4 alkyl (especially methyl) substituents thereof, norbornenyl, and bicyclo [1.0.1 ] bicyclo]Butyl, bicyclo [1.1.1]Pentyl, bicyclo [2.0.1]Pentyl, bicyclo [1.2.1]Hexyl, bicyclo [3.0.1]Hexyl, bicyclo [2.1.2]Heptyl, bicyclo [2.2.2]Octyl, adamantyl, diamantanyl, decahydronaphthyl, decahydroazulenyl, and the like.
R7And R8The aryl group having 6 to 10 carbon atoms in (b) is specifically a phenyl group or a naphthyl group, and preferably a phenyl group.
R7And R8The heteroaryl group having 2 to 10 carbon atoms is specifically pyrrole, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiazoylExamples of the substituent include a group having a monocyclic structure of 6-or 5-membered ring, such as oxadiazolyl, 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, indolizinyl, furyl, benzofuryl, isobenzofuryl, thienyl, benzothienyl, furazanyl, oxadiazolyl, etc.
With respect to R7And R8Preferably, the combination of (a): r7And R8One is halogen, alkyl group having 1 to 4 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms or phenyl group, and the other is hydrogen, alkyl group having 1 to 4 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms or phenyl group, preferably R7And R8The sum of the molecular weights of (a) and (b) is small. Further, more preferably: one is methyl, t-butyl or phenyl and the other is hydrogen, methyl, t-butyl or phenyl. Further, it is more preferable that: one is methyl or tert-butyl and the other is hydrogen or methyl. In addition, it is particularly preferable that: one is methyl and the other is hydrogen or methyl. In addition, most preferred are: one is methyl and the other is hydrogen. In addition, it is preferable that one of the above-mentioned groups is R7The "other" is R8。
From the viewpoint of synthesis of the compound of the general formula (1), it is preferably located at R7R of symmetrical position5Is a group other than hydrogen, more preferably R7And R5Are the same group. In addition, similarly, in R8When the group is other than hydrogen, it is preferably located at R8R of symmetrical position10Is also a group other than hydrogen, more preferably R8And R10Are the same group.
The polycyclic aromatic compound and multimers thereof of the present invention can be used as materials for organic devices. Examples of the organic device include: organic electroluminescent devices, organic field effect transistors, organic thin film solar cells, and the like. In particular, in the organic electroluminescent element, a compound in which X is > N-R or a compound in which X is > O is preferable as a dopant material of the light-emitting layer, and a compound in which X is > O is preferable as a host material of the light-emitting layer.
The polycyclic aromatic compound represented by the general formula (1) and the multimer thereof will be described in more detail below. X in the general formula (1) is > O, > N-R, > S or > Se, and when the structure of the compound of the general formula (1) is related to the compound number thereof, the general formula (1) is also described as the general formula (BOL-1, formula (BNL-1), formula (BSL-1) or formula (BEL-1), respectively, X is preferably > O or > N-R from the viewpoint of luminous efficiency and luminous wavelength, more specifically, X is preferably > O from the viewpoint of short luminous wavelength, X is preferably > N from the viewpoint of high luminous efficiency, and hereinafter, the definition of symbols in the general formula representing the general structure of the compound is the same as that of the general formula (1), and R may be omitted in the general formula for simplification of expression1～R14The symbol of (2). Such omission is not made in the formula which is not a general formula but represents the structure of a specific compound. In the case where a plurality of substituents, rings, or the like at equivalent positions are present in one general formula, a symbol representing a substituent, a ring, or the like may be given a "or" a ", and the symbol may be defined as in general formula (1). For example, the presence of a plurality of groups corresponding to R in a formula4In the case of a substituent at the position of (1), except for "R 4"R" may be other than "R'4"or" R4"denotes, the definition of these symbols and R in the general formula (1)4The same definition is applied.
[ solution 50]
Figure BDA0002815937380000251
[ solution 51]
Figure BDA0002815937380000261
The polycyclic aromatic compound of the general formula (1) may be a polymer having a common ring a to cThe number of the rings in common may be one or more. In the case of multimers, preferably, b-rings or c-rings are shared, and more preferably, b-rings are shared. For example, the following general formula (20) to (25) and formula (30) polymer. In addition, B (boron) as a central element is preferably meta to each other. From the viewpoint of synthesis, a structure having high symmetry is preferable, and specifically, multimers of the following general formula (20), formula (22), formula (23), and formula (30) are preferable. From the viewpoint of characteristics, the following formula (22BOCz-0001) is preferable. Having R in the a-ring in the multimeric structure2R ' in the a ' ring '2And a "R in the Ring2In the case of (1), R2、R'2And/or R ″)2Is hydrogen.
[ solution 52]
Figure BDA0002815937380000271
[ Hua 53]
Figure BDA0002815937380000281
In the general formula (1), L is a single bond, > C (-R)2O, S and N-R, and are represented by the general formula (BXCz-1)), the formula (BXAd-1), the formula (BXPx-1), the formula (BXPt-1) and the formula (BXPz-1), respectively. From the viewpoint of luminous efficiency, L is preferably a single bond and > C (-R)2From the viewpoint of adjusting the emission wavelength, a single bond, > C (-R) is preferable 2O and > N-R. More specifically, the emission wavelength is increased by a strong negative bond, and from the viewpoint of a short emission wavelength, a single bond and > C (-R) are preferable2。
[ solution 54]
Figure BDA0002815937380000282
In the general formula (1), L is represented by > C (-R)2When expressed, the formula (BXAd-1) is from the viewpoint of luminous efficiency andpreferred are the formulae (BXAdM-1), (BXAdP-1) and (BXAdF-1), and more preferred is the formula (BXAdM-1) from the viewpoint of synthesis.
[ solution 55]
Figure BDA0002815937380000291
In the general formula (1), X is > O, > N-R, > S or > Se, and L is a single bond, > C (-R)2And > O, > S and > N-R, and are represented by the general formula (BOCz-1), the formula (BOAd-1), the formula (BOPx-1), the formula (BOPt-1), the formula (BOPz-1), the formula (BNCz-1), the formula (BNAd-1), the formula (BNPt-1), the formula (BNPz-1), the formula (BSCz-1), the formula (BSAd-1), the formula (BSPx-1)), the formula (BSPt-1), the formula (BSPz-1), the formula (BECz-1), the formula (BEAd-1), the formula (BEPx-1), the formula (BEPt-1) and the formula (BEPz-1), respectively. From the viewpoint of luminous efficiency, it is preferred that X is > O or > N-R, and L is a single bond or > C (-R)2. From the viewpoint of adjusting the emission wavelength, L is preferably a single bond, > C (-R)2O and > N-R. From the viewpoint of achieving both the light-emitting efficiency and the light-emitting wavelength, it is preferable that X is > O or > N-R, and L is a single bond or > C (-R) 2。
[ solution 56]
Figure BDA0002815937380000292
[ solution 57]
Figure BDA0002815937380000301
[ solution 58]
Figure BDA0002815937380000302
[ chemical 59]
Figure BDA0002815937380000311
In general formulae (20) to (25) as the multimer of general formula (1), it is preferable that as many as possible of X be > O from the viewpoint of reducing the molecular weight. In addition, Δ E is decreasedSTFrom the viewpoint of short delayed fluorescence lifetime, it is preferable that X is > N-R as much as possible. From the viewpoint of synthesis, a structure having high symmetry is preferable, and specifically, general formula (20BOCz-0001), formula (22BOCz-0001), formula (23BOCz-0001), formula (30BOCz-0001), formula (20BNCz-0001), formula (22BNCz-0001), formula (20BOCz/NCz-0001), and formula (22BOCz/NCz-0001) are preferable. From the viewpoint of characteristics, preferred are the formula (22BOCz-0001), the formula (22BNCz-0001), and the formula (22 BOCz/NCz-0001).
[ solution 60]
Figure BDA0002815937380000321
[ solution 61]
Figure BDA0002815937380000331
[ solution 62]
Figure BDA0002815937380000341
[ solution 63]
Figure BDA0002815937380000342
R in the general formula (1)1～R14Independently of one another, hydrogen, aryl, heteroaryl, diarylamino, diarylboron (two aryl groups may also be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy or aryloxy, at least one hydrogen of which may in turn be substituted by aryl, heteroaryl, alkyl or cycloalkyl, and R1～R3、R4～R7、R8～R10And R11～R14Wherein adjacent groups may also be bonded to each other and form an aryl or heteroaryl ring together with at least one of the a, b, c and d rings, at least one hydrogen in the formed ring may also be substituted by aryl, heteroaryl, diarylamino, diarylboron (two aryl groups may also be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy or aryloxy, at least one hydrogen of which may in turn be substituted by aryl, heteroaryl, alkyl or cycloalkyl.
In addition, R in the general formula (BNCz-1), the formula (BNAd-1), the formula (BNPt-1), the formula (BNPz-1), the formula (BOAd-1), the formula (BOPz-1), the formula (BSCz-1), the formula (BSPz-1), the formula (BECz-1) and the formula (BEPz-1) may be the same as R1～R14The same is considered.
For example, in the formula (BOCz-1), in R1～R14When hydrogen is used, it is represented by the general formula (BOCz-0001).
[ solution 64]
Figure BDA0002815937380000351
Further, R in the formula (BOCz-1)1～R14When a substituent other than hydrogen is present, the following structures are exemplified. From the viewpoint of the three-dimensional mixture state, R2、R3、R4、R5、R6、R9、R10、R11、R12And R13May have any substituent, and from the viewpoint of synthesis, the substitution position is preferably R2、R3、R4、R5、R6、R9、R12And R13。
[ solution 65]
Figure BDA0002815937380000361
[ solution 66]
Figure BDA0002815937380000371
[ solution 67]
Figure BDA0002815937380000381
[ solution 68]
Figure BDA0002815937380000391
[ solution 69]
Figure BDA0002815937380000401
[ solution 70]
Figure BDA0002815937380000411
[ solution 71]
Figure BDA0002815937380000421
[ chemical formula 72]
Figure BDA0002815937380000431
[ solution 73]
Figure BDA0002815937380000441
[ chemical formula 74]
Figure BDA0002815937380000451
[ solution 75]
Figure BDA0002815937380000461
[ 76]
Figure BDA0002815937380000471
[ solution 77]
Figure BDA0002815937380000481
[ solution 78]
Figure BDA0002815937380000491
[ solution 79]
Figure BDA0002815937380000501
[ solution 80]
Figure BDA0002815937380000511
In the general formula (1), the aromatic ring formed by the c-ring, the d-ring and the L (the carbazole ring, the acridine ring, the phenoxazine ring, the phenothiazine ring and the phenazine ring may be formed as partial structures, respectively) preferably has a substituent in a line symmetry with respect to the a-ring-N bond from the viewpoint of ease of synthesis. That is, R is preferable8And R13、R9And R12And R10And R11Have the same substituents.
For example, at R9The general formula (BOCz-1) having a substituent at (A) is preferably R 12The above also have the same substituents, and are represented by the general formula (BOCz-09# # S).
[ solution 81]
Figure BDA0002815937380000521
[ solution 82]
Figure BDA0002815937380000531
[ solution 83]
Figure BDA0002815937380000541
R of the general formula (1)1～R14A plurality of (2) may also have a substituent. From the viewpoint of ease of synthesis, the substitution position is selected in such a manner that steric hindrance is interconverted little. In the case where the ring may have a substituent at an adjacent position, a group having a small steric hindrance is preferable, and for example, a methyl group and a phenyl group are preferable. In addition, R of the general formula (1)1～R14The number of the substituent(s) in (1) may be any number, but R is preferably R1～R14The total number of carbon atoms of the substituents of (2) is 36 or less.
R in the general formula (1) as a substituent of the b ring4～R7In the case of having a plurality of substituents, it is preferable from the viewpoint of synthesis to have the substituents in line symmetry with respect to the B-ring-B bond or the B-ring-X bond.
R as formula (1)2When having a diarylamino group, a carbazolyl group, an acridinyl group, a phenoxazinyl group, a phenothiazinyl group, and a phenazinyl group, it is preferable that the carbazolyl group or a carbon atom adjacent to the N-bonded carbon atom bonded to the a-ring has a substituent from the viewpoint of synthesis.
[ solution 84]
Figure BDA0002815937380000561
[ solution 85]
Figure BDA0002815937380000571
[ solution 86]
Figure BDA0002815937380000581
[ solution 87]
Figure BDA0002815937380000591
[ solution 88]
Figure BDA0002815937380000601
[ solution 89]
Figure BDA0002815937380000611
[ solution 90]
Figure BDA0002815937380000621
[ solution 91]
Figure BDA0002815937380000631
[ solution 92]
Figure BDA0002815937380000641
[ solution 93]
Figure BDA0002815937380000651
[ solution 94]
Figure BDA0002815937380000661
[ solution 95]
Figure BDA0002815937380000671
[ solution 96]
Figure BDA0002815937380000681
[ solution 97]
Figure BDA0002815937380000691
[ solution 98]
Figure BDA0002815937380000701
[ solution 99]
Figure BDA0002815937380000711
[ solution 100]
Figure BDA0002815937380000721
[ solution 101]
Figure BDA0002815937380000731
[ solution 102]
Figure BDA0002815937380000741
[ solution 103]
Figure BDA0002815937380000751
[ solution 104]
Figure BDA0002815937380000761
[ solution 105]
Figure BDA0002815937380000771
[ solution 106]
Figure BDA0002815937380000781
[ solution 107]
Figure BDA0002815937380000791
[ solution 108]
Figure BDA0002815937380000801
[ solution 109]
Figure BDA0002815937380000811
[ solution 110]
Figure BDA0002815937380000821
[ solution 111]
Figure BDA0002815937380000831
[ solution 112]
Figure BDA0002815937380000841
[ solution 113]
Figure BDA0002815937380000851
For example, in the formula (BNCz-1), R1～R14When hydrogen is used, it is represented by the general formula (BNCz-0001).
[ chemical formula 114]
Figure BDA0002815937380000861
R in N-R is preferably phenyl, biphenyl or terphenyl, more preferably phenyl.
For example, in the general formula (BNCz-0001), when R > N-R is phenyl, biphenyl, terphenyl, it is represented by the general formula (BNpCz-0001), the formula (BNbCz-0001), the formula (BNcCz-0001), the formula (BNdCz-0001), the formula (BNeCz-0001), the formula (BNfCz-0001), the formula (BNgCz-0001), and the formula (BNhCz-0001). From the viewpoint of stability during synthesis, the formula (BNpCz-0001) is preferred. From the viewpoint of cohesiveness, a compound having a substituent at the ortho position is preferable, and examples thereof are preferably those of the formulae (BNbCz-0001), (BNeCz-0001), (BNfCz-0001), and (BNgCz-0001).
[ solution 115]
Figure BDA0002815937380000862
Further, R in the general formula (BNpCz-1)1～R14When a substituent other than hydrogen is present, the following structures are exemplified. From the viewpoint of the three-dimensional mixture state, R2、R5、R6、R9、R10、R11、R12And R13May have any substituent, and from the viewpoint of synthesis, the substitution position is preferably R 2、R5、R6、R9、R12And R13。
[ solution 116]
Figure BDA0002815937380000871
[ solution 117]
Figure BDA0002815937380000881
[ chemical formula 118]
Figure BDA0002815937380000891
[ solution 119]
Figure BDA0002815937380000901
[ chemical formula 120]
Figure BDA0002815937380000911
[ solution 121]
Figure BDA0002815937380000921
In the general formula (1), the aromatic ring formed by the c-ring, the d-ring and the L (the carbazole ring, the acridine ring, the phenoxazine ring, the phenothiazine ring and the phenazine ring may be formed as partial structures, respectively) preferably has a substituent in a line symmetry with respect to the a-ring-N bond from the viewpoint of ease of synthesis. That is, R is preferable8And R13、R9And R12And R10And R11Have the same substituents.
For example, at R9The general formula (BOCz-1) having a substituent at (A) is preferably R12The above also have the same substituents, and are represented by the general formula (BOCz-09# # S).
[ chemical formula 122]
Figure BDA0002815937380000931
[ solution 123]
Figure BDA0002815937380000941
[ solution 124]
Figure BDA0002815937380000951
R of the general formula (1)1～R14A plurality of (2) may also have a substituent. From the viewpoint of ease of synthesis, the substitution position is selected in such a manner that steric hindrance is interconverted little. In the case where the ring may have a substituent at an adjacent position, a group having a small steric hindrance is preferable, and for example, a methyl group and a phenyl group are preferable. In addition, R of the general formula (1)1～R14The number of the substituent(s) in (1) may be any number, but R is preferably R1～R14The total number of carbon atoms of the substituents of (2) is 36 or less.
R in the general formula (1) as a substituent of the b ring4～R7In the case of having a plurality of substituents, it is preferable from the viewpoint of synthesis to have the substituents in line symmetry with respect to the B-ring-B bond or the B-ring-X bond.
R as formula (1)2When having a diarylamino group, a carbazolyl group, an acridinyl group, a phenoxazinyl group, a phenothiazinyl group, and a phenazinyl group, it is preferable that the carbazolyl group or a carbon atom adjacent to the N-bonded carbon atom bonded to the a-ring has a substituent from the viewpoint of synthesis.
[ solution 125]
Figure BDA0002815937380000961
[ solution 126]
Figure BDA0002815937380000971
[ solution 127]
Figure BDA0002815937380000981
[ solution 128]
Figure BDA0002815937380000991
[ solution 129]
Figure BDA0002815937380001001
[ solution 130]
Figure BDA0002815937380001011
[ solution 131]
Figure BDA0002815937380001021
[ solution 132]
Figure BDA0002815937380001031
[ solution 133]
Figure BDA0002815937380001041
[ solution 134]
Figure BDA0002815937380001051
[ solution 135]
Figure BDA0002815937380001061
[ solution 136]
Figure BDA0002815937380001071
[ solution 137]
Figure BDA0002815937380001081
[ 138]
Figure BDA0002815937380001091
[ solution 139]
Figure BDA0002815937380001101
[ solution 140]
Figure BDA0002815937380001111
[ solution 141]
Figure BDA0002815937380001121
[ solution 142]
Figure BDA0002815937380001131
[ solution 143]
Figure BDA0002815937380001141
[ solution 144]
Figure BDA0002815937380001151
[ solution 145]
Figure BDA0002815937380001161
[ solution 146]
Figure BDA0002815937380001171
[ solution 147]
Figure BDA0002815937380001181
[ solution 148]
Figure BDA0002815937380001191
[ 149]
Figure BDA0002815937380001201
[ solution 150]
Figure BDA0002815937380001211
[ solution 151]
Figure BDA0002815937380001221
[ solution 152]
Figure BDA0002815937380001231
[ solution 153]
Figure BDA0002815937380001241
[ solution 154]
Figure BDA0002815937380001251
In the general formula (22), the multiple resonance effect of the shared B-ring is emphasized by B and N or O, thereby reducing Δ ESTAnd/or delay of fluorescence lifetime, and attempt to improve element characteristics. The substituents on the a, b and a' rings, which are strongly affected by the multiple resonance effect, have a strong influence on the multiple resonance effect on the bonded rings and also on the substituents themselves. Thus, at R1～R14In the case of having a substituent other than hydrogen, it is preferable to have a substituent on the c ring, the d ring, the c 'ring and the d' ring from the viewpoint of stability. In addition, when the ring a, the ring b, and the ring a' have a substituent, the substituent preferably has a substituent which reduces the multiple resonance effect from the viewpoint of stability. From the viewpoint of shortening the emission wavelength, it is preferable to have many O, and from the viewpoint of lengthening the emission wavelength, it is preferable to have many N. From the viewpoint of enhancing the multiple resonance effect, it is preferable to have a large number of N, and if the multiple resonance effect is enhanced, Δ E is generally used STAnd becomes smaller. From the viewpoint of increasing the planarity of the molecule, it is preferable that the amount of O is large, and when the planarity is high, the light emission efficiency is high.
[ solution 155]
Figure BDA0002815937380001252
[ solution 156]
Figure BDA0002815937380001261
[ chemical formula 157]
Figure BDA0002815937380001271
[ solution 158]
Figure BDA0002815937380001281
[ chemical formula 159]
Figure BDA0002815937380001291
[ solution 160]
Figure BDA0002815937380001301
[ solution 161]
Figure BDA0002815937380001311
[ chemical 162]
Figure BDA0002815937380001321
[ chemical 163]
Figure BDA0002815937380001331
[ 164]
Figure BDA0002815937380001341
By imparting strain to the molecule, the spin-orbit interaction can be increased. This shortens the delayed fluorescence lifetime, and exhibits the TADF mechanism, thereby improving the light emission efficiency of the element. For this purpose, in the general formula (1), R is7And/or R8The substituent group Z described below is introduced.
In the general formula (1), R7And/or R8Z is halogen, alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 14 carbon atoms, aryl having 6 to 10 carbon atoms or heteroaryl having 2 to 10 carbon atoms, and specifically, the following partial structural formula (m), formula (e), formula (v), formula (t), formula (h), formula (p), formula (q), formula (r), formula(s), formula (y), formula (u), formula (w), formula (j), formula (k), formula (f), formula (c), formula (b), formula (i) and formula (n) are preferable, and among these, the formula (m), formula (t), formula (p), formula (f) and formula (n) are more preferable, and the formula (m) and formula (t) are still more preferable.
[ solution 165]
Figure BDA0002815937380001351
From the viewpoint of shortening the delayed fluorescence lifetime by imparting strain to the molecule and exhibiting the TADF mechanism, R is preferable 7And R8Are both Z. From the viewpoint of attaining a high fluorescence quantum yield (PLQY) and the stability of the molecule, R is preferably used7And R8Only any one of is Z. From the viewpoint of ease of synthesis, R is preferred7Is Z.
In view of ease of synthesis, when R7When Z is present, it is preferably at R5Has a substituent on, likewise, when R is8When Z is present, it is preferably at R10And/or R13Has a substituent on, likewise, when R is10When Z is present, it is preferably at R8And/or R12Having a substituent thereon. In addition, from the viewpoint of ease of synthesis and stability, the substituent is preferably small, and the above-mentioned groups of formula (m), formula (e), formula (v), formula (t), formula (h), formula (p), formula (q), formula (r), formula(s), formula (j), formula (k), formula (f), formula (c), formula (b), formula (i) and formula (n) are preferable, among these, the groups of formula (m), formula (e), formula (v), formula (t), formula (p), formula (f) and formula (n) are more preferable, the groups of formula (m) and formula (t) are even more preferable, and the group of formula (m) is most preferable.
For example, in the formula (BOCz-0001), when R is7And/or R8Z is represented as follows.
[ solution 166]
Figure BDA0002815937380001352
In the general formulae (BOCz-7z-0001), formula (BOCz-8z-0001) and formula (BOCz-15z-0001), R is preferably 5And/or R13With a substituent, especially when in R5And/or R13The above groups having the same substituents as those of Z are represented as follows.
[ 167]
Figure BDA0002815937380001361
For example, in the general formula (BOCz-7Z-0001), the formula (BOCz-8Z-0001), the formula (BOCz-15Z-0001), the formula (BOCz-12Z-0001), the formula (BOCz-21Z-0001), the formula (BOCz-20Z-0001), the formula (BOCz-28Z-0001) and the formula (BOCz-33Z-0001), when Z is a group of the formula (m), the formula (t) and the formula (p), it is represented by the following structural formula.
[ solution 168]
Figure BDA0002815937380001371
[ 169]
Figure BDA0002815937380001381
From the viewpoint of ease of synthesis and stability, preferred are the general formula (BOCz-7m-0001), the formula (BOCz-8m-0001), the formula (BOCz-12m-0001), and the formula (BOCz-21m-0001), and more preferred are the general formula (BOCz-7m-0001) and the formula (BOCz-12 m-0001). From the viewpoint of short delayed fluorescence lifetime, preferred are the general formula (BOCz-15m-0001), the formula (BOCz-20m-0001), the formula (BOCz-28m-0001), and the formula (BOCz-33 m-0001).
Specific examples of the structure in which a molecule is strained by a substituent group Z are as follows.
[ solution 170]
Figure BDA0002815937380001391
[ solution 171]
Figure BDA0002815937380001401
[ solution 172]
Figure BDA0002815937380001411
[ chemical formula 173]
Figure BDA0002815937380001421
[ solution 174]
Figure BDA0002815937380001431
[ chemical 175]
Figure BDA0002815937380001441
[ solution 176]
Figure BDA0002815937380001451
[ solution 177]
Figure BDA0002815937380001461
[ solution 178]
Figure BDA0002815937380001471
[ chemical 179]
Figure BDA0002815937380001481
[ solution 180]
Figure BDA0002815937380001491
[ solution 181]
Figure BDA0002815937380001501
[ solution 182]
Figure BDA0002815937380001511
[ solution 183]
Figure BDA0002815937380001521
[ solution 184]
Figure BDA0002815937380001531
[ solution 185]
Figure BDA0002815937380001541
[ solution 186]
Figure BDA0002815937380001551
[ solution 187]
Figure BDA0002815937380001561
[ solution 188]
Figure BDA0002815937380001571
[ formulation 189]
Figure BDA0002815937380001581
[ solution 190]
Figure BDA0002815937380001591
[ solution 191]
Figure BDA0002815937380001601
[ solution 192]
Figure BDA0002815937380001611
[ solution 193]
Figure BDA0002815937380001621
[ solution 194]
Figure BDA0002815937380001631
[ solution 195]
Figure BDA0002815937380001641
For example, in the general formula (BNpCz-0001) R7And/or R8Z is represented as follows.
[ solution 196]
Figure BDA0002815937380001651
In the general formulae (BNpCz-7z-0001), the formulae (BNpCz-8z-0001) and the formulae (BNpCz-15z-0001), R is preferably the group consisting of5And/or R13With a substituent, especially when in R5And/or R13The above groups having the same substituents as those of Z are represented as follows.
[ solution 197]
Figure BDA0002815937380001652
For example, in the general formula (BNpCz-7Z-0001), the formula (BNpCz-8Z-0001), the formula (BNpCz-15Z-0001), the formula (BNpCz-12Z-0001), the formula (BNpCz-21Z-0001), the formula (BNpCz-20Z-0001), the formula (BNpCz-28Z-0001), and the formula (BNpCz-33Z-0001), when Z is a group of the formula (m), the formula (t), and the formula (p), it is represented by the following structural formula.
[ chemical formula 198]
Figure BDA0002815937380001661
From the viewpoint of ease of synthesis and stability, the general formula (BNpCz-7m-0001), the formula (BNpCz-8m-0001), the formula (BNpCz-12m-0001), and the formula (BNpCz-21m-0001) are preferred, and the general formula (BNpCz-7m-0001) and the formula (BNpCz-12m-0001) are more preferred. From the viewpoint of short delayed fluorescence lifetime, preferred are the general formula (BNpCz-15m-0001), the formula (BNpCz-20m-0001), the formula (BNpCz-28m-0001), and the formula (BNpCz-33 m-0001).
Specific examples of the structure in which a molecule is strained by a substituent group Z are as follows.
[ solution 199]
Figure BDA0002815937380001671
[ solution 200]
Figure BDA0002815937380001681
[ solution 201]
Figure BDA0002815937380001691
[ solution 202]
Figure BDA0002815937380001701
[ solution 203]
Figure BDA0002815937380001711
[ 204]
Figure BDA0002815937380001721
[ formulation 205]
Figure BDA0002815937380001731
[ solution 206]
Figure BDA0002815937380001741
[ solution 207]
Figure BDA0002815937380001751
[ solution 208]
Figure BDA0002815937380001761
[ solution 209]
Figure BDA0002815937380001771
[ solution 210]
Figure BDA0002815937380001781
From the viewpoint of synthesis, it is preferable that the symmetry with respect to the a-ring-X (N > N-R in this case) is high. That is, it is preferable that the phenyl group in > N-R has substituents at the 3-position and the 5-position, specifically, it is preferable that the phenyl group has the same kind of substituent as that of the b-ring, and it is preferable that the phenyl group has methyl groups at the 3-position and the 5-position with respect to N.
[ solution 211]
Figure BDA0002815937380001791
[ solution 212]
Figure BDA0002815937380001801
[ solution 213]
Figure BDA0002815937380001811
[ solution 214]
Figure BDA0002815937380001821
[ solution 215]
Figure BDA0002815937380001831
[ 216]
Figure BDA0002815937380001841
[ solution 217]
Figure BDA0002815937380001851
[ solution 218]
Figure BDA0002815937380001861
[ solution 219]
Figure BDA0002815937380001871
From the viewpoint of ease of synthesis, R is preferred7Having substituents on Z, likewise, when R is8When Z is, it is preferably R'8Has a substituent at (A), more preferably R7And has a substituent on Z. In addition, the substituent is preferably small from the viewpoint of ease of synthesis and stability, and is preferably the aforementioned formula (m), formula (e), formula (v), formula (t), formula (h), formula (p), formula (q), formula (r), formula(s), formula (j), formula (k), formula (f)Among these, the groups of formula (m), formula (e), formula (v), formula (t), formula (p), formula (f) and formula (n) are more preferable, the groups of formula (m) and formula (t) are still more preferable, and the group of formula (m) is most preferable.
For example, it is represented by the following equation.
[ solution 220]
Figure BDA0002815937380001881
In addition, in the general formula (22), for the purpose of shortening the delayed fluorescence lifetime and improving the expression of TADF and the element efficiency by imparting strain to the molecule and increasing the spin-orbit interaction, it is also possible to use R7And/or R8A substituent group Z is introduced. From the viewpoint of symmetry, it is preferable that R is the number7Having a substituent thereon.
[ solution 221]
Figure BDA0002815937380001891
[ solution 222]
Figure BDA0002815937380001901
[ solution 223]
Figure BDA0002815937380001911
[ 224]
Figure BDA0002815937380001921
[ solution 225]
Figure BDA0002815937380001931
[ chemical 226]
Figure BDA0002815937380001941
[ formulation 227]
Figure BDA0002815937380001951
[ solution 228]
Figure BDA0002815937380001961
[ solution 229]
Figure BDA0002815937380001971
[ solution 230]
Figure BDA0002815937380001981
[ solution 231]
Figure BDA0002815937380001991
[ Hua 232]
Figure BDA0002815937380002001
In addition, the following is true for the compound of the present invention, namely R1～R3、R4～R7、R8～R10And R11～R14In the above formula (I), adjacent groups are bonded to each other and form a condensed ring together with the a-ring, the b-ring, the c-ring and/or the d-ring. The compound is prepared by utilizing the general formula (1-1), the formula (1-2) and the formula (1-3)The compounds indicated are given below. More specifically, there may be mentioned: r4～R7Wherein adjacent groups are bonded to each other and form a b' ring together with the b ring, and a compound represented by the following general formula (1-1-1).
[ 233]
Figure BDA0002815937380002002
The b' ring in the formula (1-1-1) is an aryl ring or a heteroaryl ring (preferably an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms), and examples thereof include a naphthalene ring, a phenanthrene ring, an anthracene ring, a dibenzofuran ring, a carbazole ring, a dibenzothiophene ring, a silafluorene ring, a fluorene ring, and rings in which benzene rings are condensed on these rings, and specifically, rings represented by the following partial structures. In the following partial structure, Z represents a bond with X and B, and Z is > O, > N-R, > S, > Si (-R) 2Or > C (-R)2The symbols for the substituents of each ring are omitted.
[ solution 234]
Figure BDA0002815937380002011
Z is preferably > O, > N-R, and > C (-R)2More preferably, > C (-R)2. Specific partial structures are shown below.
[ solution 235]
Figure BDA0002815937380002012
As aryl, heteroaryl, diarylamino, diarylboryl (two aryl groups may also be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, aryloxy or R (above the first substituent), which are substituted on at least one hydrogen in the formed aryl or heteroaryl ring, and aryl, heteroaryl, alkyl or cycloalkyl (above the second substituent), which are further substituted on at least one hydrogen in the first substituent, mention may be made ofIs the said R1And (c) aryl, heteroaryl, diarylamino, diarylboron, alkyl, cycloalkyl, alkoxy, or aryloxy groups of the same (first substituent).
For example, > C (-R)2R in (2) is represented by the following structural formula when R is hydrogen, methyl, phenyl, or phenyl bonded to each other to form a spirofluorenyl group.
[ solution 236]
Figure BDA0002815937380002021
The polycyclic aromatic compound represented by general formula (1a), formula (1b) or formula (1c) including a ring represented by partial structural formula (1a), formula (1b) or formula (1c), and multimers thereof will be described in further detail below. Part of the structural formula (1a), formula (1b) or formula (1c) is a part of the general formula (1a), formula (1b) or formula (1c), and the symbols used in the formulae are as defined in the general formula (1) (R) 1b～R6bAnd R1～R14The same definition of (a) is applied). X in the general formula (1a), the formula (1b) or the formula (1c) is > O, > N-R, > S or > Se, and when the structure of the compound of the general formula (1a), the formula (1b) or the formula (1c) is related to the compound number thereof, the general formula (1a), the formula (1b) or the formula (1c) is also described as the general formula (BOLa-1), the formula (BNLa-1), the formula (BSLa-1), the formula (BELa-1), the formula (BOLb-1), the formula (BNLb-1), the formula (BSLb-1), the formula (BOLc-1), the formula (Blc-1), the formula (BSLc-1) or the formula (BELc-1), respectively. From the viewpoint of the light emission efficiency and the light emission wavelength, X is preferably > O. In general formulae representing general structures of compounds, R may be omitted for the sake of simplicity1～R14The symbol of (2). Such omission is not made in the formula which is not a general formula but represents the structure of a specific compound.
[ solution 237]
Figure BDA0002815937380002022
[ solution 238]
Figure BDA0002815937380002031
[ chemical 239]
Figure BDA0002815937380002032
[ solution 240]
Figure BDA0002815937380002041
[ solution 241]
Figure BDA0002815937380002042
[ solution 242]
Figure BDA0002815937380002051
[ solution 243]
Figure BDA0002815937380002052
In addition, in the general formulae (BOLb-1) and (BOLc-1), when Z is > O, > N-R, and > C (-R)2Respectively represented by a general formula (BOLbO-1), a formula (BOLbN-1), a formula (BOLcC-1), a formula (BOLcO-1), a formula (BOLcN-1) or a formula (BOLcC-1). From the viewpoint of the emission wavelength, Z is preferably > O, > C (-R)2More preferably, > C (-R)2. Additionally, > N-R and > C (-R) 2R in (2) is preferably a substituent having 1 to 24 carbon atoms, and is preferably a substituent having a small molecular weight from the viewpoint of low sublimation purification and having a high stability. More specifically, R in > N-R is preferably phenyl, biphenyl, terphenyl, pyridine, pyrazine, pyrimidine or triazine, and more preferably phenyl. > C (-R)2R in (1) is preferably methyl, ethyl, isopropyl, tert-butyl or phenylMore preferably methyl. Additionally, > C (-R)2R in (1) may be bonded to each other to form an aryl ring, for example, spirofluorene may be formed.
[ chemical 244]
Figure BDA0002815937380002061
[ chemical 245]
Figure BDA0002815937380002062
Further, at Z > C (-R)2And R is methyl, represented by the general formula (BOLbC10-1) or the formula (BOLcC 10-1). When Z is > N-R and R is a phenyl group, the compound is represented by the general formula (OLbN20-1) or the formula (BOLcN 20-1).
[ solution 246]
Figure BDA0002815937380002071
In the general formula (1-1-1), X is > O, and Z is > C (-Me)2L is a single bond, > C (-R)2When the average molecular weight is more than one of the above formulae, > O, > S and > N-R, L is preferably a single bond from the viewpoint of luminous efficiency, L is preferably a single bond, and L is preferably a single bond, > C (-R) from the viewpoint of adjustment of the luminous wavelength 2O and > N-R. L is preferably a single bond from the viewpoint of achieving both the light emission efficiency and the light emission wavelength.
[ formulation 247]
Figure BDA0002815937380002072
[ chemical 248]
Figure BDA0002815937380002081
[ Hua 249]
Figure BDA0002815937380002082
With respect to R in the general formula (1-1-1), the formula (1a), the formula (1b) and the formula (1c)1～R5、R7～R14And R1b～R6bAnd > N-R, > C (-R)2And > Si (-R)2Wherein R is independently hydrogen, aryl, heteroaryl, diarylamino, diarylboryl (two aryl groups may be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, or aryloxy in the same manner as in the general formula (1), and at least one hydrogen of these groups may be further substituted by aryl, heteroaryl, alkyl, or cycloalkyl, and R is1～R3、R8～R10And R11～R14Wherein adjacent groups may also be bonded to each other and form an aryl or heteroaryl ring together with at least one of the a, c and d rings, at least one hydrogen in the formed ring may also be substituted by aryl, heteroaryl, diarylamino, diarylboryl (two aryl groups may also be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy or aryloxy, at least one hydrogen of which may in turn be substituted by aryl, heteroaryl, alkyl or cycloalkyl.
For example, in the formula (BOCza-1), at R1～R5、R8～R14And Rb1～Rb4In the case of hydrogen, it is represented by the general formula (BOCza-0001). In the general formula (BOCzb-1), at R 1～R4、R7～R14And Rb1～Rb4When it is hydrogen, it is represented by the general formula (BOCzb-0001). In the general formula (BOCzc-1), at R1～R4、R7～R14And Rb1～Rb6When it is hydrogen, it is represented by the general formula (BOCzc-0001).
[ solution 250]
Figure BDA0002815937380002091
R in the formula (BOCza-1)1～R5、R8～R14And Rb1～Rb4When the substituent other than hydrogen is present, the following structural formula can be exemplified. From the viewpoint of the three-dimensional mixture state, R2、R3、R4、R5、R9、R10、R11、R12、R13And R14May have any substituent, and from the viewpoint of synthesis, the substitution position is preferably R2、R5、R9、R10、R12、R13And R14。
[ solution 251]
Figure BDA0002815937380002101
[ solution 252]
Figure BDA0002815937380002111
[ solution 253]
Figure BDA0002815937380002121
From the viewpoint of emission wavelength and emission efficiency, the substituent is preferably a nitrogen atom, and specific substituents are preferably diphenylamine, carbazole and phenoxazine, more preferably diphenylamine and carbazole, and still more preferably diphenylamine. The hydrogen atoms in the diphenylamine carbazoles and phenoxazines can also be substituted with aryl, heteroaryl, alkyl or cycloalkyl groups. The substitution position is preferably a para-position substitution with respect to a boron atom, and more specifically R is preferably R2、R5And R10More preferably R2And R5More preferably R5。
[ solution 254]
Figure BDA0002815937380002131
[ solution 255]
Figure BDA0002815937380002141
[ solution 256]
Figure BDA0002815937380002151
R in the formula (BOCzb-1)1～R4、R7～R14And Rb1～Rb4When the substituent other than hydrogen is present, the following structural formula can be exemplified. From the viewpoint of the three-dimensional mixture state, R 2、R3、R4、R9、R10、R11、R12、R13And R14May have any substituent, and from the viewpoint of synthesis, the substitution position is preferably R2、R9、R12、R13And R14。
[ solution 257]
Figure BDA0002815937380002161
[ Hua 258]
Figure BDA0002815937380002171
[ solution 259]
Figure BDA0002815937380002181
[ solution 260]
Figure BDA0002815937380002191
From the viewpoint of emission wavelength and emission efficiency, the substituent is preferably a nitrogen atom, and specific substituents are preferably diphenylamine, carbazole and phenoxazine, more preferably diphenylamine and carbazole, and still more preferably diphenylamine. The hydrogen atoms in the diphenylamine carbazoles and phenoxazines can also be substituted with aryl, heteroaryl, alkyl or cycloalkyl groups. The substitution position is preferably at the para-position or R relative to the boron atom1b～R4bIs preferably R2、R10、R1b、R2b、R3bAnd R4bMore preferably R2And R3bMore preferably R3b。
[ solution 261]
Figure BDA0002815937380002201
[ solution 262]
Figure BDA0002815937380002211
[ solution 263]
Figure BDA0002815937380002221
R in the formula (BOCzc-1)1～R4、R7～R14And Rb1～Rb6When the substituent other than hydrogen is present, the following structural formula can be exemplified. From the viewpoint of the three-dimensional mixture state, R2、R3、R4、R9、R10、R11、R12、R13And R14May have any substituent, and from the viewpoint of synthesis, the substitution position is preferably R2、R9、R12、R13And R14。
[ chemical 264]
Figure BDA0002815937380002231
[ solution 265]
Figure BDA0002815937380002241
[ solution 266]
Figure BDA0002815937380002251
[ solution 267]
Figure BDA0002815937380002261
From the viewpoint of emission wavelength and emission efficiency, the substituent is preferably a nitrogen atom, and specific substituents are preferably diphenylamine, carbazole and phenoxazine, more preferably diphenylamine and carbazole, and still more preferably diphenylamine. The hydrogen atoms in the diphenylamine carbazoles and phenoxazines can also be substituted with aryl, heteroaryl, alkyl or cycloalkyl groups. The substitution position is preferably at the para-position or R relative to the boron atom 5bOr R6bMore specifically, R is preferable2、R10And R5bMore preferably R2And R5bMore preferably R5b。
[ solution 268]
Figure BDA0002815937380002271
[ 269]
Figure BDA0002815937380002281
[ solution 270]
Figure BDA0002815937380002291
In the general formula (BNL-1), R in > N-R contains an atom having a large electronegativity, thereby enabling a reduction in wavelength. In particular, R in > N-R of the general formula (BNL-1) is an aryl or heteroaryl group, preferably an aryl or heteroaryl group bonded to a nitrogen atom, comprising at least one atom having a electronegativity greater than carbon, more preferably at least one fluorine atom. In order to reduce the wavelength, it is preferable that the aryl or heteroaryl group bonded to the nitrogen atom connecting the a-ring and the b-ring has a large number of atoms having a large electronegativity, and that the atom has a large electronegativity in the ortho position with respect to the nitrogen atom connecting the a-ring and the b-ring.
For example, the following partial structural formulae can be cited. The nitrogen atom in the partial structural formula represents a nitrogen atom connecting the a ring and the b ring. The effect of shortening the wavelength of the partial structural formula (Pf) is the greatest. From the viewpoint of stability and synthesis, formula (F2), formula (F4), formula (F24), formula (F26), and formula (F246) are preferable, formula (F2), formula (F24), and formula (F26) are more preferable, and formula (F26) is still more preferable.
[ 271]
Figure BDA0002815937380002301
In the general formula (BNpCz-1), when R > N-R is represented by the formula (F26), the following structural formula can be exemplified. From the viewpoint of the three-dimensional mixture state, R 2、R5、R6、R9、R10、R11、R12And R13May have any substituent, and from the viewpoint of synthesis, the substitution position is preferably R2、R5、R6、R9、R12And R13。
For ease of synthesis, further shortening of the emission wavelength, high emission efficiency, and high TADF activity, it is preferable that R is the number2、R5、R6、R9And R12Having an alkyl or cycloalkyl group thereon. The substitution can inhibit the aggregation of the compound by introducing a soft substituent or a substituent having a large steric hindrance. For ease of synthesis, longer emission wavelength, and very high emission efficiency, it is preferable that R is the number2、R5、R6、R9And R12Having an aryl group thereon. The introduction of the aryl group imparts high luminous efficiency. For the purpose of shortening the emission wavelength, achieving very high emission efficiency and high TADF activity, it is preferable that the emission wavelength is R2And R5Having a diarylamino group and a carbazolyl group. By taking into consideration the symmetry of the molecule, the ease of synthesis can be improved also in the diarylamino group and the carbazolyl group.
[ solution 272]
Figure BDA0002815937380002311
[ 273]
Figure BDA0002815937380002321
[ solution 274]
Figure BDA0002815937380002331
[ design 275]
Figure BDA0002815937380002341
[ 276]
Figure BDA0002815937380002351
[ Hua 277]
Figure BDA0002815937380002361
[ 278]
Figure BDA0002815937380002371
[ chemical No. 279]
Figure BDA0002815937380002381
[ solution 280]
Figure BDA0002815937380002391
[ Hua 281]
Figure BDA0002815937380002401
[ solution 282]
Figure BDA0002815937380002411
[ 283] chemical reaction
Figure BDA0002815937380002421
[ CHEMICAL 284]
Figure BDA0002815937380002431
[ solution 285]
Figure BDA0002815937380002441
[ solution 286]
Figure BDA0002815937380002451
[ CHEMICAL 287]
Figure BDA0002815937380002461
[ solution 288]
Figure BDA0002815937380002471
2. Method for producing polycyclic aromatic compound
The polycyclic aromatic compound represented by the general formula (1) and multimers thereof can be synthesized, for example, by applying the method disclosed in International publication No. 2015/102118. That is, as shown in the following scheme, a desired polycyclic aromatic compound and multimers thereof can be synthesized by synthesizing an intermediate having a linker L and cyclizing the intermediate by a Tandem heteredo-Friedel-Crafts Reaction (successive aromatic electrophilic substitution Reaction). In the following schemes, Y represents halogen or hydrogen, and the other symbols are as defined above.
[ 289]
Figure BDA0002815937380002481
The intermediate before cyclization in the above-mentioned scheme can be synthesized by the method shown in International publication No. 2015/102118 and the like. That is, an intermediate having a desired substituent can be synthesized by appropriately combining a Buchwald-Hartwig reaction, a suzuki coupling reaction, an etherification reaction by a nucleophilic substitution reaction, an Ullmann (Ullmann) reaction, or the like.
The cyclization by the tandem heterofriedel-quardt reaction shown in the above-mentioned scheme is a reaction in which B (boron) bonding an a ring, a B ring and a c ring is introduced. First, Y (hydrogen atom) between X and N (nitrogen) is ortho-metalated using N-butyllithium, sec-butyllithium, tert-butyllithium, or the like. Then, after metal exchange of lithium-boron by adding boron trichloride, boron tribromide or the like, a Bronsted base (e.g., N-diisopropylethylamine) is added to carry out a Tandem borohybrid-quart Reaction (Tandem Bora-Friedel-Crafts Reaction), and the target compound can be obtained. Here, in order to accelerate the reaction, Lewis acid (Lewis acid) such as aluminum trichloride may be added.
In addition to the method of introducing lithium to a desired position by ortho-metallation, a halogen such as bromine atom may be introduced to a position to which lithium is to be introduced, and lithium may be introduced to a desired position by halogen-metal exchange.
In addition, cyclization can also be performed by a tandem heterofriedel-quardt reaction without performing ortho-metalation of Y (hydrogen atom) between X and N (nitrogen) in the above-mentioned flow, and in the case of adding boron trichloride, boron tribromide, boron triiodide, and the like to the raw material and refluxing. In this case, a Bronsted base such as N, N-diisopropylethylamine and/or a Lewis acid such as aluminum trichloride may be added to promote the reaction.
Also, the polycyclic aromatic compound represented by the general formula (1a), the formula (1b) or the formula (1c) including the ring represented by the partial structural formula (1a), the formula (1b) or the formula (1c) can be synthesized by the above method using a raw material corresponding to the target compound.
3. Organic device
In the chemical structural formulae exemplified below, "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. Examples of the organic device include: organic electroluminescent devices, organic field effect transistors, organic thin film solar cells, and 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 electroluminescent 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.
The organic electroluminescent element 100 may have, for example, the following structure in which the manufacturing order is reversed: 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.
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 arbitrarily provided. In addition, each of the layers may include a single layer, or may include a plurality of layers.
The form of the layer constituting the organic electroluminescent element may be, in addition to the form of the "substrate/anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode", substrate/anode/hole transport 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 "), The structural forms of "substrate/anode/light-emitting layer/electron transport layer/electron injection layer/cathode", "substrate/anode/hole transport layer/light-emitting layer/electron transport layer/cathode", "substrate/anode/hole injection layer/light-emitting layer/electron injection layer/cathode", "substrate/anode/hole injection layer/light-emitting layer/electron transport layer/cathode", "substrate/anode/light-emitting layer/electron injection layer/cathode".
< substrate in organic electroluminescent element >
The substrate 101 is a support of the organic electroluminescent 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 the purpose, and for example, a glass plate, a metal foil, a plastic film, a plastic sheet, or the like can be used. 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 the mechanical strength, and therefore, for example, the thickness may be 0.2mm or more. The upper limit of the thickness is, for example, 2mm or less, preferably 1mm or less. As for the material of the glass, the less the ion eluted from the glass, the better, so it is preferably alkali-free glass, because of applying SiO2Etc. soda lime glass is also commercially available, and therefore the soda lime glass can be used. 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 particularly, when a synthetic resin plate, film or sheet having low gas barrier property is used as the substrate 101, it is 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 the hole injection layer 103 and/or the hole transport layer 104 are provided between the anode 102 and the light-emitting layer 105, holes are injected into the light-emitting layer 105 through these layers.
Examples of the material for forming the anode 102 include inorganic compounds and organic compounds. 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, it can be used by appropriately selecting from substances used as an anode of an organic electroluminescent 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 since a substrate of about 10 Ω/γ can be provided at present, 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, it is used in many cases between 50nm and 300 nm.
< hole injection layer, 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. In addition, 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 injected holes be efficiently transported with high hole injection efficiency. Therefore, a substance having a small ionization potential, a large hole mobility, and excellent stability, and being less likely to generate impurities serving as a well (trap) during production and use, is preferable.
As the 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, p-type semiconductors, and conventional compounds used in hole injection layers and hole transport layers of organic electroluminescent devices.
Specific examples of these materials include carbazole derivatives (e.g., N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis (N-arylcarbazole) and bis (N-alkylcarbazole), triarylamine derivatives (e.g., 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' -di (3-methylphenyl) -4,4 '-diaminobiphenyl, N' -diphenyl-N, N '-dinaphthyl-4, 4' -diaminobiphenyl, N '-diphenyl-N, N' -di (3-methylphenyl) -4,4 '-diphenyl-1, 1' -diamine, and mixtures thereof, N, N '-dinaphthyl-N, N' -diphenyl-4, 4 '-diphenyl-1, 1' -diamine, N4,N4'-diphenyl-N4,N4'-bis (9-phenyl-9H-carbazol-3-yl) - [1,1' -biphenyl]4,4' -diamine, N4,N4,N4',N4'-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, and the like), stilbene derivatives, phthalocyanine derivatives (nonmetal, copper phthalocyanine, and the like), 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-hexacarbonitrile, and the like), heterocyclic compounds such as porphyrin derivatives, polysilanes, and the like. Among the polymer systems, preferred is a polycarbonate having the monomer in a side chain or The styrene derivative, polyvinylcarbazole, polysilane, and the like are not particularly limited as long as they form a thin film necessary for manufacturing a light-emitting element, and are compounds which can inject holes from an anode and can transport holes.
In addition, it is also known that the conductivity of an organic semiconductor is strongly affected by its doping. Such an organic semiconductor matrix (matrix) substance contains a compound having a good electron donating property or a compound having a good electron accepting property. For the doping of electron-donating substances, strong electron acceptors such as Tetracyanoquinodimethane (TCNQ) or 2,3,5, 6-tetrafluorotetracyanoquinodimethane (2,3,5,6-tetrafluorotetracyano-1, 4-quinodimethane (2,3,5, 6-tetrafluoro-1, 4-benzoquinodimethane, F4TCNQ) are known (see, for example, the documents "m. faffy, a. bayer, t. friez, k. rio (m. pfeiffer, a. beyer, t.fritz, k.leo), the application physics promo (app. phys. lett.),73 (73), (22),3202- -3204 (1998)" and the documents "j. bulohowez, m. faffy, t. friez, k. jeftz, k. bewez, p. phys. lett, p. philis. 731, p. philis.t., t.t., p. peff 72z)", the documents "pp. beweftz, t. These generate so-called holes by an electron transfer process of 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 or the like), a starburst amine derivative (4,4',4 ″ -tris (N, N-diphenylamino) triphenylamine, TDATA, or the like), or a specific metal phthalocyanine (in particular, zinc phthalocyanine (ZnPc) or the like) is known (japanese patent laid-open No. 2005-167175).
< 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 forming the light-emitting layer 105 may be a compound (light-emitting compound) which emits light by being excited by recombination of holes and electrons, and is preferably a compound which can be formed into a stable thin film shape and which exhibits strong light emission (fluorescence) efficiency in a solid state. In the present invention, as a material for the light-emitting layer, a polycyclic aromatic compound represented by the above general formula (1) can be used.
The light-emitting layer may be a single layer or may include a plurality of layers, and each of the 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 dopant material may be included within the bulk of the host material, or may be included 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 in which the host material is mixed in advance, or a wet film-forming method in which the host material is mixed with an organic solvent in advance and then the film is formed.
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 differs depending on the type 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.
On the other hand, in the organic electroluminescent element using the thermally activated delayed fluorescence dopant material, when the amount of the dopant material used is low, it is preferable in terms of preventing the concentration quenching phenomenon, but when the amount of the dopant material used is high, it is preferable in terms of the efficiency of the thermally activated delayed fluorescence mechanism. Further, in the organic electroluminescent element using the thermally activated 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 activated delayed fluorescence mechanism of the 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 respectively 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%, and 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. The compound of the present invention and a polymer compound thereof can also be used as an auxiliary dopant material.
Examples of the host material include condensed ring derivatives such as anthracene and pyrene, bisstyryl derivatives such as bisstyrylanthracene derivatives and distyrylbenzene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, fluorene derivatives, and benzofluorene derivatives, which have been known as light emitters from the past.
From the viewpoint of not inhibiting but promoting the generation of TADF in the light-emitting layer, the T1 energy of the host material is preferably higher than the T1 energy of the dopant or the auxiliary dopant having the highest T1 energy in the light-emitting layer, and specifically, the T1 energy of the host is preferably 0.01eV or more, more preferably 0.03eV or more, and still more preferably 0.1eV or more. In addition, a compound having TADF activity may be used as the host material.
Examples of the host material include a compound represented by the following general formula (3) and a compound represented by the following general formula (4). The compound represented by the general formula (3) is preferable.
[ solution 290]
Figure BDA0002815937380002521
In the formula (3), L1Is an arylene group having 6 to 30 carbon atoms or a heteroarylene group having 2 to 30 carbon atoms, 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, further preferably a heteroarylene group having 2 to 20 carbon atoms, furtherPreferably, the heteroarylene group has 2 to 15 carbon atoms, and particularly preferably has 2 to 10 carbon atoms. Specific examples of the arylene group include: 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, a pentacene ring, and the like. Specific examples of the heteroarylene group include: pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, oxadiazole ring, thiadiazole ring, triazole ring, tetrazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring, cinnoline ring, quinazoline ring, quinoxaline ring, phthalazine ring, naphthyridine ring, purine ring, pteridine ring, carbazole ring, acridine ring, phenoxathidine ring, phenoxazine ring, phenothiazine ring, phenazine azine ring, phenazasil (phenazasil) ring, indolizine ring, furan ring, benzofuran ring, isobenzofuran ring, dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, furazan ring, oxadiazole ring, thiadiazole ring, indolizine ring, indoxazole ring, indole ring, 1H-indazole ring, and so, Benzo-indole-carbazole ring and naphthobenzofuran ring.
In the formula (4), L2And L3Each independently 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 specifically, there can be mentioned: 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 includes: 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 triazine ring, a pyridine ring, a triazine,A monovalent group such as 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, a Phenazasiline (Phenazasiline) 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 furazan ring, an oxadiazole ring, a thianthrene ring, an indolocarbazole ring, a benzindolocarbazole ring, a benzindoline ring, and a naphthobenzofuran ring.
At least one hydrogen in the compound represented by formula (3) or (4) may be substituted by 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.
Examples of the host material include compounds represented by the following general formula (5).
[ formulation 291]
Figure BDA0002815937380002531
(in the above-mentioned formula (5),
R1～R11independently of one another, hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboron (two aryl groups may be bonded via a single bond or a linking group), alkyl or cycloalkyl (above the first substituent), at least one hydrogen of which may in turn be substituted by aryl, heteroaryl, diarylamino, diarylboron (two aryl groups may be bonded via a single bond or a linking group), alkyl or cycloalkyl (above the second substituent),
R1～R11wherein adjacent radicals may also be bonded to each other and together with the a-, b-or c-ring form an aryl or heteroaryl ring, and at least one hydrogen in the ring formed may also be replaced by aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylArylamino, diarylboron (two aryl groups may be bonded via a single bond or a linking group), alkyl, or cycloalkyl (the above being the first substituent), at least one hydrogen of which may in turn be substituted by aryl, heteroaryl, diarylamino, diarylboron (two aryl groups may be bonded via a single bond or a linking group), alkyl, or cycloalkyl (the above being the second substituent),
At least one hydrogen in the compound represented by the formula (5) may also be independently substituted with halogen or deuterium, respectively)
Preferably, in the formula (5),
R1～R11independently hydrogen, 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 diarylboron group (wherein each aryl group is an aryl group having 6 to 12 carbon atoms, and both aryl groups may be bonded via a single bond or a linking group), an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 16 carbon atoms, and at least one hydrogen of these groups may be further 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 diarylboron group (wherein each aryl group is an aryl group having 6 to 12 carbon atoms, and both aryl groups may be bonded via a single bond or a linking group), an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 16 carbon atoms,
R1～R11wherein adjacent groups 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 or c ring, at least one hydrogen in the 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), a diarylboron group (wherein each aryl group is an aryl group having 6 to 12 carbon atoms and both aryl groups may be bonded via a single bond or a linking group), 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 the group 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), a diarylboron group (wherein each aryl group is an aryl group having 6 to 12 carbon atoms and both aryl groups may be bonded via a single bond or a linking group), C1-12 alkyl or C3-16 cycloalkane And (4) substituting the group.
More preferably, in the formula (5),
R1～R11independently hydrogen, 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), a diarylboron group (wherein each aryl group is an aryl group having 6 to 10 carbon atoms, and both aryl groups may be bonded via a single bond or a linking group), an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 14 carbon atoms, and at least one hydrogen of these groups may be further substituted with 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), a diarylboron group (wherein each aryl group is an aryl group having 6 to 10 carbon atoms, and both aryl groups may be bonded via a single bond or a linking group), an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 14 carbon atoms,
R1～R11wherein adjacent groups 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 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), a diarylboron group (wherein each aryl group is an aryl group having 6 to 10 carbon atoms and both aryl groups may be bonded via a single bond or a linking group), 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 the group 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), a diarylboron group (wherein each aryl group is an aryl group having 6 to 10 carbon atoms and both aryl groups may be bonded via a single bond or a linking group), Alkyl group having 1 to 6 carbon atoms or 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 and arylheteroarylamino group may be exemplified as follows.
Specific examples of the "aryl group" include aryl groups having 6 to 30 carbon atoms, preferably aryl groups having 6 to 24 carbon atoms, more preferably aryl groups having 6 to 20 carbon atoms, still more preferably aryl groups having 6 to 16 carbon atoms, particularly preferably aryl groups having 6 to 12 carbon atoms, and most preferably aryl groups having 6 to 10 carbon atoms. Examples thereof include: phenyl as monocyclic aryl; (2-, 3-, 4-) biphenyl as a bicyclic aryl group; (1-, 2-) naphthyl as a condensed bicyclic aryl; 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, 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 tricyclic aryl groups; 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; tetrabiphenyl group (5' -phenyl-m-terphenyl-2-yl, 5' -phenyl-m-terphenyl-3-yl, 5' -phenyl-m-terphenyl-4-yl, m-quaterphenyl) as a tetracyclic aryl group; triphenylene- (1-, 2-) yl, pyrene- (1-, 2-, 4-) yl, tetracene- (1-, 2-, 5-) yl as condensed tetra-ring system aryl; perylene- (1-, 2-, 3-) group, pentacene- (1-, 2-, 5-, 6-) group, and the like as condensed five-ring system aryl group.
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: furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzofuranyl, benzo [ b ] thienyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxathiin, thianthrenyl, indolizinyl and the like.
The "alkyl group" in the first substituent and the second substituent may be either a straight chain or branched chain, and examples thereof include 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 (a branched chain alkyl group having 3 to 18 carbon atoms), more preferably an alkyl group having 1 to 12 carbon atoms (a branched chain alkyl group having 3 to 12 carbon atoms), still more preferably an alkyl group having 1 to 6 carbon atoms (a branched chain alkyl group having 3 to 6 carbon atoms), particularly preferably an alkyl group having 1 to 4 carbon atoms (a branched chain 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, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 2, 6-dimethyl-4-heptyl, 3,5, 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.
In the first substituent and the second substituent, as the "cycloalkyl group", there may be mentioned: a cycloalkyl group having 3 to 24 carbon atoms, 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 5 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a cycloalkyl group having 5 carbon atoms, and the like.
As specific cycloalkyl groups, there may be mentioned: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and substituents of these groups having 1 to 4 carbon atoms of alkyl (particularly methyl), norbornenyl, bicyclo [1.0.1] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.0.1] pentyl, bicyclo [1.2.1] hexyl, bicyclo [3.0.1] hexyl, bicyclo [2.1.2] heptyl, bicyclo [2.2.2] octyl, adamantyl, diamantanyl, decahydronaphthyl, decahydroazulenyl, and the like.
In the first substituent and the second substituent, the term "aryl" in the "diarylboron group" is usedAnd "may refer to the description of said aryl group. In addition, the two aryl groups may also be linked via a single bond or a linking group (e.g., > C (-R)2O, > S or > N-R). Here, > C (-R)2And R > N-R is aryl, heteroaryl, diarylamino, alkyl, or cycloalkyl (above the first substituent), which may be further substituted on at least one hydrogen in the first substituent (above the second substituent), and as specific examples of these groups, mention may be made of aryl, heteroaryl, diarylamino, alkyl, or cycloalkyl as the first and second substituents.
The substitution position when the first substituent is an aryl group is preferably R1、R3、R4、R5、R10And R11For example, more preferably to R1And R3Substituted with respect to R5And R10Substituted with respect to R4And R11Aryl is preferably phenyl.
The substitution position when the first substituent is heteroaryl is preferably R1、R2、R3、R4、R5、R6、R9、R10And R11For example, more preferably to R1Substituted with respect to R2Substituted with respect to R3Substituted with respect to R1And R3Substituted with respect to R4And R11Substituted with respect to R5And R10Substituted with respect to R6And R9The heteroaryl group is preferably a carbazolyl group. The heteroaryl (e.g., carbazolyl) may also be substituted to the position via a phenylene group.
Specific examples of the compound represented by the formula (5) include compounds represented by the following structural formulae. Further, "Me" in the formula is a methyl group.
[ solution 292]
Figure BDA0002815937380002561
The compound represented by formula (5) is first prepared by bonding the a-ring to the c-ring with a bonding group (-O-) to produce an intermediate (first reaction), and then by bonding the a-ring to the c-ring with B (boron) to produce a final product (second reaction). In the first reaction, for example, a nucleophilic substitution reaction, an ullmann reaction, or other common etherification reaction can be used. In the second reaction, a tandem heterofriedel-quardt reaction (a continuous 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.
In addition, as for the host Material, for example, the host Materials described in Advanced Materials (Advanced Materials), 2017,29,1605444, journal of Materials Chemistry C (journal of Material Chemistry C), 2016,4,11355-11381, Chemical Science, 2016,7,3355-3363, Solid Thin film (Thin Solid Films), 2016,619,120-124, and the like can be used as other examples. In addition, since a host material of a light-emitting layer of a TADF organic EL element requires high T1 energy, the host material suitable for a phosphorescent organic EL element described in chemical Society Reviews 2011,40, 2943-.
More specifically, the host compound is a compound having at least one structure selected from the group of partial structures (H-A) represented by the following formula, at least one hydrogen atom in each structure in the group of partial structures (H-A) may be substituted by any one of the group of partial structures (H-A) or the group of partial structures (H-B), and at least one hydrogen atom in these structures may be substituted by deuterium, halogen, cyano, alkyl group having 1 to 4 carbon atoms (e.g., methyl or tert-butyl), cycloalkyl group having 5 to 10 carbon atoms (e.g., cyclohexyl or adamantyl), trimethylsilyl group, or phenyl group.
[ Hua 293]
Figure BDA0002815937380002571
[ solution 294]
Figure BDA0002815937380002572
The main compound is preferably a compound represented by any one of the structural formulae listed below, and among these, a compound having 1 to 3 structures selected from the group of the partial structure (H-a) and 1 structure selected from the group of the partial structure (H-B) is more preferred, and a compound having a carbazolyl group as the group of the partial structure (H-a) is even more preferred, and a compound represented by the following formula (3-201), formula (3-202), formula (3-203), formula (3-204), formula (3-212), formula (3-221), formula (3-222), formula (3-261), or formula (3-262) is particularly preferred. In the structural formulae given below, at least one hydrogen may be substituted with a halogen, a cyano group, an alkyl group having 1 to 4 carbon atoms (e.g., methyl or tert-butyl), a cycloalkyl group having 5 to 10 carbon atoms (e.g., cyclohexyl or adamantyl), a phenyl group, a naphthyl group, or the like.
[ solution 295]
Figure BDA0002815937380002581
[ solution 296]
Figure BDA0002815937380002582
[ Hua 297]
Figure BDA0002815937380002591
[ 298]
Figure BDA0002815937380002592
[ 299]
Figure BDA0002815937380002593
In addition, the following polymer host materials can also be used.
[ equation 300]
Figure BDA0002815937380002601
In the formula (B-6), the MUs are each independently at least one selected from the group consisting of divalent groups of compounds represented by the general formulae (B-1) to (B-5), two hydrogens of the MUs are substituted with EC or MU, EC is each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, or aryloxy, at least one hydrogen of these may be further substituted with aryl, heteroaryl, or diarylamino, and k is an integer of 2 to 50000. k is preferably an integer of 100 to 40000, more preferably an integer of 500 to 25000.
The compounds represented by the general formulae (B-1) to (B-5) are the following compounds. Preferred are compounds represented by the general formulae (B-3) to (B-5).
[ solution 301]
Figure BDA0002815937380002602
In the formulae (B-1) to (B-4), Ar is independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino or aryloxy, at least one hydrogen of these may be further substituted by aryl, heteroaryl or diarylamino, adjacent groups in Ar may be bonded to each other and form an aryl ring or heteroaryl ring together with the parent skeleton of the anthracene ring, pyrene ring, fluorene ring or carbazole ring, respectively, and at least one hydrogen in the formed ring may be substituted by aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino or aryloxy. Specific descriptions of each group may be cited above with reference to the description of the polycyclic aromatic compound of the general formula (1) or the general formula (2). In each formula, n is an integer of 1 to 6, preferably an integer of 1 to 4, more preferably an integer of 1 to 2, and particularly preferably 1.
Specific examples of "Ar" in the formulae (B-1) to (B-4) include monovalent groups derived from the following structures or monovalent groups derived from a combination of the following structures.
[ solution 302]
Figure BDA0002815937380002611
In the formula (B-5), R1～R11Independently of one another, hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino or aryloxy, at least one hydrogen of which may in turn be substituted by aryl, heteroaryl or diarylamino,
R1～R11may also be bonded to each other and together with the a-, b-or c-ring form an aryl or heteroaryl ring, at least one hydrogen in the ring formed may also be substituted by aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino or aryloxy, at least one hydrogen of which may in turn be substituted by aryl, heteroaryl or diarylamino.
Specific descriptions of the respective groups may be cited as the description of the polycyclic aromatic compound of the general formula (1) described above.
At least one hydrogen in the compounds represented by the formulae (B-1) to (B-5) may be substituted by a group represented by the following formula (FG-1), a group represented by the following formula (FG-2), an alkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms, a halogen or deuterium, and any of the alkyl groups may further be-CH2Or may also be composed of-O-or-Si (CH)3)2-substituted, except for-CH in the alkyl group directly bonded to the compound represented by the formulae (B-1) to (B-5) 2Any other than-CH2And optionally substituted by an arylene group having 6 to 24 carbon atoms, wherein any hydrogen in the alkyl or cycloalkyl group may be substituted by fluorine.
At least one hydrogen of EC in the formula (B-6) may be substituted by a group represented by the following general formula (FG-1), a group represented by the following general formula (FG-2), an alkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms, a halogen or deuterium, and the above-mentioned alkaneAny of-CH in the group2Or may also be composed of-O-or-Si (CH)3)2-substitution in the alkyl group except-CH directly bonded to EC in formula (B-6)2Any other than-CH2And optionally substituted by an arylene group having 6 to 24 carbon atoms, wherein any hydrogen in the alkyl or cycloalkyl group may be substituted by fluorine.
[ solution 303]
Figure BDA0002815937380002621
(in the formula (FG-1),
r is independently fluorine, trimethylsilyl, trifluoromethyl, C1-C24 alkyl or C3-C24 cycloalkyl, and any-CH in the alkyl2-may also be substituted by-O-, of said alkyl groups other than-CH directly bonded to phenyl or phenylene2Any other than-CH2Optionally substituted by C6-24 arylene, at least one hydrogen of the cycloalkyl is optionally substituted by C1-24 alkyl or C6-12 aryl,
when two adjacent R's are alkyl or cycloalkyl, these may also be bonded to form a ring,
m is independently an integer of 0 to 4, n is an integer of 0 to 5, and p is an integer of 1 to 5)
[ solution 304]
Figure BDA0002815937380002622
(in the formula (FG-2),
r is independently fluorine, trimethylsilyl, trifluoromethyl, C1-24 alkyl, C3-24 cycloalkyl or C6-12 aryl, and any-CH in the alkyl2-may also be substituted by-O-, of said alkyl groups other than-CH directly bonded to phenyl or phenylene2Any other than-CH2The cycloalkyl group may be substituted with an arylene group having 6 to 24 carbon atoms, and at least one hydrogen in the cycloalkyl group may be substituted with an alkyl group having 1 to 24 carbon atoms or an aryl group having 6 to 12 carbon atomsAt least one hydrogen in the aryl group may be substituted by an alkyl group having 1 to 24 carbon atoms,
when two adjacent R's are alkyl or cycloalkyl, these may also be bonded to form a ring,
m is an integer of 0 to 4, and n is an integer of 0 to 5 independently
Examples of the MU include divalent groups represented by the following general formulae (MU-1-1) to (MU-1-12), the following general formulae (MU-2-1) to (MU-2-202), the following general formulae (MU-3-1) to (MU-3-201), the following general formulae (MU-4-1) to (MU-4-122), and the following general formulae (MU-5-1) to (MU-5-12). Examples of EC include those represented by the following general formulae (EC-1) to (EC-29). In these, MU is bonded to MU or EC at one site, and EC is bonded to MU at one site.
Further, from the viewpoint of charge transport, the compound represented by the formula (B-6) preferably has at least one divalent group represented by the formula (B-6-X1) in the molecule, and more preferably has 10% or more of the divalent group represented by the formula (B-6-X1) relative to the molecular weight of the compound represented by the formula (B-6). Here, the divalent group represented by the formula (B-6-X1) is bonded to MU or EC at one position.
[ solution 305]
Figure BDA0002815937380002631
[ solution 306]
Figure BDA0002815937380002632
[ solution 307]
Figure BDA0002815937380002641
[ chemical 308]
Figure BDA0002815937380002642
[ solution 309]
Figure BDA0002815937380002643
[ chemical 310]
Figure BDA0002815937380002651
[ solution 311]
Figure BDA0002815937380002652
From the viewpoint of solubility and coating film formation properties, the compound represented by the formula (B-6) is preferably one in which 10 to 100% of the MUs in the total number (n) of MUs in the molecule have an alkyl group having 1 to 24 carbon atoms or a cycloalkyl group having 3 to 24 carbon atoms, more preferably 30 to 100% of the MUs in the total number (n) of MUs in the molecule have an alkyl group having 1 to 18 carbon atoms (branched chain alkyl group having 3 to 18 carbon atoms) or a cycloalkyl group having 3 to 20 carbon atoms, and further preferably 50 to 100% of the MUs in the total number (n) of MUs in the molecule have an alkyl group having 1 to 12 carbon atoms (branched chain alkyl group having 3 to 12 carbon atoms) or a cycloalkyl group having 3 to 16 carbon atoms. On the other hand, from the viewpoint of in-plane orientation and charge transport, 10 to 100% of the MUs of the total number of MUs (n) in a molecule preferably have an alkyl group having 7 to 24 carbon atoms or a cycloalkyl group having 3 to 24 carbon atoms, and more preferably 30 to 100% of the MUs of the total number of MUs (n) in a molecule have an alkyl group having 7 to 24 carbon atoms (branched chain alkyl group having 7 to 24 carbon atoms) or a cycloalkyl group having 3 to 24 carbon atoms.
The dopant material is not particularly limited, and a known compound can be used, and can be selected from various materials according to a desired emission color. Specific examples thereof include: phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphthopyrene, dibenzopyrene, rubrene and
Figure BDA0002815937380002653
iso-condensed ring derivatives, benzoxazole derivatives, benzothiazole derivatives, benzimidazole derivatives, benzotriazole derivativesBioses, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, imidazole derivatives, thiadiazole derivatives, triazole derivatives, pyrazoline derivatives, stilbene derivatives, thiophene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives or distyrylbenzene derivatives (Japanese patent application laid-open No. Hei 1-245087), bisstyrylarylene derivatives (Japanese patent application laid-open No. Hei 2-247278), diazabenzodiindene (diazaindene) derivatives, furan derivatives, benzofuran derivatives, phenylisobenzofuran, ditrimethylphenylisobenzofuran, bis (2-methylphenyl) isobenzofuran, bis (2-trifluoromethylphenyl) isobenzofuran, isobenzofuran derivatives such as phenylisobenzofuran, dibenzofuran derivatives, 7-dialkylaminocoumarin derivatives, 7-piperidylcoumarin derivatives, 7-hydroxycoumarin derivatives, 7-methoxycoumarin derivatives, 7-acetoxycoumarin derivatives, 3-benzothiazolenecoumarin derivatives, 3-benzimidazolylcoumarin derivatives, coumarin derivatives such as 3-benzoxazolino coumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, polymethine derivatives, cyanine derivatives, oxobenzanthrene derivatives, xanthene derivatives, rhodamine derivatives, fluorescein derivatives, pyrylium derivatives, carbostyril derivatives, acridine derivatives, oxazine derivatives, phenylene oxide derivatives, quinacridone derivatives, quinazoline derivatives, pyrrolopyridine derivatives, Furopyridine derivatives, 1,2, 5-thiadiazolopyridine derivatives, pyrromethene derivatives, perinone derivatives, pyrrolopyrrole derivatives, squarylium (squarylium) derivatives, violanthrone (violanthrone) derivatives, phenazine derivatives, acridone derivatives, deazaflavin (deazaflavin) derivatives, fluorene derivatives, and benzofluorene derivatives, and the like.
As exemplified by the color-emitting light, examples of the blue to blue-green dopant materials include: naphthalene, anthracene, phenanthrene, pyrene, triphenylene, perylene, fluorene, indene,
Figure BDA0002815937380002661
And aromatic hydrocarbon compounds or derivatives thereof, furan, pyrrole, thiophene, silole (silole), 9-silafluorene (silafluorene), 9' -spirodisilylfluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, aromatic heterocyclic compounds such as phenanthroline, pyrazine, naphthyridine, quinoxaline, pyrrolopyridine, and thianthrene (thioxanthe) and derivatives thereof, distyrylbenzene derivatives, tetraphenylbutadiene derivatives, stilbene derivatives, aldazine derivatives, coumarin derivatives, azole derivatives such as imidazole, thiazole, thiadiazole, carbazole, oxazole, oxadiazole, and triazole, and metal complexes thereof, and aromatic amine derivatives represented by N, N '-diphenyl-N, N' -bis (3-methylphenyl) -4,4 '-diphenyl-1, 1' -diamine.
Further, examples of the green to yellow dopant materials include: preferred examples of the dopant material include coumarin derivatives, phthalimide derivatives, naphthalimide derivatives, perinone derivatives, pyrrolopyrrole derivatives, cyclopentadiene derivatives, acridone derivatives, quinacridone derivatives, and tetracene derivatives such as rubrene, and further include compounds obtained by introducing a substituent capable of increasing the wavelength of blue to blue-green, 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 to blue-green dopant materials.
Further, examples of the orange to red dopant materials include: naphthalimide derivatives such as bis (diisopropylphenyl) perylenetetracarboxylic acid imide, perinone derivatives, rare earth complexes such as Eu complexes using acetylacetone or benzoylacetone and phenanthroline as ligands, 4- (dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyrane or analogues thereof, 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 salt derivatives, violanthrone derivatives, phenazine derivatives, phenoxazine derivatives, phenoxazone derivatives, and thiadiazolopyridine derivatives, and the like, and further, there may be mentioned compounds exemplified as the above-mentioned blue to blue-green and green to yellow dopant materials, to which an aryl group, a substituted aryl group, a, Preferred examples of the compound include a substituent capable of attaining a longer wavelength such as heteroaryl, arylvinyl, amino, cyano and the like.
The dopant may be appropriately selected from compounds described in 2004, 6/13, and references cited therein.
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 312]
Figure BDA0002815937380002671
In the formula, Ar1Is an m-valent group derived from an aryl group having 6 to 30 carbon atoms, Ar2And Ar3Each independently an aryl group having 6 to 30 carbon atoms, Ar1～Ar3At least one of them having a stilbene structure, Ar1～Ar3Or an aryl group, a heteroaryl group, an alkyl group, a cycloalkyl group, a trisubstituted silyl group (a silyl group trisubstituted by an aryl group, an alkyl group and/or a cycloalkyl group), 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 313]
Figure BDA0002815937380002672
In the formula, Ar2And Ar3Each independently an aryl group having 6 to 30 carbon atoms, Ar2And Ar3Also from aryl, heteroaryl, alkyl, cycloalkyl, trisubstituted silyl (from aryl, alkyl and/or cycloalkane)Groups that are trisubstituted silyl) or cyano.
Specific examples of the aryl group having 6 to 30 carbon atoms include: phenyl, naphthyl, acenaphthenyl, fluorenyl, phenalkenyl, phenanthryl, anthracenyl, fluoranthenyl, triphenylenyl, pyrenyl, phenanthrenyl, triphenylenyl, pyrenyl, phenanthrenyl, phenanthr,
Figure BDA0002815937380002673
Mesitylene, perylene, 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 ' -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, toluene, xylene, 2, 7-bis [4' -bis (diphenylamino) styryl ] -9, 9-dimethylfluorene, 4' -bis (9-ethyl-3-carbazolylenediyl) -biphenyl, 4' -bis (9-phenyl-3-carbazolylenediyl) -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 Nos. 11-97178, 2000-133457, 2000-26324, 2001-267079, 2001-267078, 2001-267076, 2000-34234, 2001-267075, and 2001-217077 may be used.
Examples of 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 314]
Figure BDA0002815937380002681
In the formula, Ar4Is an n-valent group derived from an aryl group having 6 to 30 carbon atoms, Ar5And Ar6Each independently an aryl group having 6 to 30 carbon atoms, Ar 4～Ar6Or an aryl group, a heteroaryl group, an alkyl group, a cycloalkyl group, a trisubstituted silyl group (a silyl group trisubstituted by an aryl group, an alkyl group and/or a cycloalkyl group), or a cyano group, and n is an integer of 1 to 4.
In particular, Ar4Is derived from anthracene,
Figure BDA00028159373800026815
Divalent radicals of fluorene, benzofluorene or pyrene, Ar5And Ar6Each independently an aryl group having 6 to 30 carbon atoms, Ar4～Ar6The aromatic amine derivative 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 an aryl group, an alkyl group and/or 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, acenaphthenyl, fluorenyl, phenanthrenyl, and phenanthrenyl,Phenanthryl, anthryl, fluoranthenyl, triphenylenyl, pyrenyl,
Figure BDA0002815937380002683
Mesityl, tetracenyl, perylenyl, pentacenyl, and the like.
As the aromatic amine derivative, there may be mentioned,
Figure BDA0002815937380002684
examples thereof include: n, N, N ', N' -tetraphenyl
Figure BDA0002815937380002685
6, 12-diamine, N, N, N ', N' -tetrakis (p-tolyl)
Figure BDA0002815937380002686
6, 12-diamine, N, N, N ', N' -tetrakis (m-tolyl)
Figure BDA0002815937380002687
6, 12-diamine, N, N, N ', N' -tetrakis (4-isopropylphenyl)
Figure BDA0002815937380002688
-6, 12-diamine, N, N, N ', N' -tetrakis (naphthalen-2-yl)
Figure BDA0002815937380002689
6, 12-diamine, N '-diphenyl-N, N' -di (p-tolyl)
Figure BDA00028159373800026810
-6, 12-diamine, N '-diphenyl-N, N' -bis (4-ethylphenyl)
Figure BDA00028159373800026811
6, 12-diamine, N '-diphenyl-N, N' -bis (4-isopropylphenyl)
Figure BDA00028159373800026812
-6, 12-diamine, N '-diphenyl-N, N' -bis (4-tert-butylphenyl)
Figure BDA00028159373800026813
6, 12-diamine, NN '-bis (4-isopropylphenyl) -N, N' -di (p-tolyl)
Figure BDA00028159373800026814
6, 12-diamine, and the like.
Further, examples of pyrene series include: n, N, N ', N ' -tetraphenylpyrene-1, 6-diamine, N, N, N ', N ' -tetra (p-tolyl) pyrene-1, 6-diamine, N, N, N ', N ' -tetra (m-tolyl) pyrene-1, 6-diamine, N, N, N ', N ' -tetra (4-isopropylphenyl) pyrene-1, 6-diamine, N, N, N ', N ' -tetra (3, 4-dimethylphenyl) pyrene-1, 6-diamine, N, N ' -diphenyl-N, N ' -di (p-tolyl) pyrene-1, 6-diamine, N, N ' -diphenyl-N, N ' -bis (4-ethylphenyl) pyrene-1, 6-diamine, N, N ' -diphenyl-N, n ' -bis (4-isopropylphenyl) pyrene-1, 6-diamine, N, N ' -diphenyl-N, N ' -bis (4-t-butylphenyl) pyrene-1, 6-diamine, N, N ' -bis (4-isopropylphenyl) -N, N ' -di (p-tolyl) pyrene-1, 6-diamine, N, N, N ', N ' -tetrakis (3, 4-dimethylphenyl) -3, 8-diphenylpyrene-1, 6-diamine, N, N-tetraphenylpyrene-1, 8-diamine, N, N ' -bis (biphenyl-4-yl) -N, N ' -diphenylpyrene-1, 8-diamine1,N6-diphenyl-N1,N6-bis- (4-trimethylsilyl-phenyl) -1H, 8H-pyrene-1, 6-diamine and the like.
Further, the anthracene series includes, for example: 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-tert-butylphenyl) anthracene-9, 10-diamine, N, N' -bis (4-isopropylphenyl) -N, N '-di (p-tolyl) anthracene-9, 10-diamine, 2, 6-di-tert-butyl-N, N, N', N '-tetra (p-tolyl) anthracene-9, 10-diamine, 2, 6-di-tert-butyl-N, N' -diphenyl-N, N '-bis (4-isopropylphenyl) anthracene-9, 10-diamine, 2, 6-di-tert-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-tert-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, a salt thereof, a base material thereof, and a pharmaceutically acceptable carrier, 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' -bis [ 6-diphenylaminonaphthalen-2-yl ] biphenyl, 4 '-bis [ 4-diphenylaminonaphthalen-1-yl ] -p-terphenyl, 4' -bis [ 6-diphenylaminonaphthalen-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.
Coumarin derivatives include: coumarin-6, coumarin-334 and the like.
Further, coumarin derivatives described in Japanese patent laid-open Nos. 2004-43646, 2001-76876, and 6-298758 may be used.
Examples of the pyran derivative include pyranecarbonitrile Derivatives (DCM) and (E) -4- (Dicyanomethylene) -2-tert-butyl-6- (1,1,7, 7-tetramethyljulidin-4-yl-vinyl) -4H-pyran (4- (Dicyanomethylene) -2-tert-butyl-6- (1,1,7, 7-tetramethyljunolidin-4-yl-vinyl) -4H-pyran, DCJTB).
[ solution 315]
Figure BDA0002815937380002691
Further, pyran derivatives described in Japanese patent laid-open Nos. 2005-126399, 2005-097283, 2002-234892, 2001-220577, 2001-081081090, 2001-052869, and the like can also be used.
< 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 transport layer 106 and the electron injection layer 107 are formed by laminating and mixing one or more kinds of electron transport/injection materials, or are formed by mixing an electron transport/injection material and a polymer binder.
The electron injection/transport layer is a layer that manages the injection of electrons from the cathode and the transport of electrons, and it is desirable that the injected electrons be efficiently transported with high electron injection efficiency. Therefore, a substance having a high electron affinity, a high electron mobility, and excellent stability is preferable, and impurities serving as wells are not easily generated during production and use. However, when considering the balance between the transport of holes and electrons, in the case where the function of efficiently preventing holes from the anode from flowing to the cathode side without recombination is mainly exerted, even if the electron transport ability is not so high, the effect of improving the light emission efficiency is obtained as much as that of a material having a high electron transport ability. 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 for forming the electron transport layer 106 or the electron injection layer 107 (electron transport material) can be selected from any of 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.
The material used for the electron transport layer or the electron injection layer preferably contains at least one selected from the group consisting of an aromatic ring or heteroaromatic ring compound containing at least one atom selected from carbon, hydrogen, oxygen, sulfur, silicon, and phosphorus, a pyrrole derivative or a fused ring derivative thereof, and a metal complex having electron-accepting nitrogen. Specifically, there may be mentioned: 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: a hydroxyazole complex such as a hydroxyphenyl oxazole complex, an azomethine complex, a tropolone metal complex, a flavonol metal complex, a benzoquinoline metal complex, and the like. 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, benzoxazole (benzoxazole) -based compounds, gallium complexes, pyrazole derivatives, perfluorinated phenylene derivatives, triazine derivatives, and mixtures thereof, Pyrazine derivatives, benzoquinoline derivatives (e.g., 2' -bis (benzo [ h ] quinolin-2-yl) -9,9' -spirobifluorene), imidazopyridine derivatives, borane derivatives, benzimidazole derivatives (e.g., tris (N-phenylbenzimidazol-2-yl) benzene), benzoxazole derivatives, benzothiazole derivatives, quinoline derivatives, terpyridine derivatives, oligopyridine derivatives such as terpyridine, bipyridine derivatives, terpyridine derivatives (e.g., 1, 3-bis (4' - (2,2 ': 6'2 "-terpyridyl)) benzene), naphthyridine derivatives (e.g., bis (1-naphthyl) -4- (1, 8-naphthyridin-2-yl) phenylphosphine oxide), aldazine derivatives, carbazole derivatives, indole derivatives, and the like, 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 may be used alone or in admixture with different materials.
Among the above materials, preferred are borane derivatives, pyridine derivatives, fluoranthene derivatives, BO-based derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, and hydroxyquinoline-based metal complexes.
Borane derivatives
Examples of the borane derivatives are compounds represented by the following general formula (ETM-1), and are disclosed in detail in Japanese patent laid-open No. 2007-27587.
[ chemical 316]
Figure BDA0002815937380002711
In the formula (ETM-1), R11And R12Each independently is at least one of hydrogen, alkyl, cycloalkyl, aryl which may be substituted, silyl which may be substituted, nitrogen-containing heterocycle which may be substituted, or cyano, R13～R16Each independently represents an alkyl group which may be substituted, a cycloalkyl group which may be substituted, or an aryl group which may be substituted, X represents an arylene group which may be substituted, Y represents an aryl group having 16 or less carbon atoms which may be substituted, a substituted boron group, or a substituted carbazolyl group, and n is an integer of 0 to 3. In addition, as the substituent in the case of "may be substituted" or "substituted", there may be mentioned: aryl, heteroaryl, alkyl or cycloalkyl, and the like.
Among the compounds represented by the above general formula (ETM-1), a compound represented by the following general formula (ETM-1-1) or a compound represented by the following general formula (ETM-1-2) is preferable.
[ chemical 317]
Figure BDA0002815937380002712
In the formula (ETM-1-1), R11And R12Each independently is at least one of hydrogen, alkyl, cycloalkyl, aryl which may be substituted, silyl which may be substituted, nitrogen-containing heterocycle which may be substituted, or cyano, R13～R16Each independently an alkyl group which may be substituted, a cycloalkyl group which may be substituted, or an aryl group which may be substituted, R21And R22Each independently is at least one of hydrogen, alkyl, cycloalkyl, aryl which may be substituted, silyl which may be substituted, nitrogen-containing heterocycle which may be substituted, or cyano, X1Is an arylene group having 20 or less carbon atoms which may be substituted, n is independently an integer of 0 to 3, and m is independently an integer of 0 to 4. In addition, as the substituent in the case of "may be substituted" or "substituted", there may be mentioned: aryl, heteroaryl, alkyl or cycloalkyl, and the like.
[ solution 318]
Figure BDA0002815937380002721
In the formula (ETM-1-2), R11And R12Each independently is at least one of hydrogen, alkyl, cycloalkyl, aryl which may be substituted, silyl which may be substituted, nitrogen-containing heterocycle which may be substituted, or cyano, R 13～R16Each independently an alkyl group which may be substituted, a cycloalkyl group which may be substituted, or an aryl group which may be substituted, X1Is an arylene group having 20 or less carbon atoms which may be substituted, and n is an integer of 0 to 3 independently. In addition, as the substituent in the case of "may be substituted" or "substituted", there may be mentioned: aryl, heteroaryl, alkyl or cycloalkyl, and the like.
As X1In a specific embodiment, canThere are exemplified divalent groups represented by any one of the following formulae (X-1) to (X-9).
[ formulation 319]
Figure BDA0002815937380002722
(in the formulae, RaEach independently is alkyl, cycloalkyl or phenyl which may be substituted)
Specific examples of the borane derivative include the following compounds.
[ solution 320]
Figure BDA0002815937380002731
The borane derivatives can be produced using conventional starting materials and conventional synthesis methods.
< pyridine derivatives >
The pyridine derivative is, for example, a compound represented by the following formula (ETM-2), and preferably a compound represented by the formula (ETM-2-1) or the formula (ETM-2-2).
[ solution 321]
Phi- (pyridine substituent) n (ETM-2)
Figure BDA0002815937380002732
Phi is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is an integer of 1-4.
In the formula (ETM-2-1), R 11～R18Each independently represents hydrogen, an alkyl group (preferably an alkyl group having 1 to 24 carbon atoms), a cycloalkyl group (preferably a cycloalkyl group having 3 to 12 carbon atoms) or an aryl group (preferably an aryl group having 6 to 30 carbon atoms).
In the formula (ETM-2-2), R11And R12Each independently hydrogen, alkyl (preferably C1-C24 alkyl), cycloalkyl (preferably C3-C12 cycloalkyl), orAryl (preferably C6-30 aryl), R11And R12May be bonded to form a ring.
In each formula, the "pyridine substituent" is any one of the following formulae (Py-1) to (Py-15), and the pyridine substituent may be independently substituted by an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms. In addition, the pyridine substituent may be bonded to φ, anthracene ring or fluorene ring in each formula via phenylene or naphthylene.
[ solution 322]
Figure BDA0002815937380002741
The pyridine substituent is any one of the above formulae (Py-1) to (Py-15), and among these, any one of the following formulae (Py-21) to (Py-44) is preferable.
[ solution 323]
Figure BDA0002815937380002751
At least one hydrogen of each pyridine derivative may be substituted with deuterium, and one of the two "pyridine substituents" in the formula (ETM-2-1) and the formula (ETM-2-2) may be substituted with an aryl group.
As R11～R18The "alkyl group" in (1) may be either a straight chain or branched chain, and examples thereof include a straight chain alkyl group having 1 to 24 carbon atoms and a branched chain alkyl group having 3 to 24 carbon atoms. The preferred "alkyl group" is an alkyl group having 1 to 18 carbon atoms (branched chain alkyl group having 3 to 18 carbon atoms). More preferably, the "alkyl group" is an alkyl group having 1 to 12 carbon atoms (branched chain alkyl group having 3 to 12 carbon atoms). Further preferred "alkyl group" is an alkyl group having 1 to 6 carbon atoms (branched chain alkyl group having 3 to 6 carbon atoms). Particularly preferred "alkyl group" is an alkyl group having 1 to 4 carbon atoms (branched chain alkyl group having 3 to 4 carbon atoms).
Specific examples of the "alkyl group" include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 2, 6-dimethyl-4-heptyl, 3,5, 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.
As the alkyl group having 1 to 4 carbon atoms substituted on the pyridine substituent, the description of the alkyl group can be cited.
As R11～R18Examples of the "cycloalkyl group" in (1) include cycloalkyl groups having 3 to 12 carbon atoms. The preferable "cycloalkyl group" is a cycloalkyl group having 3 to 10 carbon atoms. More preferably, the "cycloalkyl group" is a cycloalkyl group having 3 to 8 carbon atoms. Further preferred "cycloalkyl group" is a cycloalkyl group having 3 to 6 carbon atoms.
Specific "cycloalkyl" groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, dimethylcyclohexyl, or the like.
As the cycloalkyl group having 5 to 10 carbon atoms substituted on the pyridine substituent, the description thereof can be cited.
As R11～R18The "aryl group" in (1) is preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 18 carbon atoms, still more preferably an aryl group having 6 to 14 carbon atoms, and particularly preferably an aryl group having 6 to 12 carbon atoms.
Specific examples of the "aryl group having 6 to 30 carbon atoms" include: phenyl as monocyclic aryl; (1-, 2-) naphthyl as a condensed bicyclic aryl; 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; triphenylene- (1-, 2-) yl, pyrene- (1-, 2-, 4-) yl, tetracene- (1-, 2-, 5-) yl as condensed tetra-ring system aryl; perylene- (1-, 2-, 3-) group, pentacene- (1-, 2-, 5-, 6-) group, and the like as condensed five-ring system aryl group.
Preferred examples of the "aryl group having 6 to 30 carbon atoms" include phenyl, naphthyl, phenanthryl,
Figure BDA0002815937380002762
Examples of the group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and a phenanthryl group, and examples of the group include a phenyl group, a 1-naphthyl group and a 2-naphthyl group.
R in the formula (ETM-2-2) 11And R12A ring may be formed by bonding, and as a result, cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, fluorene, indene, or the like may be spiro-bonded to the 5-membered ring of the fluorene skeleton.
Specific examples of the pyridine derivative include the following compounds.
[ solution 324]
Figure BDA0002815937380002761
The pyridine derivative can be produced using a conventional raw material and a conventional synthesis method.
< fluoranthene derivative >
Fluoranthene derivatives are, for example, compounds represented by the following general formula (ETM-3), and are disclosed in detail in international publication No. 2010/134352.
[ solution 325]
Figure BDA0002815937380002771
In the formula (ETM-3), X12～X21Represents hydrogen, halogen, linear, branched or cyclic alkyl, linear, branched or cyclic alkoxy, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. Here, as the substituent in the case of substitution, there may be mentioned: aryl, heteroarylalkyl or cycloalkyl, and the like.
Specific examples of the fluoranthene derivative include the following compounds.
[ chemical 326]
Figure BDA0002815937380002772
< BO series derivative >
The BO derivative is, for example, a polycyclic aromatic compound represented by the following formula (ETM-4) or a polymer of a polycyclic aromatic compound having a plurality of structures represented by the following formula (ETM-4).
[ solution 327]
Figure BDA0002815937380002781
R1～R11Each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryl groups may also be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, or aryloxy, at least one hydrogen of which may also be substituted by aryl, heteroaryl, alkyl, or cycloalkyl.
In addition, R1～R11Wherein adjacent groups may also be bonded to each other and together with the a-, b-or c-ring form an aryl or heteroaryl ring, at least one hydrogen in the formed ring may also be substituted by an aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboron group (two aryl groups may also be bonded via a single bond or a linking group), an alkyl, cycloalkyl, alkoxy or aryloxy group, at least one hydrogen of which may also be substituted by an aryl, heteroaryl, alkyl or cycloalkyl group.
In addition, at least one hydrogen in the compound or structure represented by formula (ETM-4) may also be substituted with halogen or deuterium.
As for the form of the substituent or ring in the formula (ETM-4) and the description of the multimer formed by combining a plurality of the structures of the formula (ETM-4), the description of the compound represented by the above general formula (1) or the multimer thereof can be cited.
Specific examples of the BO-based derivative include the following compounds.
[ solution 328]
Figure BDA0002815937380002782
The BO-based derivative can be produced using a conventional raw material and a conventional synthesis method.
< Anthracene derivatives >
One of the anthracene derivatives is, for example, a compound represented by the following formula (ETM-5-1).
[ solution 329]
Figure BDA0002815937380002791
Ar is each independently divalent benzene or naphthalene, R1～R4Each independently represents hydrogen, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms.
Ar may be appropriately selected from divalent benzene or naphthalene, and two Ar may be different or the same, and are preferably the same from the viewpoint of ease of synthesis of the anthracene derivative. Ar is bonded to pyridine to form "a site including Ar and pyridine", and the site is bonded to anthracene as a group represented by any one of the following formulae (Py-1) to (Py-12), for example.
[ solution 330]
Figure BDA0002815937380002792
Among these groups, those represented by any one of the formulae (Py-1) to (Py-9) are preferred, and those represented by any one of the formulae (Py-1) to (Py-6) are more preferred. The two "sites containing Ar and pyridine" bonded to anthracene may be the same or different in structure, and the same structure is preferable from the viewpoint of ease of synthesis of the anthracene derivative. Among them, from the viewpoint of device characteristics, it is preferable that the two "sites containing Ar and pyridine" have the same or different structures.
With respect to R1～R4The alkyl group having 1 to 6 carbon atoms in the group (C) may be either a straight chain or branched chain. Namely, a linear alkyl group having 1 to 6 carbon atoms or a branched chain alkyl group having 3 to 6 carbon atoms. More preferably an alkyl group having 1 to 4 carbon atoms (branched chain alkyl group having 3 to 4 carbon atoms). Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, and 2-ethylbutyl, and preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, and more preferably methyl, ethyl, or tert-butyl.
As R1～R4Specific examples of the cycloalkyl group having 3 to 6 carbon atoms in (b) include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, dimethylcyclohexyl, or the like.
With respect to R1～R4The aryl group having 6 to 20 carbon atoms in (A) is preferably an aryl group having 6 to 16 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and particularly preferably an aryl group having 6 to 10 carbon atoms.
Specific examples of the "aryl group having 6 to 20 carbon atoms" include: phenyl, (o, m, p) tolyl, (2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-) xylyl, mesityl (2,4, 6-trimethylphenyl), (o, m, p) cumenyl, which is a monocyclic aryl group; (2-, 3-, 4-) biphenyl as a bicyclic aryl group; (1-, 2-) naphthyl as a condensed bicyclic aryl; 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, 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 tricyclic aryl groups; anthracene- (1-, 2-, 9-) radical, acenaphthene- (1-, 3-, 4-, 5-) radical, fluorene- (1-, 2-, 3-, 4-, 9-) radical, phenalene- (1-, 2-) radical, (1-, 2-, 3-, 4-, 9-) phenanthrene radical as condensed tricyclic aryl radicals; triphenylene- (1-, 2-) yl, pyrene- (1-, 2-, 4-) yl, tetracene- (1-, 2-, 5-) yl as condensed tetra-ring system aryl; perylene- (1-, 2-, 3-) groups as condensed five-ring system aryl groups, and the like.
The "aryl group having 6 to 20 carbon atoms" is preferably a phenyl group, a biphenyl group, a terphenyl group or a naphthyl group, more preferably a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group or an m-terphenyl-5' -yl group, further preferably a phenyl group, a biphenyl group, a 1-naphthyl group or a 2-naphthyl group, and most preferably a phenyl group.
One of the anthracene derivatives is, for example, a compound represented by the following formula (ETM-5-2).
[ solution 331]
Figure BDA0002815937380002801
Ar1Each independently a single bond, divalent benzene, naphthalene, anthracene, fluorene, or phenalene.
Ar2As the aryl group having 6 to 20 carbon atoms, the same description as "aryl group having 6 to 20 carbon atoms" in the formula (ETM-5-1) can be cited. Preferably an aryl group having 6 to 16 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and particularly preferably an aryl group having 6 to 10 carbon atoms. Specific examples thereof include: phenyl, biphenyl, naphthyl, terphenyl, anthracenyl, acenaphthenyl, fluorenyl, phenalkenyl, phenanthrenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, and the like.
R1～R4Each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms, as described in the above formula (ETM-5-1).
Specific examples of the anthracene derivative include the following compounds.
[ chemical 332]
Figure BDA0002815937380002811
These anthracene derivatives can be produced using conventional raw materials and conventional synthesis methods.
< benzofluorene derivative >
The benzofluorene derivative is, for example, a compound represented by the following formula (ETM-6).
[ 333]
Figure BDA0002815937380002812
Ar1As the aryl group having 6 to 20 carbon atoms, the same description as "aryl group having 6 to 20 carbon atoms" in the formula (ETM-5-1) can be cited. Preferably an aryl group having 6 to 16 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and particularly preferably an aryl group having 6 to 10 carbon atoms. Specific examples thereof include: phenyl, biphenyl, naphthyl, terphenyl, anthracenyl, acenaphthenyl, fluorenyl, phenalkenyl, phenanthrenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, and the like.
Ar2Independently represents hydrogen, alkyl (preferably C1-C24 alkyl), cycloalkyl (preferably C3-C12 cycloalkyl) or aryl (preferably C6-C30 aryl), or two Ar2May be bonded to form a ring.
As Ar2The "alkyl group" in (1) may be either a straight chain or branched chain, and examples thereof include a straight chain alkyl group having 1 to 24 carbon atoms and a branched chain alkyl group having 3 to 24 carbon atoms. The preferred "alkyl group" is an alkyl group having 1 to 18 carbon atoms (branched chain alkyl group having 3 to 18 carbon atoms). More preferably, the "alkyl group" is an alkyl group having 1 to 12 carbon atoms (branched chain alkyl group having 3 to 12 carbon atoms). Further preferred "alkyl group" is an alkyl group having 1 to 6 carbon atoms (branched chain alkyl group having 3 to 6 carbon atoms). Particularly preferred "alkyl group" is an alkyl group having 1 to 4 carbon atoms (branched chain alkyl group having 3 to 4 carbon atoms). Specific examples of the "alkyl group" include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl and the like.
As Ar2Examples of the "cycloalkyl group" in (1) include carbonA number of 3 to 12 cycloalkyl groups. The preferable "cycloalkyl group" is a cycloalkyl group having 3 to 10 carbon atoms. More preferably, the "cycloalkyl group" is a cycloalkyl group having 3 to 8 carbon atoms. Further preferred "cycloalkyl group" is a cycloalkyl group having 3 to 6 carbon atoms. Specific "cycloalkyl" groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, dimethylcyclohexyl, or the like.
As Ar2The "aryl group" in (1) is preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 18 carbon atoms, still more preferably an aryl group having 6 to 14 carbon atoms, and particularly preferably an aryl group having 6 to 12 carbon atoms.
Specific examples of the "aryl group having 6 to 30 carbon atoms" include: phenyl, naphthyl, acenaphthenyl, fluorenyl, phenalkenyl, phenanthrenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, pentacenyl, and the like.
Two Ar2A ring may be formed by bonding, and as a result, cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, fluorene, indene, or the like may be spiro-bonded to the 5-membered ring of the fluorene skeleton.
Specific examples of the benzofluorene derivative include the following compounds.
[ chemical formula 334]
Figure BDA0002815937380002821
The benzofluorene derivative can be produced using conventional raw materials and conventional synthesis methods.
< phosphine oxide derivative >
The phosphine oxide derivative is, for example, a compound represented by the following formula (ETM-7-1). Details are also described in international publication No. 2013/079217.
[ solution 335]
Figure BDA0002815937380002822
R5Is a warpA substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 5 to 20 carbon atoms,
R6CN, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, heteroalkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, heteroaryl group having 5 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms or aryloxy group having 6 to 20 carbon atoms,
R7and R8Independently represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a heteroaryl group having 5 to 20 carbon atoms,
R9is oxygen or sulfur, and is selected from the group consisting of,
j is 0 or 1, k is 0 or 1, r is an integer of 0 to 4, and q is an integer of 1 to 3.
Here, as the substituent in the case of substitution, there may be mentioned: aryl, heteroaryl, alkyl or cycloalkyl, and the like.
The phosphine oxide derivative may be, for example, a compound represented by the following formula (ETM-7-2).
[ 336]
Figure BDA0002815937380002831
R1～R3Which may be the same or different, is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aralkyl, alkenyl, cycloalkenyl, alkynyl, alkoxy, alkylthio, cycloalkylthio, aryl ether, arylthioether, aryl, heterocyclic, halogen, cyano, aldehyde, carbonyl, carboxyl, amino, nitro, silane, and a fused ring formed between adjacent substituents.
Ar1May be the same or different and is an arylene or heteroarylene group, Ar2Which may be the same or different, are aryl or heteroaryl. Wherein Ar is1And Ar2Has a substituent, or forms a condensed ring with an adjacent substituent. n is an integer of 0 to 3, and when n is 0, no unsaturated moiety is present, and when n is 3, no R is present1。
Among these substituents, the alkyl group means, for example, a saturated aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group, or a butyl group, and may be unsubstituted or substituted. The substituent in the case of substitution is not particularly limited, and examples thereof include an alkyl group, an aryl group, and a heterocyclic group, and these are also common in the following description. The number of carbons of the alkyl group is not particularly limited, and is usually in the range of 1 to 20 in terms of easiness of obtaining and cost.
The cycloalkyl group means a saturated alicyclic hydrocarbon group such as a cyclopropyl group, a cyclohexyl group, a norbornyl group, an adamantyl group and the like, and may be unsubstituted or substituted. The number of carbon atoms in the alkyl moiety is not particularly limited, and is usually within a range of 3 to 20.
The aralkyl group means an aromatic hydrocarbon group via an aliphatic hydrocarbon such as a benzyl group or a phenylethyl group, and both the aliphatic hydrocarbon and the aromatic hydrocarbon may be unsubstituted or substituted. The number of carbon atoms in the aliphatic moiety is not particularly limited, and is usually in the range of 1 to 20.
The alkenyl group means an unsaturated aliphatic hydrocarbon group containing a double bond such as a vinyl group, an allyl group, or a butadienyl group, and may be unsubstituted or substituted. The number of carbon atoms of the alkenyl group is not particularly limited, and is usually in the range of 2 to 20.
The cycloalkenyl group means an unsaturated alicyclic hydrocarbon group having a double bond, such as cyclopentenyl group, cyclopentadienyl group, cyclohexenyl group, and the like, and may be unsubstituted or substituted.
The alkynyl group means an unsaturated aliphatic hydrocarbon group containing a triple bond such as an ethynyl group, and may be unsubstituted or substituted. The carbon number of the alkynyl group is not particularly limited, and is usually in the range of 2 to 20.
The alkoxy group means, for example, an aliphatic hydrocarbon group having an ether bond such as a methoxy group, and the aliphatic hydrocarbon group may be unsubstituted or substituted. The number of carbon atoms of the alkoxy group is not particularly limited, and is usually in the range of 1 to 20.
The alkylthio group is a group in which an oxygen atom of an ether bond of an alkoxy group is substituted with a sulfur atom.
The cycloalkylthio group is a group in which an oxygen atom of an ether bond of a cycloalkoxy group is substituted with a sulfur atom.
The aryl ether group means an aromatic hydrocarbon group such as a phenoxy group via an ether bond, and the aromatic hydrocarbon group may be unsubstituted or substituted. The number of carbon atoms of the aryl ether group is not particularly limited, and is usually in the range of 6 to 40.
The arylthioether group is a group in which an oxygen atom of an ether bond of an arylether group is substituted with a sulfur atom.
The aryl group represents, for example, an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, a biphenyl group, a phenanthryl group, a terphenyl group, or a pyrenyl group. The aryl group may be unsubstituted or substituted. The number of carbons of the aryl group is not particularly limited, and is usually in the range of 6 to 40.
The heterocyclic group represents a cyclic structural group having an atom other than carbon, such as a furyl group, a thienyl group, an oxazolyl group, a pyridyl group, a quinolyl group, and a carbazolyl group, and may be unsubstituted or substituted. The number of carbon atoms of the heterocyclic group is not particularly limited, and is usually in the range of 2 to 30.
Halogen means fluorine, chlorine, bromine and iodine.
The aldehyde group, carbonyl group, and amino group may include groups substituted with aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, heterocycles, and the like.
Further, the aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, and heterocyclic ring may be unsubstituted or substituted.
The silyl group means, for example, a silicon compound group such as a trimethylsilyl group, which may be unsubstituted or substituted. The number of carbon atoms of the silyl group is not particularly limited, and is usually in the range of 3 to 20. The number of silicon is usually 1 to 6.
The condensed ring formed between the adjacent substituent is, for example, Ar1And R2、Ar1And R3、Ar2And R2、Ar2And R3、R2And R3、Ar1And Ar2Etc. are conjugated or non-conjugated fused rings formed therebetween. Here, when n is 1, two R's may be used1Form conjugated or non-conjugated condensed rings with each other. These condensed rings may also be present inThe ring-inside structure contains a nitrogen atom, an oxygen atom, and a sulfur atom, and may be condensed with other rings.
Specific examples of the phosphine oxide derivative include the following compounds.
[ solution 337]
Figure BDA0002815937380002841
The phosphine oxide derivative can be produced using an existing raw material and an existing synthesis method.
[ pyrimidine derivative ]
The pyrimidine derivative is, for example, a compound represented by the following formula (ETM-8), and preferably a compound represented by the following formula (ETM-8-1). Details are also described in international publication No. 2011/021689.
[ solution 338]
Figure BDA0002815937380002842
Ar is independently aryl which may be substituted or heteroaryl which may be substituted. n is an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 2 or 3.
Examples of the "aryl group" of the "aryl group which may be substituted" include aryl groups having 6 to 30 carbon atoms, preferably aryl groups having 6 to 24 carbon atoms, more preferably aryl groups having 6 to 20 carbon atoms, and still more preferably aryl groups having 6 to 12 carbon atoms.
Specific "aryl" groups include: phenyl as monocyclic aryl; (2-, 3-, 4-) biphenyl as a bicyclic aryl group; (1-, 2-) naphthyl as a condensed bicyclic aryl; 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, 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 tricyclic aryl groups; 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; tetrabiphenyl group (5' -phenyl-m-terphenyl-2-yl, 5' -phenyl-m-terphenyl-3-yl, 5' -phenyl-m-terphenyl-4-yl, m-quaterphenyl) as a tetracyclic aryl group; triphenylene- (1-, 2-) yl, pyrene- (1-, 2-, 4-) yl, tetracene- (1-, 2-, 5-) yl as condensed tetra-ring system aryl; perylene- (1-, 2-, 3-) group, pentacene- (1-, 2-, 5-, 6-) group, and the like as condensed five-ring system aryl group.
Examples of the "heteroaryl group" of the "heteroaryl group which may be substituted" 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 of the heteroaryl group include heterocyclic rings containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen as ring-constituting atoms in addition to carbon.
Specific examples of the heteroaryl group include: furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzofuranyl, benzo [ b ] thienyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxathiin, thianthrenyl, indolizinyl and the like.
The aryl and heteroaryl groups may be substituted, and may be substituted with, for example, the aryl or heteroaryl groups, respectively.
Specific examples of the pyrimidine derivative include the following compounds.
[ chemical 339]
Figure BDA0002815937380002851
The pyrimidine derivative can be produced using conventional starting materials and conventional synthetic methods.
< carbazole derivative >
The carbazole derivative is, for example, a compound represented by the following formula (ETM-9), or a polymer in which a plurality of carbazole derivatives are bonded to each other by a single bond or the like. The details are described in U.S. patent application publication No. 2014/0197386.
[ solution 340]
Figure BDA0002815937380002861
Ar is independently aryl which may be substituted or heteroaryl which may be substituted. n is independently an integer of 0 to 4, preferably an integer of 0 to 3, more preferably 0 or 1.
Examples of the "aryl group" of the "aryl group which may be substituted" include aryl groups having 6 to 30 carbon atoms, preferably aryl groups having 6 to 24 carbon atoms, more preferably aryl groups having 6 to 20 carbon atoms, and still more preferably aryl groups having 6 to 12 carbon atoms.
Specific "aryl" groups include: phenyl as monocyclic aryl; (2-, 3-, 4-) biphenyl as a bicyclic aryl group; (1-, 2-) naphthyl as a condensed bicyclic aryl; 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, 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 tricyclic aryl groups; 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; tetrabiphenyl group (5' -phenyl-m-terphenyl-2-yl, 5' -phenyl-m-terphenyl-3-yl, 5' -phenyl-m-terphenyl-4-yl, m-quaterphenyl) as a tetracyclic aryl group; triphenylene- (1-, 2-) yl, pyrene- (1-, 2-, 4-) yl, tetracene- (1-, 2-, 5-) yl as condensed tetra-ring system aryl; perylene- (1-, 2-, 3-) group, pentacene- (1-, 2-, 5-, 6-) group, and the like as condensed five-ring system aryl group.
Examples of the "heteroaryl group" of the "heteroaryl group which may be substituted" 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 of the heteroaryl group include heterocyclic rings containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen as ring-constituting atoms in addition to carbon.
Specific examples of the heteroaryl group include: furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzofuranyl, benzo [ b ] thienyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxathiin, thianthrenyl, indolizinyl and the like.
The aryl and heteroaryl groups may be substituted, and may be substituted with, for example, the aryl or heteroaryl groups, respectively.
The carbazole derivative may be a polymer in which a plurality of compounds represented by the formula (ETM-9) are bonded by a single bond or the like. In this case, the bond may be formed through an aryl ring (preferably, a polyvalent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring, or triphenylene ring) in addition to a single bond.
Specific examples of the carbazole derivative include the following compounds.
[ solution 341]
Figure BDA0002815937380002871
The carbazole derivative can be produced using a conventional raw material and a conventional synthesis method.
< triazine derivative >
The triazine derivative is, for example, a compound represented by the following formula (ETM-10), and preferably a compound represented by the following formula (ETM-10-1). The details are described in U.S. patent application publication No. 2011/0156013.
[ solution 342]
Figure BDA0002815937380002872
Ar is independently aryl which may be substituted or heteroaryl which may be substituted. n is an integer of 1 to 3, more preferably 2 or 3.
Examples of the "aryl group" of the "aryl group which may be substituted" include aryl groups having 6 to 30 carbon atoms, preferably aryl groups having 6 to 24 carbon atoms, more preferably aryl groups having 6 to 20 carbon atoms, and still more preferably aryl groups having 6 to 12 carbon atoms.
Specific "aryl" groups include: phenyl as monocyclic aryl; (2-, 3-, 4-) biphenyl as a bicyclic aryl group; (1-, 2-) naphthyl as a condensed bicyclic aryl; 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, 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 tricyclic aryl groups; 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; tetrabiphenyl group (5' -phenyl-m-terphenyl-2-yl, 5' -phenyl-m-terphenyl-3-yl, 5' -phenyl-m-terphenyl-4-yl, m-quaterphenyl) as a tetracyclic aryl group; triphenylene- (1-, 2-) yl, pyrene- (1-, 2-, 4-) yl, tetracene- (1-, 2-, 5-) yl as condensed tetra-ring system aryl; perylene- (1-, 2-, 3-) group, pentacene- (1-, 2-, 5-, 6-) group, and the like as condensed five-ring system aryl group.
Examples of the "heteroaryl group" of the "heteroaryl group which may be substituted" 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 of the heteroaryl group include heterocyclic rings containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen as ring-constituting atoms in addition to carbon.
Specific examples of the heteroaryl group include: furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzofuranyl, benzo [ b ] thienyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxathiin, thianthrenyl, indolizinyl and the like.
The aryl and heteroaryl groups may be substituted, and may be substituted with, for example, the aryl or heteroaryl groups, respectively.
Specific examples of the triazine derivative include the following compounds.
[ solution 343]
Figure BDA0002815937380002881
The triazine derivative can be produced using a conventional raw material and a conventional synthesis method.
< benzimidazole derivative >
The benzimidazole derivative is, for example, a compound represented by the following formula (ETM-11).
[ solution 344]
Phi- (benzimidazole substituent) n (ETM-11)
Phi is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), n is an integer of 1 to 4, the 'benzimidazole substituent' is a substituent in which the pyridyl group in the 'pyridine substituent' of the formula (ETM-2), the formula (ETM-2-1) or the formula (ETM-2-2) is substituted by the benzimidazole group, and at least one hydrogen in the benzimidazole derivative can also be substituted by deuterium.
[ solution 345]
Figure BDA0002815937380002882
R in said benzimidazolyl group11Hydrogen, an alkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or an aryl group having 6 to 30 carbon atoms, and R in the above formulae (ETM-2-1) and (ETM-2-2)11And (4) description.
φ is further preferably an anthracycline or fluorene ring, and the structure in this case can be referred to the description in said formula (ETM-2-1) or formula (ETM-2-2), R in each formula 11～R18Reference may be made to the description in said formula (ETM-2-1) or formula (ETM-2-2). In addition, although the formula (ETM-2-1) or the formula (ETM-2-2) has been described as the form in which two pyridine substituents are bonded, when these are substituted with benzimidazole substituents, two pyridine substituents may be substituted with benzimidazole substituents (that is, n ═ 2), or any one pyridine substituent may be substituted with benzimidazole substituents and R may be substituted with benzimidazole substituents11～R18Substituted with another pyridine substituent (i.e., n ═ 1). Furthermore, R in the formula (ETM-2-1) may be substituted with a benzimidazole substituent11～R18At least one of R and11～R18substituted "pyridine-based substituents".
Specific examples of the benzimidazole derivative include: 1-phenyl-2- (4- (10-phenylanthren-9-yl) phenyl) -1H-benzo [ d ] imidazole, 2- (4- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1-phenyl-1H-benzo [ d ] imidazole, 2- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1-phenyl-1H-benzo [ d ] imidazole, 5- (10- (naphthalen-2-yl) anthracen-9-yl) -1, 2-diphenyl-1H-benzo [ d ] imidazole, 1- (4- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -2-phenyl-1H-imidazole H-benzo [ d ] imidazole, 2- (4- (9, 10-di (naphthalen-2-yl) anthracen-2-yl) phenyl) -1-phenyl-1H-benzo [ d ] imidazole, 1- (4- (9, 10-di (naphthalen-2-yl) anthracen-2-yl) phenyl) -2-phenyl-1H-benzo [ d ] imidazole, 5- (9, 10-di (naphthalen-2-yl) anthracen-2-yl) -1, 2-diphenyl-1H-benzo [ d ] imidazole, and the like.
[ 346]
Figure BDA0002815937380002891
The benzimidazole derivative can be produced using conventional raw materials and conventional synthetic methods.
[ phenanthroline derivative ]
The phenanthroline derivative is, for example, a compound represented by the following formula (ETM-12) or formula (ETM-12-1). The details are described in international publication No. 2006/021982.
[ 347]
Figure BDA0002815937380002892
Phi is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is an integer of 1-4.
Of the formulae R11～R18Each independently represents hydrogen, an alkyl group (preferably an alkyl group having 1 to 24 carbon atoms), a cycloalkyl group (preferably a cycloalkyl group having 3 to 12 carbon atoms) or an aryl group (preferably an aryl group having 6 to 30 carbon atoms). Further, in the formula (ETM-12-1), R11～R18Is bonded to phi as the aryl ring.
At least one hydrogen in each phenanthroline derivative may also be substituted by deuterium.
As R11～R18The alkyl, cycloalkyl and aryl in (1) can be citedR in the formula (ETM-2)11～R18And (4) description. Further, phi includes, for example, the following structural formulae in addition to the above examples. In the following structural formulae, R is independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenyl or terphenyl.
[ Hua 348]
Figure BDA0002815937380002901
Specific examples of the phenanthroline derivative include: 4, 7-diphenyl-1, 10-phenanthroline, 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline, 9, 10-bis (1, 10-phenanthroline-2-yl) anthracene, 2, 6-bis (1, 10-phenanthroline-5-yl) pyridine, 1,3, 5-tris (1, 10-phenanthroline-5-yl) benzene, 9' -difluoro-bis (1, 10-phenanthroline-5-yl), 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline (bathocopine), 1, 3-bis (2-phenyl-1, 10-phenanthroline-9-yl) benzene, and the like.
[ chemical 349]
Figure BDA0002815937380002911
The phenanthroline derivative can be produced using a conventional raw material and a conventional synthesis method.
< hydroxyquinoline-based metal complex >
The hydroxyquinoline metal complex is, for example, a compound represented by the following general formula (ETM-13).
[ solution 350]
Figure BDA0002815937380002912
In the formula, R1～R6Each independently is hydrogen, fluorine, alkyl, cycloalkyl, aralkyl, alkenyl, cyano, alkoxy or aryl, M is Li, Al, Ga, Be or Zn, and n is an integer of 1 to 3.
Specific examples of the hydroxyquinoline metal complex include: lithium 8-quinolinolate, aluminum tris (8-quinolinolate), aluminum tris (4-methyl-8-quinolinolate), aluminum tris (5-methyl-8-quinolinolate), aluminum tris (3, 4-dimethyl-8-quinolinolate), aluminum tris (4, 5-dimethyl-8-quinolinolate), aluminum tris (4, 6-dimethyl-8-quinolinolate), aluminum bis (2-methyl-8-quinolinolate) (phenoxide), aluminum bis (2-methyl-8-quinolinolate) (2-methylphenol), aluminum bis (2-methyl-8-quinolinolate) (3-methylphenol), aluminum bis (2-methyl-8-quinolinolate) (4-methylphenol), aluminum tris (4-methyl-8-quinolinolate), Bis (2-methyl-8-quinolinolato) (2-phenylphenol) aluminum, bis (2-methyl-8-quinolinolato) (3-phenylphenol) aluminum, bis (2-methyl-8-quinolinolato) (4-phenylphenol) aluminum, bis (2-methyl-8-quinolinolato) (2, 3-dimethylphenol) aluminum, bis (2-methyl-8-quinolinolato) (2, 6-dimethylphenol) aluminum, bis (2-methyl-8-quinolinolato) (3, 4-dimethylphenol) aluminum, bis (2-methyl-8-quinolinolato) (3, 5-dimethylphenol) aluminum, bis (2-methyl-8-quinolinolato) (3, 5-di-tert-butylphenol) aluminum, bis (2-methyl-8-quinolinolato) (2, 6-diphenylphenol) aluminum, bis (2-methyl-8-quinolinolato) (2,4, 6-triphenylpheno) aluminum, bis (2-methyl-8-quinolinolato) (2,4, 6-trimethylphenol) aluminum, bis (2-methyl-8-quinolinolato) (2,4,5, 6-tetramethylphenol) aluminum, bis (2-methyl-8-quinolinolato) (1-naphthol) aluminum, bis (2-methyl-8-quinolinolato) (2-naphthol) aluminum, bis (2, 4-dimethyl-8-quinolinolato) (2-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-naphthol) aluminum, bis (2, 4-dimethyl-8-quinolinolato) (3-phenylphenol) aluminum, bis (2, 4-dimethyl-8-quinolinolato) (4-phenylphenol) aluminum, bis (2, 4-dimethyl-8-quinolinolato) (3, 5-dimethylphenol) aluminum, bis (2, 4-dimethyl-8-quinolinolato) (3, 5-di-tert-butylphenol) aluminum, bis (2-methyl-8-quinolinolato) aluminum- μ -oxo-bis (2-methyl-8-quinolinolato) aluminum, bis (2, 4-dimethyl-8-quinolinolato) aluminum- μ -oxo-bis (2, 4-dimethyl-8-quinolinolato) aluminum, aluminum, Bis (2-methyl-4-ethyl-8-quinolinolato) aluminum- μ -oxo-bis (2-methyl-4-ethyl-8-quinolinolato) aluminum, bis (2-methyl-4-methoxy-8-quinolinolato) aluminum- μ -oxo-bis (2-methyl-4-methoxy-8-quinolinolato) aluminum, bis (2-methyl-5-cyano-8-quinolinolato) aluminum- μ -oxo-bis (2-methyl-5-cyano-8-quinolinolato) aluminum, bis (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum- μ -oxo-bis (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum -hydroxyquinoline) aluminum, bis (10-hydroxybenzo [ h ] quinoline) beryllium, and the like.
The hydroxyquinoline metal complex can be produced using a conventional raw material and a conventional synthesis method.
< thiazole derivatives and benzothiazole derivatives >
Examples of the thiazole derivative include compounds represented by the following formula (ETM-14-1).
[ solution 351]
Phi- (thiazole substituent) n (ETM-14-1)
The benzothiazole derivative is, for example, a compound represented by the following formula (ETM-14-2).
[ solution 352]
Phi- (benzothiazole substituent) n (ETM-14-2)
Phi is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), n is an integer of 1 to 4, and the "thiazole substituent" or "benzothiazole substituent" is a substituent in which the pyridyl group in the "pyridine substituent" of the formulae (ETM-2), (ETM-2-1) and (ETM-2-2) is substituted by the following thiazolyl group or benzothiazolyl group, and at least one hydrogen in the thiazole derivative and the benzothiazole derivative may be substituted by deuterium.
[ Change 353]
Figure BDA0002815937380002921
φ is further preferably an anthracycline or fluorene ring, and the structure in this case can be referred to the description in said formula (ETM-2-1) or formula (ETM-2-2), R in each formula11～R18Reference may be made to the description in said formula (ETM-2-1) or formula (ETM-2-2). In addition, although the formula (ETM-2-1) or the formula (ETM-2-2) has been described as a form in which two pyridine substituents are bonded, when these are substituted with a thiazole substituent (or a benzothiazole substituent), two pyridine substituents (i.e., n ═ 2) may be substituted with a thiazole substituent (or a benzothiazole substituent), and one of the pyridine substituents may be substituted with a thiazole substituent (or a benzothiazole substituent) and R may be substituted with an R 11～R18Substituted with another pyridine substituent (i.e., n ═ 1). Furthermore, for example, R in the formula (ETM-2-1) may be substituted with a thiazole-based substituent (or a benzothiazole-based substituent)11～R18At least one of R and11～R18substituted "pyridine-based substituents".
These thiazole derivatives or benzothiazole derivatives can be produced using conventional starting materials and conventional synthetic methods.
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 they have 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 suitably used.
Preferred reducing substances include: an alkali metal such as Na (work function of 2.36eV), K (work function of 2.28eV), Rb (work function of 2.16eV), or Cs (work function of 1.95eV), or an alkaline earth metal such as Ca (work function of 2.9eV), Sr (work function of 2.0 to 2.5eV), or Ba (work function of 2.52eV), and particularly preferably a substance having a work function of 2.9eV or less. Among these, K, Rb or Cs is more preferable as the alkali metal, Rb or Cs is more preferable, and Cs is most preferable. These alkali metals have particularly high reducing power, and by adding a relatively small amount of these alkali metals to a material for forming the electron transporting layer or the electron injecting layer, the emission luminance of the organic EL element can be improved or the lifetime thereof can be prolonged. In addition, as the reducing substance having a work function of 2.9eV or less, a combination of two or more kinds of the 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 reduction ability can be efficiently exhibited, and by adding Cs to a material for forming an electron transport layer or an electron injection layer, the emission luminance of an organic EL element can be improved or the lifetime thereof can be prolonged.
< 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, it is effective to use lithium, sodium, potassium, cesium, calcium, magnesium, or an alloy containing these low work function metals. However, these low work function metals are generally unstable in the atmosphere in many cases. In order to improve this, for example, a method of doping a minute amount of lithium, cesium, or magnesium into an organic layer and using an electrode having high stability is known. As the other dopant, inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide, and cesium oxide can also be used. But is not limited thereto.
Further, the following preferable examples are listed: 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, and hydrocarbon-based polymer compounds are laminated to protect the electrodes. The method for producing 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 alone 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 oxide (polyphenylene oxide), 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 as a polymer binder, or a curable resin such as phenol resin, xylene resin, petroleum resin, urea resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, or silicone resin.
< method for manufacturing organic electroluminescent element >
Each layer constituting the organic electroluminescent 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 manner is not particularly limited, and may be appropriately set according to the properties of the material, but is usually in the range of 2nm to 5000 nm. The film thickness can be measured by a crystal oscillation 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, in general, a heating temperature of +50 ℃ to +400 ℃ and a degree of vacuum of 10 ℃ in a crucible for deposition -6Pa～10-3Pa, 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.
< example of application of organic electroluminescent element >
The present invention can also be applied to a display device including an organic electroluminescent element, a lighting device including an organic electroluminescent element, or the like.
The display device or the lighting device including the organic electroluminescent element can be manufactured by a conventional method such as connecting the organic electroluminescent 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 (for example, refer to 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 (matrix) mode and a segment (segment) mode. Further, the matrix display and the segment display may coexist in the same 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. In this case, a delta type and a stripe type 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 may be more excellent, and therefore the driving method needs to be used in different ways depending on the application.
In the segment 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 on a digital clock or a thermometer, operation state display on an audio device or an induction cooker, panel display on an automobile, and the like.
Examples of the lighting device include: for example, a lighting device for indoor lighting, a backlight (backlight) for a liquid crystal display device, and the like (for example, refer to japanese patent laid-open nos. 2003-257621, 2003-277741, and 2004-119211). The backlight is mainly used for improving visibility of a display device which does not emit light, and is used for a liquid crystal display device, a clock, an audio device, an automobile panel, a display panel, a sign, and the like. In particular, as a backlight for a liquid crystal display device or a personal computer in which thinning is an issue, considering that thinning is difficult in the conventional method including a fluorescent lamp or a light guide plate, the backlight using the light emitting element of the present embodiment has features of thinness 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, or the like, in addition to the organic electroluminescent element.
An organic field effect transistor is a transistor that controls current by an electric field generated by voltage input, and includes a gate electrode in addition to a source 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 is 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 and drain electrodes/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 thus configured can be applied to a liquid crystal display of an active matrix driving method, a pixel driving switching element of an organic electroluminescence display, or the like.
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. The polycyclic aromatic compound of the present invention can function as a hole transport material or an electron transport material in an organic thin film solar cell. The organic thin-film solar cell may also be provided with a hole blocking layer, an electron injection layer, a hole injection layer, a smoothing layer, and the like as appropriate, in addition to the above. 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.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The following are compounds synthesized by examples.
Synthesis example (1)
Compound (BOCz-0001): synthesis of 5-oxa-8 b-aza-15 b-borabenzo [ a ] naphtho [1,2,3-hi ] aceanthrylene
[ solution 354]
Figure BDA0002815937380002951
A flask containing 1, 6-difluoro-2-bromobenzene (1.68ml, 15mmol), carbazole (1.62g, 10mmol), tert-BuOK (1.68g, 15mmol) and 1, 3-dimethyl-2-imidazolidinone (DMI, 30ml) was heated to 120 ℃ under a nitrogen atmosphere and stirred for 20 hours. The reaction solution was cooled to room temperature, and after DMI was distilled off under reduced pressure, the reaction solution was filtered by means of a silica gel short path column (eluent: hexane), and the solvent was distilled off under reduced pressure, whereby 9- (2-bromo-3-fluorophenyl) -9H-carbazole (1.56g, yield 56%) was obtained.
[ solution 355]
Figure BDA0002815937380002952
The structure of the obtained compound was confirmed by Nuclear Magnetic Resonance (NMR) measurement.
1H-NMR(400MHz,CDCl3)：δ＝7.07(d,2H),7.30-7.36(m,4H),7.41(t,2H),7.51(d,1H),8.15(d,2H).
A flask containing phenol (0.367g, 3.9mmol), 9- (2-bromo-3-fluorophenyl) -9H-carbazole (1.02g, 3.0mmol), cesium carbonate (1.47g, 4.5mmol), and N-methylpyrrolidone (NMP, 10ml) was heated to 120 ℃ under a nitrogen atmosphere and stirred for 20 hours. After the reaction solution was cooled to room temperature and toluene (20ml) was added, it was extracted 3 times with a 0.5N aqueous sodium hydroxide solution (50ml), whereby 9- (2-bromo-3-phenoxyphenyl) -9H-carbazole (0.862mg, yield 70%) was obtained.
[ chemical 356]
Figure BDA0002815937380002961
The structure of the obtained compound was confirmed by NMR measurement.
1H-NMR(500MHz,CDCl3)：δ＝7.08-7.14(m,5H),7.19(t,1H),7.25-7.32(m,3H),7.39-7.45(m,5H),8.15(d,2H).
To a flask containing 9- (2-bromo-3-phenoxyphenyl) -9H-carbazole (0.249g, 0.6mmol) and tert-butyl benzene (3.0ml) was added a 1.6M n-butyllithium hexane solution (0.41ml) at-42 ℃ under a nitrogen atmosphere. After stirring for 30 minutes, the temperature was raised to 0 ℃ and the butane bromide was removed by evaporation under reduced pressure for 30 minutes. Thereafter, it was cooled to-42 ℃ and boron tribromide (62.4. mu.l) was added, and stirred for 30 minutes. The temperature was raised to 0 ℃ and N, N-diisopropylethylamine (0.21ml) was added thereto, followed by heating and stirring at 100 ℃ for 15 hours. Thereafter, the mixture was filtered through a short-path column of silica gel (eluent: toluene), and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was then washed with acetonitrile, whereby compound (BOCz-0001) (35.6mg, yield 18%) was obtained.
[ chemical 357]
Figure BDA0002815937380002962
The structure of the obtained compound was confirmed by NMR measurement.
1H-NMR(500MHz,(CDCl3))：δ＝7.28(d,1H),7.37-7.45(m,2H),7.53-7.64(m,3H),7.68(t,1H),7.85(t,1H),8.17-8.20(m,2H),8.33-8.39(dd,2H),8.76-8.81(dd,2H).
13C-NMR(126MHz,(CDCl3))：107.7(1C),109.6(1C),114.4(1C),118.0(1C),120.9(1C),122.1(1C),122.4(1C),122.8(1C),122.9(1C),124.0(1C),126.9(1C),127.0(1C),133.1(1C),133.3(1C),134.1(1C),135.0(1C),140.0(1C),142.5(1C),143.3(1C),159.3(1C),160.0(1C).
No NMR signal of carbon α for boron was observed.
Synthesis example (2)
Compound (BNpCz-12 mS-0230-1): synthesis of N, N, 5-tris (3, 5-dimethylphenyl) -1, 3-dimethyl-5H-5, 8 b-diaza-15 b, borabenzo [ a ] naphtho [1,2,3-hi ] aceanthren-7-amine
[ 358]
Figure BDA0002815937380002963
A flask containing 1-fluoro-3, 5-dibromobenzene (3.77g, 15mmol), carbazole (17.4g, 18mmol), cesium carbonate (9.77g, 30mmol), and N-methylpyrrolidone (NMP, 50ml) was heated to 120 ℃ under a nitrogen atmosphere and stirred for 20 hours. The reaction solution was cooled to room temperature, and after NMP was distilled off under reduced pressure, the solvent was distilled off under reduced pressure by filtration using a silica gel short path column (eluent: hexane), whereby 9- (3, 5-dibromophenyl) -9H-carbazole (2.69g, yield 47%) was obtained.
[ 359]
Figure BDA0002815937380002971
The structure of the obtained compound was confirmed by NMR measurement.
1H-NMR(400MHz,CDCl3)：δ＝7.29(s,2H),7.40-7.46(m,4H),7.70(s,2H),7.76(s,1H),8.12(d,2H).
Under nitrogen atmosphere, bis (3, 5-dimethylphenyl) amine (2.97g, 13mmol), 9- (3, 5-dibromophenyl) -9H-carbazole (0.976g, 5.0mmol), Pd were placed2(dba)3A flask of (54.9mg, 0.060mmol), tri-tert-butylphosphine (24.3mg, 0.12mmol), NaOtBu (1.73g, 18mmol) and toluene (60ml) was heated to 80 ℃ and stirred for 40 hours. The reaction mixture was cooled to room temperature, filtered through a silica gel short path column (eluent: toluene), and the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was washed with methanol, thereby obtaining 5- (9H-carbazol-9-yl) -N as a white solid1,N1,N3,N3Tetrakis (3, 5-dimethylphenyl) benzene-1, 3-diamine (3.66g, 88% yield).
[ solution 360]
Figure BDA0002815937380002972
The structure of the obtained compound was confirmed by NMR measurement.
1H-NMR(400MHz,CDCl3)：δ＝2.23(s,24H),6.64(s,4H),6.72(s,2H),6.76-6.79(m,9H),7.22(t,2H),7.36(d,2H),7.44(d,2H),8.05(d,2H).
Under nitrogen atmosphere, 5- (9H-carbazole-9-yl) -N is put into the reactor at room temperature1,N1,N3,N3A flask of tetrakis (3, 5-dimethylphenyl) benzene-1, 3-diamine (0.207mg, 0.3mmol) and toluene (3.0ml) was charged with boron tribromide (341.7 μ l, 3.6 mmol). After the end of the dropwise addition, the temperature was raised to 130 ℃ and the mixture was stirred for 30 hours. Thereafter, the reaction mixture was cooled to room temperature again, and a phosphoric acid buffer solution (pH7, 20ml) was added to the reaction mixture Of the resulting mixture, the aqueous layer was separated and extracted with dichloromethane (20ml, 3 times). Thereafter, the reaction solution was distilled off to obtain a crude product. The obtained crude product was washed with acetonitrile, whereby compound (BNpCz-12mS-0230-1) (0.160mg, yield 77%) was obtained.
[ solution 361]
Figure BDA0002815937380002981
The structure of the obtained compound was confirmed by NMR measurement.
1H-NMR(500MHz,(CDCl2)2)：δ＝2.24(s,12H),2.30(m,9H),2.84(s,3H),5.79(s,1H),6.42(s,1H),6.75(m,3H),6.79-6.82(m,6H),6.93(s,1H),7.02(s,1H),7.34(t,1H),7.52(t,1H),7.60(s,1H),7.77(d,1H),8.16(d,1H),8.21(d,1H),8.33(d,2H).
13C-NMR(126MHz,CDCl3)：21.2(2C),21.2(4C),22.0(1C),25.0(1C),98.5(1C),101.0(1C),114.0(1C),114.7(1C),120.8(1C),120.9(1C),121.6(1C),121.7(1C),122.6(1C),122.8(1C),123.7(4C),124.0(1C),125.1(1C),125.2(1C),125.7(2C),126.1(1C),127.1(1C),127.5(2C),129.5(1C),134.7(1C),138.8(4C),139.4(1C),140.1(2C),140.3(1C),141.8(1C),142.1(1C),143.2(1C),143.7(1C),146.6(2C),147.3(1C),148.4(1C),151.6(1C).
Synthesis example (3)
Compound (BNpCz-0230): synthesis of N, N, 5-triphenyl-5H-5, 8 b-diaza-15 b-borabenzo [ a ] naphtho [1,2,3-hi ] aceanthrenyl-7-amine
[ solution 362]
Figure BDA0002815937380002982
Under nitrogen atmosphere, 5- (9H-carbazole-9-yl) -N is put into the reactor at room temperature1,N1,N3,N3A flask of (57.6mg, 0.1mmol) tetraphenylbenzene-1, 3-diamine and (1.0ml) toluene was charged with boron tribromide (40.0. mu.l, 0.4 mmol). After the end of the dropwise addition,the temperature is raised to 120 ℃ and the mixture is stirred for 20 hours. Thereafter, the reaction mixture was cooled to room temperature again, a phosphoric acid buffer solution (pH7, 20ml) was added to the reaction mixture, and the aqueous layer was separated and extracted with toluene (40ml, 1 time) and dichloromethane (40ml, 2 times). Thereafter, the reaction solution was purified by means of a silica gel column (eluent: hexane/toluene-2/1 (volume ratio)), whereby compound (BNpCz-0230) (12.6mg, yield 22%) was obtained.
[ solution 363]
Figure BDA0002815937380002991
The structure of the obtained compound was confirmed by NMR measurement.
1H-NMR(400MHz,(CDCl3))：δ＝5.90(s,1H),6.73(d,1H),7.10(s,2H),7.19(d,4H),7.26-7.33(m,9H),7.39(d,2H),7.48-7.52(m,2H),7.61-7.64(m,2H),7.70(d,1H),8.15(d,1H),8.28(d,1H),8.88(d,1H),8.97(d,1H).
Synthesis example (4)
Compound (BNpCz-0230/0611-1): synthesis of 2- (tert-butyl) -N, N, 5-tris (4- (tert-butyl) phenyl) -5H-5,8 b-diaza-15 b-borabenzo [ a ] naphtho [1,2,3-hi ] aceanthren-7-amine
[ solution 364]
Figure BDA0002815937380002992
Under nitrogen atmosphere, N is put into the reactor at room temperature1,N1,N3,N3A flask of (tetrakis (4- (tert-butyl) phenyl) -5- (9H-carbazol-9-yl) benzene-1, 3-diamine (79.8mg, 0.1mmol) and toluene (1.0ml) was charged with boron tribromide (40.0. mu.l, 0.4 mmol). After the end of the dropwise addition, the temperature was raised to 120 ℃ and the mixture was stirred for 20 hours. Thereafter, the reaction mixture was cooled to room temperature again, a phosphoric acid buffer solution (pH7, 20ml) was added to the reaction mixture, and the aqueous layer was separated and extracted with toluene (40ml, 1 time) and dichloromethane (40ml, 2 times). Thereafter, the reaction mixture was purified by silica gel column chromatography (eluent: hexane/toluene 2/1 (volume ratio))The solution was purified, whereby compound (BNpCz-0230/0611-1) (45.1mg, yield 56%) was obtained.
[ solution 365]
Figure BDA0002815937380002993
The structure of the obtained compound was confirmed by NMR measurement.
1H-NMR(400MHz,(CDCl3))：δ＝1.34(s,9H),1.35(s,18H),1.47(s,9H),6.18(s,1H),6.66(s,1H),7.11(d,4H),7.14-7.24(m,8H),7.46-7.52(m,6H),7.58(d,1H),7.62(t,1H),8.14(d,1H),8.27(d,1H).
Synthesis example (5)
Compound (BNpCz-0230/0611/0911S-F26-1): synthesis of 2,11, 14-tri-tert-butyl-N- (4- (tert-butyl) phenyl) -N, 5-bis (2, 6-difluorophenyl) -5H-5,8 b-diaza-15 b-borabenzo [ a ] naphtho [1,2,3-hi ] aceanthren-7-amine
[ solution 366]
Figure BDA0002815937380003001
Under nitrogen atmosphere, N is put into the reactor at room temperature1,N3-bis (4- (tert-butyl) phenyl) -5- (3, 6-di-tert-butyl-9H-carbazol-9-yl) -N1,N3A flask of-bis (2, 6-difluorophenyl) benzene-1, 3-diamine (87.1mg, 0.1mmol) and chlorobenzene (1.0ml) was charged with boron tribromide (40.0. mu.l, 0.4 mmol). After the end of the dropwise addition, the temperature was raised to 140 ℃ and the mixture was stirred for 20 hours. Thereafter, the reaction mixture was cooled to room temperature again, a phosphoric acid buffer solution (pH7, 40ml) was added to the reaction mixture, and the aqueous layer was separated and extracted with dichloromethane (40ml, 3 times). Thereafter, the reaction solution was purified by a silica gel column (eluent: hexane/toluene (volume ratio) 2/1), and the solvent was distilled off under reduced pressure to obtain a crude product. After washing the obtained crude product with hexane, washing was performed with acetonitrile, whereby compound (BNpCz-0230/0611/0911S-F26-1) (12.5mg, yield 14%) was obtained.
[ 367]
Figure BDA0002815937380003002
The structure of the obtained compound was confirmed by NMR measurement.
1H-NMR(500MHz,(CDCl3))：δ＝1.38(s,9H),1.44(s,9H),1.47(s,9H),1.61(s,9H),5.65(s,1H),6.70(d,1H),6.95-6.98(m,2H),7.01-7.05(m,2H),7.26-7.28(m,2H),7.30(d,2H),7.33-7.36(m,1H),7.38-7.40(m,3H),7.50-7.53(m,2H),8.15(s,1H)8.32(s,1H),9.05(s,1H),9.07(s,1H).
13C-NMR(127MHz,(CDCl3))：31.4(3C),31.6(3C),31.7(3C),32.3(3C),34.3(1C),34.5(1C),34.6(1C),35.1(1C),94.0(1C),95.3(1C),112.3(4C),112.5(1C),112.6(1C),112.8(1C),113.2(1C),114.7(1C),116.9(1C),118.5(1C),118.7(1C),119.2(1C),123.1(1C),123.5(1C),125.8(2C),126.3(2C),126.9(1C),127.7(1C),129.4(1C),129.5(1C),129.9(1C),131.5(1C),137.8(1C),141.5(1C),141.9(1C),142.6(1C),144.0(1C),144.1(1C),144.1(1C),144.5(1C),147.7(1C),148.5(1C),152.0(1C),159.3(2C),161.3(2C).
Synthesis example (6)
Compound (BOCz-12 m-0220/0910S-1): synthesis of 7-mesityl-1, 3,11, 14-tetramethyl-5-oxa-8 b-aza-15 b-borabenzo [ a ] naphtho [1,2,3-hi ] aceanthrene
[ solution 368]
Figure BDA0002815937380003011
3, 5-dimethylphenol (6.3g) and 1-bromo-3, 5-difluorobenzene (10g) were dissolved in N-methylpyrrolidone (NMP, 32ml) under a nitrogen atmosphere, and potassium carbonate (14.3g) was added thereto, followed by stirring at 180 ℃ for 6 hours. After the reaction, water and heptane were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Thereafter, the organic layer was concentrated to obtain a crude product. The crude product was purified by means of a silica gel short column (eluent: heptane), whereby 1-bromo-3- (3, 5-dimethylphenoxy) -5-fluorobenzene (12.0g) was obtained.
[ Hua 369]
Figure BDA0002815937380003012
1-bromo-3- (3, 5-dimethylphenoxy) -5-fluorobenzene (11.5g), 2,4, 6-trimethylphenylboronic acid (6.7g), dichlorobis [ (di-tert-butyl (4-dimethylaminophenyl) phosphino) ] palladium (Pd-132, 0.27g) as a palladium catalyst, sodium carbonate (8.2g), tetrabutylammonium bromide (TBAB, 2.5g), water (120ml) and cyclopentyl methyl ether (CPME, 120ml) were put into a flask under a nitrogen atmosphere, and heated under reflux for 3 hours. After the reaction, water and toluene were added to the reaction solution, and the mixture was stirred, and then the organic layer was separated and washed with water. Thereafter, the organic layer was concentrated to obtain a crude product. The crude product was purified by means of a short column of silica gel (eluent: heptane), whereby 3' - (3, 5-dimethylphenoxy) -5' -fluoro-2, 4, 6-trimethyl-1, 1' -biphenyl (11.4g) was obtained.
[ solution 370]
Figure BDA0002815937380003021
3' - (3, 5-dimethylphenoxy) -5' -fluoro-2, 4, 6-trimethyl-1, 1' -biphenyl (8.5g) and 3, 6-dimethyl-9H-carbazole (5.3g) were dissolved in N-methylpyrrolidone (NMP, 34ml) under a nitrogen atmosphere, and cesium carbonate (20.0g) was added thereto and stirred at 180 ℃ for 5 hours. After the reaction, water and toluene were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Thereafter, the organic layer was concentrated to obtain a crude product. The crude product was purified by means of a short column of silica gel (eluent: toluene/heptane-1/2 (volume ratio)), whereby 9- (5- (3, 5-dimethylphenoxy) -2',4',6 '-trimethyl- [1,1' -biphenyl ] -3-yl) -3, 6-dimethyl-9H-carbazole (11.8g) was obtained.
[ 371]
Figure BDA0002815937380003022
9- (5- (3, 5-dimethylphenoxy) -2',4',6 '-trimethyl- [1,1' -biphenyl ] -3-yl) -3, 6-dimethyl-9H-carbazole (3.5g), a 1M boron tribromide-heptane solution (82.4ml), and aluminum chloride (0.96g) were dissolved in chlorobenzene (70ml) under a nitrogen atmosphere, and stirred under heating and reflux for 3 hours. The reaction solution was cooled to room temperature, and an aqueous sodium acetate solution cooled by an ice bath and toluene were sequentially added thereto to separate the reaction solution. The organic layer was concentrated and purified by a short column of silica gel (eluent: toluene/heptane 1/3 (volume ratio)). The obtained crude product was subjected to reprecipitation using heptane, thereby obtaining compound (BOCz-12m-0220/0910S-1) (1.0 g).
[ CHEMICAL 372]
Figure BDA0002815937380003023
The structure of the obtained compound was confirmed by NMR measurement.
1H-NMR(400MHz,(CDCl3))：δ＝2.12(s,6H),2.40(s,3H),2.49(s,3H),2.56(s,3H),2.69(s,3H),2.92(s,3H),7.04(s,2H),7.05(d,1H),7.08(s,1H),7.22(br,1H),7.30(dd,1H),7.89(d,1H),7.98(br,1H),8.09(d,1H),8.13(d,1H),8.32(br,1H).
Synthesis example (7)
Compound (BOCzb-3b 30): synthesis of 14, 14-dimethyl-N, N-diphenyl-14H-8-oxa-4 b-aza-15 b-borabenzo [ a ] indeno [1',2':6,7] naphtho [1,2,3-hi ] acenaphthylene-12-amine
[ 373]
Figure BDA0002815937380003031
Carbazole (1 eq), 1-bromo-3-fluorobenzene (1.2 eq), palladium (II) acetate (Pd (OAc)20.04 equivalent), tri (tert-butyl) phosphine (t-Bu)3P, 0.12 equivalents), potassium phosphate (4 equivalents), and xylene (volume (ml): 10 times the weight (g) of carbazole) was put into a flask And refluxed for 10 hours or more. After the reaction, the reaction solution was cooled, filtered to remove the solid, the filtrate was concentrated under reduced pressure, and the obtained crude product was purified by a silica gel column (eluent: heptane/toluene mixed solvent), whereby 9- (3-fluorophenyl) -9H-carbazole was obtained. At this time, the ratio of toluene in the eluent is gradually increased to elute the target substance.
[ solution 374]
Figure BDA0002815937380003032
A flask containing 7- (diphenylamino) -9, 9-dimethyl-9H-fluoren-3-ol (1 equivalent), 9- (3-fluorophenyl) -9H-carbazole (1 equivalent), potassium carbonate (2.5 equivalents) and NMP (capacity (ml): 4 times the weight (g) of 7- (diphenylamino) -9, 9-dimethyl-9H-fluoren-3-ol) was heated and stirred at reflux temperature under nitrogen atmosphere for 5 hours or more. After completion of the reaction, the reaction solution was cooled to room temperature, water was added thereto, and the precipitated precipitate (crude product) was collected by suction filtration. The obtained crude product was washed with water and methanol in this order, and then purified by a silica gel column (eluent: heptane/toluene mixed solvent), whereby 6- (3- (9H-carbazol-9-yl) phenoxy) -9, 9-dimethyl-N, N-diphenyl-9H-fluoren-2-amine was obtained. At this time, the ratio of toluene in the eluent is gradually increased to elute the target substance.
[ solution 375]
Figure BDA0002815937380003033
In chlorobenzene (capacity (ml): 20 times the weight (g) of 6- (3- (9H-carbazol-9-yl) phenoxy) -9, 9-dimethyl-N, N-diphenyl-9H-fluoren-2-amine), 1M boron tribromide in heptane solution (12 equivalents), and aluminum chloride (1.1 equivalent) were dissolved under a nitrogen atmosphere, and stirred under reflux for 3 hours or more. After the reaction, the reaction solution was cooled to room temperature, and an aqueous sodium acetate solution cooled by an ice bath and toluene were sequentially added thereto to separate the reaction solution. The organic layer was concentrated and purified by means of a silica gel column (eluent: heptane/toluene mixed solvent), whereby compound (BOCzb-3b30) was obtained. At this time, the ratio of toluene in the eluent is gradually increased to elute the target substance.
[ chemical 376]
Figure BDA0002815937380003041
Synthesis example (8)
Compound (BOCza-0530): synthesis of N, N-diphenyl-7-oxa-10 b-aza-17 b-bora-fluorantheno [1,2,3-no ] benzanthracene-5-amine
[ 377]
Figure BDA0002815937380003042
A flask containing 4- (diphenylamino) naphthalen-2-ol (1 equivalent), 9- (3-fluorophenyl) -9H-carbazole (1 equivalent), potassium carbonate (2.5 equivalents) and NMP (volume (ml): 4 times the weight (g) of 4- (diphenylamino) naphthalen-2-ol) was heated and stirred at reflux temperature under nitrogen atmosphere for 5 hours or more. After completion of the reaction, the reaction solution was cooled to room temperature, water was added thereto, and the precipitated precipitate (crude product) was collected by suction filtration. The obtained crude product was washed with water and methanol in this order, and then purified by a silica gel column (eluent: heptane/toluene mixed solvent), whereby 3- (3- (9H-carbazol-9-yl) phenoxy) -N, N-diphenylnaphthalene-1-amine was obtained. At this time, the ratio of toluene in the eluent is gradually increased to elute the target substance.
[ chemical 378]
Figure BDA0002815937380003043
In a nitrogen atmosphere, 3- (3- (9H-carbazol-9-yl) phenoxy) -N, N-diphenoxynaphthalene-1-amine (1 equivalent), 1M boron tribromide heptane solution (12 equivalents), and aluminum chloride (1.1 equivalent) were dissolved in chlorobenzene (capacity (ml): 20 times the weight (g) of 3- (3- (9H-carbazol-9-yl) phenoxy) -N, N-diphenylnaphthalene-1-amine), and the mixture was stirred under reflux with heating for 3 hours or more. After the reaction, the reaction solution was cooled to room temperature, and an aqueous sodium acetate solution cooled by an ice bath and toluene were sequentially added thereto to separate the reaction solution. The organic layer was concentrated and purified by means of a silica gel column (eluent: heptane/toluene mixed solvent), whereby compound (BOCza-0530) was obtained. At this time, the ratio of toluene in the eluent is gradually increased to elute the target substance.
[ solution 379]
Figure BDA0002815937380003051
By appropriately changing the compounds as starting materials, other compounds of the present invention can be synthesized by the methods according to the synthesis examples.
Then, the evaluation of the basic properties of the compound of the present invention, and the production and evaluation of an organic EL device using the compound of the present invention are described.
< evaluation of basic physical Properties >
Preparation of samples
In the case of evaluating the absorption characteristics and the light emission characteristics (fluorescence and phosphorescence) of a compound to be 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, depending on the form of use of the compound to be evaluated in the organic EL element, 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.
As the matrix material, a commercially available transparent polymer such as PMMA (polymethyl methacrylate) or PSt (polystyrene) can be used. Film samples dispersed in PMMA can be made, for example, as follows: PMMA and a compound to be evaluated were dissolved in toluene, and then a thin film was formed on a transparent support substrate (10mm × 10mm) made of quartz by a spin coating method. When other transparent polymers are used, a film can be produced in the same order.
In addition, a method for producing a film sample when the host material is a matrix material is described below. A quartz transparent support substrate (10mm × 10mm × 1.0mm) was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by the long-state industry), and a molybdenum vapor deposition boat containing a host material and a molybdenum vapor deposition boat containing a dopant material were mounted thereon. Then, the vacuum vessel was depressurized to 5X 10-4Pa, the vapor deposition boat containing the host material and the vapor deposition boat containing the host material were heated at the same time, and vapor deposition was performed so as to have an appropriate film thickness, thereby forming a mixed thin film of the host material and the dopant material. The deposition rate is controlled according to the set weight ratio of the host material to the dopant material.
Evaluation of absorption characteristics and light emission characteristics
The absorption spectrum of the sample was measured using an ultraviolet-visible near-infrared spectrophotometer (Shimadzu corporation, UV-2600). The measurement of the fluorescence spectrum or phosphorescence spectrum of the sample was performed using a spectrofluorometer (manufactured by Hitachi high-tech, Ltd., F-7000).
For the measurement of fluorescence spectrum, photoluminescence (photoluminescence) is measured by excitation at an appropriate excitation wavelength at room temperature. For the measurement of 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 light chopper (optical chopper) was used to adjust the delay time from the irradiation of the excitation light to the start of the measurement. The sample is excited at an appropriate excitation wavelength and photoluminescence is measured.
In addition, fluorescence quantum yield (PLQY) was measured using an absolute PL quantum yield measurement device (manufactured by Hamamatsu Photonics (Inc.), C9920-02G).
Evaluation of fluorescence lifetime (delayed fluorescence)
The fluorescence lifetime was measured at 300K using a fluorescence lifetime measuring device (manufactured by Hamamatsu Photonics (Strand), C11367-01). The advance component and the retardation component of the fluorescence lifetime (fluorescence lifetime of 0.1 microsecond (. mu.sec) or more) are observed at the maximum emission wavelength measured at an appropriate excitation wavelength. The fluorescence lifetime of the delayed fluorescence component (delay) was determined from the time constant obtained by fitting (fitting) the intensity (number of photons) of a point (standard, 5 times the fluorescence lifetime of the advanced fluorescence component) at which the advanced fluorescence component could not be observed any more (prompt)) as a starting point and the intensity 1/10 with respect to the starting point as an end point as a single exponential function. In the measurement of the fluorescence lifetime of a general organic EL material emitting fluorescence at room temperature, the triplet component is deactivated by heat, and thus a retardation component in which the triplet component derived from phosphorescence participates is hardly observed. When a delayed component is observed in a compound to be evaluated, triplet energy indicating a long excitation lifetime is shifted to singlet energy by thermal activation, and is observed as delayed fluorescence.
Calculation of energy gap (Eg)
From the long wavelength end a (nm) of the absorption spectrum obtained by the method, Eg 1240/a was calculated.
S T STE. Calculation of E and Δ E
Maximum luminescence wavelength B (nm) according to fluorescence spectrum by ESSinglet excitation energy (E) was calculated as 1240/BS). In addition, the maximum luminescence wavelength C (nm) in the phosphorescence spectrum is measured by ETTriplet excitation energy (E) was calculated as 1240/CT)。
ΔESTIs composed of ESAnd ETEnergy difference of (i.e.. DELTA.E)ST＝ES-ETAnd (4) defining. In addition,. DELTA.ESTFor example, 100% conversion from electro-optical to can also be achieved with "pure organic electroluminescent materials" (pure organic electroluminescent material conversion 100% conversion from electro-optical tolight) ", h.wei, h.suzuki, t.fukushima, f.suzuki, a. jugong, y.village, c.zu (h.kaji, h.suzuki, t.fukushima, k.shizu, k.katsuaki, s.kubo, t.kominio, h.oiwa, f.suzuki, a.wakamiya, y.murata, c.adachi), natural communication (nat.commun.)2015,6,8476.
Evaluation of basic physical Properties of Compound (BOCz-0001)
[ 380]
Figure BDA0002815937380003061
[ absorption characteristics and light-emitting characteristics in Dispersion film ]
As a result of the measurement, deep blue light emission having an absorption peak wavelength of 425nm, a fluorescence peak wavelength of 447nm, a fluorescence peak wavelength of 450nm at 77K, a phosphorescence peak wavelength of 480nm at 77K, a fluorescence peak half-value width of 40nm, and a PLQY of 75% and a narrow half-value width was obtained. In addition, Δ E was calculated from the fluorescence peak wavelength at 77K and the phosphorescence peak wavelength at 77K STIs 0.17 eV.
As described above, the compound (BOCz-0001) emits light in deep blue with a narrow half-value width, and therefore is expected as a fluorescent light-emitting material in deep blue.
Compound (BOCz-0001) achieves high PLQY without decreasing oscillator strength and has a small Δ ESTSince the light-emitting diode emits deep blue light with a narrow half-value width, the light-emitting diode is suitable as a dopant for an Organic Light Emitting Diode (OLED).
Evaluation of basic Properties of Compound (BNpCz-12mS-0230-1)
[ chemical 381]
Figure BDA0002815937380003071
[ absorption characteristics and light-emitting characteristics in a dilute solution ]
Compound (BNpCz-12mS-0230-1) at 2.0X 10-5The concentration of mol/L was dissolved in toluene, and the absorption spectrum and fluorescence spectrum were measured. The excitation wavelength in the fluorescence spectrum measurement is arbitrarily selected so as not to overlap with the fluorescence spectrum.
As a result of the measurement, deep blue light emission having an absorption peak wavelength of 447nm, a fluorescence peak wavelength of 463nm, a fluorescence peak half-value width of 24nm and PLQY of 65% and a narrow half-value width was obtained.
[ delayed fluorescence lifetime in dilute solution ]
The delayed fluorescence lifetime of compound (BNpCz-12mS-0230-1) in solution was measured. The delayed fluorescence lifetime tau (Delay) calculated from the decay curve was 2.4 μ sec.
According to the above, the compound (BNpCz-12mS-0230-1) can obtain deep blue luminescence with narrow half-value width and small Delta ESTAnd small tau (delay), and therefore, is expected as a thermally activated delayed fluorescence material.
[ absorption characteristics and light-emitting characteristics in Dispersion film ]
The absorption property and the luminescence property were measured with respect to a film prepared by dispersing the compound (BNpCz-12mS-0230-1) in PMMA at a concentration of 1% by weight. As a result of the measurement, deep blue light emission having a narrow half-value width of 446nm as an absorption peak wavelength, 465nm as a fluorescence peak wavelength, 466nm as a fluorescence peak wavelength at 77K, 495nm as a phosphorescence peak wavelength at 77K, 30nm as a fluorescence peak half-value width, and 83% PLQY was obtained. In addition, Δ E was calculated from the fluorescence peak wavelength and the phosphorescence peak wavelengthSTIs 0.15 eV.
[ delayed fluorescence lifetime in Dispersion film ]
The delayed fluorescence lifetime was measured with respect to a film prepared by dispersing a compound (BNpCz-12mS-0230-1) in PMMA at a concentration of 1% by weight. The delayed fluorescence lifetime tau (delay) calculated from the decay curve was 26 μ sec.
The compound (BNpCz-12mS-0230-1) is at Z of b ring of general formula (1)1Has a methyl group thereon, and the plane formed by the molecules is deformed, so that the spin-orbit interaction can be enhanced, and a very small delayed fluorescence lifetime can be obtained. On the other hand, the planar deformation of the molecules lowers the oscillator strength, and therefore PLQY is often lowered, However, sufficient PLQY can be obtained by appropriate molecular design. The compound (BNpCz-12mS-0230-1) has good PLQY, very small tau (delay) and very narrow half-value width, and emits light in deep blue, and is therefore suitable as a dopant for OLEDs utilizing the TADF mechanism.
Evaluation of basic Properties of comparative Compound 1
A compound of the formula (1-401) disclosed in International publication No. 2015/102118 was used as comparative compound 1, and the basic properties were evaluated.
[ Hua 382]
Figure BDA0002815937380003081
[ absorption characteristics and light-emitting characteristics in Dispersion film ]
As a result of the measurement, deep blue light emission having an absorption peak wavelength of 439nm, a fluorescence peak wavelength of 456nm, a fluorescence peak wavelength of 459nm at 77K, a phosphorescence peak wavelength of 492nm at 77K, a fluorescence peak half-value width of 36nm, and a PLQY of 86% and a narrow half-value width was obtained. In addition, Δ E was calculated from the fluorescence peak wavelength and the phosphorescence peak wavelengthSTIs 0.20 eV.
[ delayed fluorescence lifetime in Dispersion film ]
The delayed fluorescence lifetime was measured from a film prepared by dispersing comparative compound 1 in PMMA at a concentration of 1 wt%. The delayed fluorescence lifetime tau (delay) calculated from the decay curve was 94 μ sec.
As is clear from the above, Z in the general formula (1)1The comparative compound 1 which is hydrogen can obtain blue light emission with a narrow half-value width, and Δ E STHowever, tau (delay) is extremely small, and is not preferable as a light-emitting material of an OLED element using TADF. In addition, due to Δ ESTSmall, and therefore, there is a possibility that TADF can be expressed by improving the element configuration, but it is expected that roll off is large and performance is poor.
Evaluation of basic Properties of comparative Compound 2
A compound of formula (1-2676) disclosed in International publication No. 2015/102118 was used as comparative compound 2, and the basic properties were evaluated.
[ 383]
Figure BDA0002815937380003082
[ absorption characteristics and light-emitting characteristics in Dispersion film ]
As a result of the measurement, deep blue light emission having an absorption peak wavelength of 444nm, a fluorescence peak wavelength of 465nm, a fluorescence peak wavelength of 468nm at 77K, a phosphorescence peak wavelength of 496nm at 77K, a fluorescence peak half-value width of 29nm, and a PLQY of 95% and a narrow half-value width was obtained. In addition, Δ E was calculated from the fluorescence peak wavelength at 77K and the phosphorescence peak wavelength at 77KSTIs 0.15 eV.
[ delayed fluorescence lifetime in Dispersion film ]
The delayed fluorescence lifetime was measured from a film prepared by dispersing comparative compound 2 in PMMA at a concentration of 1 wt%. The delayed fluorescence lifetime tau (delay) calculated from the decay curve was 48 μ sec.
As is clear from the above, Z in the general formula (1)1 Comparative Compound 2, which is Hydrogen, can obtain blue light emission with a narrow half-value width, and Δ E STHowever, tau (delay) is extremely small, and is not preferable as a light-emitting material of an OLED element using TADF. In addition, due to Δ ESTSmall, and therefore, there is a possibility that TADF can be expressed by improving the element configuration, but it is expected that roll off is large and performance is poor.
Evaluation of basic physical Properties of Compound (BNpCz-0230)
[ 384]
Figure BDA0002815937380003091
[ absorption characteristics and light-emitting characteristics in a dilute solution ]
Compound (BNpCz-0230) was added at 2.0X 10-5The concentration of mol/L was dissolved in toluene, and the absorption spectrum and fluorescence spectrum were measured. Fluorescent lightThe excitation wavelength in spectrometry is arbitrarily selected so as not to overlap with the fluorescence spectrum.
As a result of the measurement, deep blue light emission having an absorption peak wavelength of 444nm, a fluorescence peak wavelength of 457nm, a fluorescence peak half-value width of 23nm (FIG. 2), and PLQY of 88% and a narrow half-value width was obtained.
[ absorption characteristics and light-emitting characteristics in Dispersion film ]
The absorption property and the luminescence property were measured from a film prepared by dispersing the compound (BNpCz-0230) in PMMA at a concentration of 1 wt%. As a result of the measurement, deep blue light emission having a narrow half-value width of 30nm, PLQY 84% and having an absorption peak wavelength of 442nm, a fluorescence peak wavelength of 461nm, a fluorescence peak wavelength of 77K, a phosphorescence peak wavelength of 492nm, a fluorescence peak half-value width of 77K was obtained. In addition, Δ E was calculated from the fluorescence peak wavelength at 77K and the phosphorescence peak wavelength at 77K STIs 0.17 eV.
[ delayed fluorescence lifetime in Dispersion film ]
The delayed fluorescence lifetime was measured from a film prepared by dispersing the compound (BNpCz-0230) in PMMA at a concentration of 1% by weight. The delayed fluorescence lifetime tau (delay) was calculated from the decay curve, and as a result, the delayed fluorescence lifetime tau (delay) was 33. mu.sec.
As described above, the compound (BNpCz-0230) emits light having a deep blue color and a narrow half-value width, and therefore, is expected as a fluorescent light-emitting material having a deep blue color. In addition, the compound (BNpCz-0230) has good PLQY, very small tau (delay), and very narrow half-value width, and emits light in deep blue, and is therefore suitable as a dopant for OLEDs utilizing the TADF mechanism.
Evaluation of basic physical Properties of Compound (BNpCz-0230/0611-1)
[ solution 385]
Figure BDA0002815937380003101
[ absorption characteristics and light-emitting characteristics in a dilute solution ]
Compound (BNpCz-0230/0611-1) was reacted with 2.0×10-5The concentration of mol/L was dissolved in toluene, and the absorption spectrum and fluorescence spectrum were measured. The excitation wavelength in the fluorescence spectrum measurement is arbitrarily selected so as not to overlap with the fluorescence spectrum.
As a result of the measurement, deep blue light emission having an absorption peak wavelength of 448nm, a fluorescence peak wavelength of 462nm, a fluorescence peak half-value width of 26nm (FIG. 2), and a PLQY of 86% and a narrow half-value width was obtained.
[ absorption characteristics and light-emitting characteristics in Dispersion film ]
The absorption characteristics and the emission characteristics were measured with respect to a film prepared by dispersing the compound (BNpCz-0230/0611-1) in PMMA at a concentration of 1% by weight. As a result of the measurement, deep blue light emission having an absorption peak wavelength of 447nm, a fluorescence peak wavelength of 465nm, a fluorescence peak wavelength of 467nm at 77K, a phosphorescence peak wavelength of 498nm at 77K, a fluorescence peak half-value width of 30nm, and a PLQY of 80% and a narrow half-value width was obtained. In addition, Δ E was calculated from the fluorescence peak wavelength at 77K and the phosphorescence peak wavelength at 77KSTIs 0.17 eV.
[ delayed fluorescence lifetime in Dispersion film ]
The delayed fluorescence lifetime was measured from a film prepared by dispersing the compound (BNpCz-0230/0611-1) in PMMA at a concentration of 1% by weight. The delayed fluorescence lifetime tau (delay) was calculated from the decay curve and found to be 31 μ sec.
As described above, the compound (BNpCz-0230/0611-1) emits light in a deep blue color with a narrow half-value width, and is therefore expected as a fluorescent light-emitting material in a deep blue color. In addition, the compound (BNpCz-0230/0611-1) has good PLQY, very small tau (delay), and very narrow half-value width, and emits light in deep blue, and thus is suitable as a dopant for OLEDs utilizing the TADF mechanism.
Evaluation of basic Properties of Compound (BNpCz-0230/0611/0911S-F26-1)
[ solution 386]
Figure BDA0002815937380003102
[ absorption characteristics and light-emitting characteristics in a dilute solution ]
The compound (BNpCz-0230/0611/0911S-F26-1) was added at 2.0X 10-5The concentration of mol/L was dissolved in toluene, and the absorption spectrum and fluorescence spectrum were measured. The excitation wavelength in the fluorescence spectrum measurement is arbitrarily selected so as not to overlap with the fluorescence spectrum.
As a result of the measurement, light emission having a deep blue color with a narrow half width of PLQY 91% and an absorption peak wavelength of 439nm, a fluorescence peak wavelength of 453nm, a fluorescence peak half width of 22nm (FIG. 2) was obtained.
As described above, the compound (BNpCz-0230/0611/0911S-F26-1) emits light in a deep blue color with a narrow half-value width, and is therefore expected as a fluorescent light-emitting material in a deep blue color. In addition, when compared with compound (BNpCz-0230) and compound (BNpCz-0230/0611-1), it was found that: the emission wavelength is shortened by the effect of the substituent of the aryl group having a fluorine atom in the ortho position with respect to the nitrogen atom.
The evaluation results of the basic properties are summarized below.
[ Table 1]
Figure BDA0002815937380003111
< evaluation of organic EL element >
As described above, the compound of the present invention has sufficiently good PLQY and very small tau (delay), and emits deep blue light with a narrow half-value width, and thus is suitable as a dopant for an OLED using a TADF mechanism.
Evaluation item and evaluation method
The evaluation items include a drive voltage (V), an emission wavelength (nm), a CIE chromaticity (x, y), an external quantum efficiency (%), a maximum wavelength (nm), a half-value width (nm), and a roll-off of an emission spectrum. The evaluation items may use values at appropriate light emission luminance.
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 spectral emission luminance (emission spectrum) and the external quantum efficiency were measured as follows. A voltage was applied using a voltage/current generator R6144 manufactured by edwaten test (Advantest), inc., whereby the element was caused to emit light. The spectral radiance in the visible light region was measured from a direction perpendicular to the light-emitting surface using a spectral radiance meter SR-3AR manufactured by TOPCON (TOPCON). Assuming that the light-emitting surface is a perfect diffusion surface, the number obtained by dividing the measured value of the spectral emission luminance 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 integrated over the entire wavelength range to be observed, and the total number of photons emitted from the element is set. The external quantum efficiency is a value obtained by dividing the applied current value by the elementary charge (elementary charge) to obtain the number of carriers injected into the device, and dividing the total number of photons emitted from the device by the number of carriers injected into the device. The half-value width of the emission spectrum is determined as the width between wavelengths around the maximum emission wavelength and the intensity of 50%.
The roll off is a phenomenon in which, when a voltage is applied to the element, the efficiency decreases with the application of the voltage, and is preferably small. In the TADF element, if tau (delay) of the dopant or the auxiliary dopant is large, the roll-off becomes large, and if tau (delay) is small, the roll-off becomes small. As a method for comparing and evaluating the degree of roll off, evaluation can be performed by comparing the efficiencies at luminance or current density at arbitrary two points. Preferably, the efficiency is high and the roll-off is small.
Production of organic EL element
An organic EL element was produced, and a voltage was applied to measure the current density, luminance, chromaticity, external quantum efficiency, and the like. As the structures of the organic EL elements produced, three structures, i.e., the following structure a (table 2), the structure B (table 3), and the structure C (table 4), were selected and evaluated. The components A to C are suitable for the thermally activated delayed fluorescence material. The composition a is an element composition expected to have high efficiency as shown in document (advanced materials 2016,28, 2777-. The component B is an element structure that can be expected to have relatively high efficiency and long-term driving stability as shown in the literature (Scientific Reports, 6,2016,22463). The composition C is an element composition which is adapted to a host material different from the composition A as shown in the literature (Solid Thin Films, 619,2016, 120-124). However, the application of the compound of the present invention is not limited to these configurations, and the film thickness and the constituent material of each layer may be appropriately changed depending on the basic physical properties of the compound of the present invention.
[ Table 2]
(constitution of organic EL element A)
Figure BDA0002815937380003121
In table 2, "HI" is N, N '-diphenyl-N, N' -dinaphthyl-4, 4 '-diaminobiphenyl, "HT" is 4,4',4 "-tris (N-carbazolyl) triphenylamine," EB "is 1, 3-bis (N-carbazolyl) benzene," EMH1 "is 3,3 '-bis (N-carbazolyl) -1,1' -biphenyl," ET "is diphenyl [4- (triphenylsilyl) phenyl ] phosphine oxide. The chemical structure is shown below.
[ 387]
Figure BDA0002815937380003122
< example 1 >
< constitution A: element using Compound (BNpCz-12mS-0230-1) as dopant
A glass substrate (manufactured by Opto Science) having a thickness of 26mm by 28mm by 0.7mm, which was prepared by polishing ITO having a thickness of 200nm formed by sputtering to a thickness of 50nm, 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 the Changzhou industry), and a vapor deposition boat made of tantalum and an aluminum nitride vapor deposition boat made of LiF and aluminum were placed therein, respectively, with HI, HT, EB, EMH1, a compound (BNpCz-12mS-0230-1) and ET being placed therein.
The following layers are sequentially formed on the ITO film of the transparent support substrate. The vacuum vessel was depressurized to 5X 10-4Pa, HI was first heated to deposit a film with a thickness of 40nm, and HT was then heated to deposit a film with a thickness of 15nm, thereby forming a hole layer including two layers. Subsequently, EB was heated to form an electron blocking layer by vapor deposition so that the film thickness became 15 nm. Then, EMH1 was heated together with the compound (BNpCz-12mS-0230-1) to deposit a film having a thickness of 20nm, thereby forming a light-emitting layer. The evaporation rate was adjusted so that the weight ratio of EMH1 to compound (BNpCz-12mS-0230-1) became about 99 to 1. Then, ET was heated to form an electron transport layer by vapor deposition so that the film thickness became 40 nm. The deposition rate of each layer is 0.01 nm/sec to 1 nm/sec. Then, LiF was heated to deposit at a deposition rate of 0.01 nm/sec to 0.1 nm/sec so that the film thickness became 1nm, and aluminum was heated to deposit at a film thickness of 100nm to form a cathode, thereby obtaining an organic EL element. In this case, the deposition rate of aluminum is adjusted to 1 nm/sec to 10 nm/sec.
The luminance, chromaticity, external quantum efficiency, and the like were measured by applying a dc voltage with the ITO electrode as the anode and the aluminum electrode as the cathode.
[ Table 3]
(constitution of organic EL element B)
Figure BDA0002815937380003131
In Table 3, "HAT-CN" is 1,4,5,8,9, 12-hexaazatriphenylhexacyano-nitrile, "Tris-PCz" is 9,9',9 "-triphenyl-9H, 9H', 9H" -3,3',6',3 "-tricarbazole," T2T "is 2,4, 6-Tris [ [1,1 '-biphenyl ] -3-yl ] -1,3, 5-triazine," BPy-TP2 "is 2, 7-bis ([2,2' -bipyridine ] -5-yl) triphenylene. The chemical structure is shown below.
[ 388]
Figure BDA0002815937380003132
< example 2 >
< constitution B: element using Compound (BNpCz-12mS-0230-1) for dopant
A glass substrate (Optic Science) having a thickness of 26mm × 28mm × 0.7mm, prepared by polishing ITO deposited by sputtering to 50nm, was used as a transparent support substrate. The transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (Changzhou industry), and a tantalum vapor deposition crucible containing HAT-CN, Tris-PCz, EMH1, a compound (BNpCz-12mS-0230-1), T2T, and BPy-TP2, and an aluminum nitride vapor deposition crucible containing LiF and aluminum were placed therein, respectively, were mounted.
The following layers are sequentially formed on the ITO film of the transparent support substrate. The vacuum vessel was depressurized to 2.0X 10 -4Pa, HAT-CN was first heated to deposit a film having a thickness of 10nm, and Tris-PCz was then heated to deposit a film having a thickness of 30nm, thereby forming a hole layer including two layers. Then, EMH1 was heated together with the compound (BNpCz-12mS-0230-1) to deposit a film having a thickness of 30nm, thereby forming a light-emitting layer. The evaporation rate was adjusted so that the weight ratio of EMH1 to compound (BNpCz-12mS-0230-1) became about 90 to 10. Subsequently, T2T was heated to deposit a film having a thickness of 10nm, and BPy-TP2 was deposited to a thickness of 30nm, thereby forming an electron transport layer including two layers. The deposition rate of each layer is 0.01 nm/sec to 1 nm/sec. Then, LiF is heated to be deposited at a deposition rate of 0.01 nm/sec to 0.1 nm/sec so that the film thickness becomes 1nm, and aluminum is heated to be deposited at a deposition rate of 0.1 nm/sec to 2 nm/sec so that the film thickness becomes 100nm, thereby forming a cathode, whereby an organic EL element can be obtained.
[ Table 4]
(constitution of organic EL element C)
Figure BDA0002815937380003141
In Table 4, "2 CZBN" is 3, 4-bis (9H-carbazol-9-yl) benzonitrile. The chemical structure is shown below.
[ Hua 389]
Figure BDA0002815937380003142
< example 3 >
< formation C: element using Compound (BNpCz-12mS-0230-1) for dopant
A glass substrate (Optic Science) having a thickness of 26mm × 28mm × 0.7mm, prepared by polishing ITO deposited by sputtering to 50nm, was used as a transparent support substrate. The transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (Changzhou industry), and a crucible for vapor deposition of tantalum and a crucible for vapor deposition of aluminum nitride containing LiF and aluminum were placed in the crucible for vapor deposition of tantalum, in which HAT-CN, Tris-PCz, EB, 2CzBN, a compound (BNpCz-12mS-0230-1), and BPy-TP2 were placed, respectively.
The following layers are sequentially formed on the ITO film of the transparent support substrate. The vacuum vessel was depressurized to 2.0X 10-4Pa, HAT-CN was heated to deposit a film with a thickness of 10nm, Tris-PCz was heated to deposit a film with a thickness of 25nm, and EB was heated to deposit a film with a thickness of 10nm, thereby forming a hole layer including three layers. Then, 2CzBN was heated together with the compound (BNpCz-12mS-0230-1) to form a light-emitting layer by vapor deposition so that the film thickness became 30 nm. The deposition rate was adjusted so that the weight ratio of 2CZBN to the compound (BNpCz-12mS-0230-1) became about 90 to 10. Subsequently, 2CzBN was heated to form a film thickness of 10nm, and BPy-TP2 was subsequently vapor-deposited to form a film thickness of 40nm, thereby forming an electron transport layer including two layers. Each layer The deposition rate of (2) is 0.01 nm/sec to 1 nm/sec. Then, LiF is heated to be deposited at a deposition rate of 0.01 nm/sec to 0.1 nm/sec so that the film thickness becomes 1nm, and aluminum is heated to be deposited at a deposition rate of 0.1 nm/sec to 2 nm/sec so that the film thickness becomes 100nm, thereby forming a cathode, whereby an organic EL element can be obtained.
Then, elements of configuration D shown in table 5 were produced. The composition D is a composition in which the charge balance in the light-emitting layer is adjusted by changing the host of the composition a which is a composition suitable for the thermally activated delayed fluorescence material. However, the application of the compound of the present invention is not limited to these configurations, and the film thickness and the constituent material of each layer may be appropriately changed depending on the basic physical properties of the compound of the present invention.
[ Table 5]
(constitution of organic EL element D)
Figure BDA0002815937380003151
In Table 5, "BH 1" is 3, 11-di-o-tolyl-5, 9-dioxa-13 b-boranaphtho [3,2,1-de ] anthracene. The chemical structure is shown below.
[ solution 390]
Figure BDA0002815937380003152
< example 4 >
< formation D: element using Compound (BNpCz-12mS-0230-1) for dopant
A glass substrate (manufactured by Opto Science) having a thickness of 26mm by 28mm by 0.7mm, which was prepared by polishing ITO having a thickness of 200nm formed by sputtering to a thickness of 50nm, 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 the Changzhou industry Co., Ltd.), and a tantalum vapor deposition boat containing HI, HT, EB, BH1, a compound (BNpCz-12mS-0230-1) and ET, and an aluminum nitride vapor deposition boat containing LiF and aluminum were placed therein, respectively.
In the transparent branchThe following layers are formed in order on the ITO film of the support substrate. The vacuum vessel was depressurized to 5X 10-4Pa, HI was first heated to deposit a film with a thickness of 40nm, and HT was then heated to deposit a film with a thickness of 15nm, thereby forming a hole layer including two layers. Subsequently, EB was heated to form an electron blocking layer by vapor deposition so that the film thickness became 15 nm. Then, BH1 was heated together with the compound (BNpCz-12mS-0230-1) to form a light-emitting layer by vapor deposition so that the film thickness became 20 nm. The evaporation rate was adjusted so that the weight ratio of BH1 to the compound (BNpCz-12mS-0230-1) became about 99 to 1. Then, ET was heated to form an electron transport layer by vapor deposition so that the film thickness became 30 nm. The deposition rate of each layer is 0.01 nm/sec to 1 nm/sec. Then, LiF was heated to deposit at a deposition rate of 0.01 nm/sec to 0.1 nm/sec so that the film thickness became 1nm, and aluminum was heated to deposit at a film thickness of 100nm to form a cathode, thereby obtaining an organic EL element. In this case, the deposition rate of aluminum is adjusted to 1 nm/sec to 10 nm/sec.
The luminance, chromaticity and external quantum efficiency were measured by applying a dc voltage to the ITO electrode as an anode and the aluminum electrode as a cathode. At 100cd/m2When the emission spectrum was emitted, the full width at half maximum (FWHM) was 26nm and the peak wavelength was 467nm, and deep blue emission with a narrow half width was observed. In addition, 100cd/m2The external quantum efficiency in light emission was 17.8% in 1000cd/m2The external quantum efficiency in light emission was 11.8%, and a high quantum efficiency was obtained.
< comparative example 1 >
< constitution A: element Using comparative Compound 2 for dopant
An EL element was obtained in the same procedure and composition as in example 4, except that the dopant was changed to comparative compound 2. At 100cd/m2When the light emission was carried out, the full width at half maximum (FWHM) of the emission spectrum was 27nm and the peak wavelength was 464nm, and deep blue emission with a narrow full width at half maximum was observed. On the other hand, in 100cd/m2External quanta in light emissionThe efficiency was 13.8% in 1000cd/m2The external quantum efficiency in light emission was 5.5%, which was lower than that in example 4 and the roll-off was also large.
Then, elements of composition E shown in table 6 were produced. The composition E is a composition suitable for use in Triplet-Triplet Fusion (TTF: singlet generation by Triplet quenching) in the light-emitting layer. However, the application of the compound of the present invention is not limited to these configurations, and the film thickness and the constituent material of each layer may be appropriately changed depending on the basic physical properties of the compound of the present invention.
[ Table 6]
(constitution of organic EL element E)
Figure BDA0002815937380003161
In Table 6, "HI 2" is N4,N4'-diphenyl-N4,N4'-bis (9-phenyl-9H-carbazol-3-yl) - [1,1' -biphenyl]-4,4 '-diamine, "HT 2" is N- ([1,1' -biphenyl)]-4-yl) -9, 9-dimethyl-N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl) -9H-fluoren-2-amine, "HT 3" is N, N-bis (4- (dibenzo [ b, d ] s]Furan-4-yl) phenyl) - [1, 1': 4', 1' -terphenyl]-4-amine, "EMH 2" is 2- (10-phenylanthracen-9-yl) naphtho [2,3-b]Benzofuran and ET2 is 4,6,8, 10-tetraphenyl [1,4 ]]Benzoxaborole heterocyclohexeno [2,3,4-k1]Phenoxyboron heterocyclohexene, "ET 3," is 3,3' - ((2-phenylanthracene-9, 10-diyl) bis (4, 1-phenylene)) bis (4-methylpyridine). The chemical structure is shown below together with "Liq".
[ 391]
Figure BDA0002815937380003171
< example 5 >
< element with EMH2 as host and BOCz-0001 as dopant >
A glass substrate (manufactured by Opto Science) having a thickness of 26mm × 28mm × 0.7mm, which was prepared by polishing ITO having a thickness of 180nm formed 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 (jet)), and a molybdenum vapor deposition boat and an aluminum nitride vapor deposition boat were loaded with HI2, HAT-CN, HT2, HT3, EMH2, compound (BOCz-0001), ET2, and ET3, respectively, and Liq, LiF, and aluminum, respectively.
The following layers are sequentially formed on the ITO film of the transparent support substrate. The vacuum vessel was depressurized to 5X 10-4Pa, HI2 was heated to form a hole layer including four layers, i.e., first, vapor deposition was performed so that the film thickness became 40nm, then HAT-CN was heated to form vapor deposition so that the film thickness became 5nm, then HT2 was heated to form vapor deposition so that the film thickness became 45nm, and then HT3 was heated to form vapor deposition so that the film thickness became 10 nm. Then, EMH2 was heated together with the compound (BOCz-0001) to form a light-emitting layer by vapor deposition so that the film thickness became 25 nm. The deposition rate was adjusted so that the weight ratio of EMH2 to compound (BOCz-0001) became about 98 to 2. Further, ET2 was heated to be deposited with a film thickness of 5nm, and then ET3 was simultaneously heated with Liq to be deposited with a film thickness of 25nm, thereby forming an electron layer including two layers. The deposition rate was adjusted so that the weight ratio of ET3 to Liq became about 50 to 50. The vapor deposition is performed at a vapor deposition rate of each layer of 0.01 nm/sec to 1 nm/sec. Then, LiF was heated to deposit at a deposition rate of 0.01 nm/sec to 0.1 nm/sec so that the film thickness became 1nm, and aluminum was heated to deposit at a film thickness of 100nm to form a cathode, thereby obtaining an organic EL element.
A direct current voltage was applied to the ITO electrode as an anode and the LiF/aluminum electrode as a cathode, thereby obtaining blue light emission.
Then, elements of composition E shown in table 7 were produced. The composition F is a composition of an auxiliary dopant suitable for a thermally activated delayed fluorescence material. The composition F is an element composition expected to have high efficiency as shown in document (advanced materials 2016,28, 2777-2781). In the constitution F, the auxiliary dopant is a thermally activated delayed fluorescence material, and the host and the light emitting dopant (emissive dopant) may or may not be a thermally activated delayed fluorescence material. However, the application of the compound of the present invention is not limited to these configurations, and the film thickness and the constituent material of each layer may be appropriately changed depending on the basic physical properties of the compound of the present invention.
[ Table 7]
(constitution of organic EL element F)
Figure BDA0002815937380003181
The chemical structure of compound (2PXZ-TAZ) in Table 7 is shown below.
[ 392]
Figure BDA0002815937380003182
< example 6 >
< formation F: element > wherein EMH1 is used as the host compound, 2PXZ-TAZ is used as the auxiliary dopant, and BNpCz-12mS-0230-1 is used as the light-emitting dopant
A glass substrate (manufactured by Opto Science) having a thickness of 26mm by 28mm by 0.7mm, which was prepared by polishing ITO having a thickness of 200nm formed by sputtering to a thickness of 50nm, 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 the Changzhou industry Co., Ltd.), and a tantalum vapor deposition boat in which HI, HT, EB, EMH1, a compound (2PXZ-TAZ), a compound (BNpCz-12mS-0230-1), and ET were placed and an aluminum nitride vapor deposition boat in which LiF and aluminum were placed, respectively, were mounted.
The following layers are sequentially formed on the ITO film of the transparent support substrate. The vacuum vessel was depressurized to 5X 10-4Pa, HI was first heated to deposit a film with a thickness of 40nm, and HT was then heated to deposit a film with a thickness of 15nm, thereby forming a hole layer including two layers. Then, EB was heated to be deposited so that the film thickness became 15nm, thereby formingAn electron blocking layer. Then, EMH1 as a host, a compound (2PXZ-TAZ) as an auxiliary dopant, and a compound (BNpCz-12mS-0230-1) as a light-emitting dopant were heated at the same time, and co-evaporation was performed so that the thickness of the layer became 20nm to form a light-emitting layer. The deposition rate was adjusted so that the weight ratio of the host, the auxiliary dopant, and the light-emitting dopant was about 90 to 9 to 1. Then, ET was heated to form an electron transport layer by vapor deposition so that the film thickness became 30 nm. The deposition rate of each layer is set to 0.01 nm/sec to 1 nm/sec. Then, LiF was heated to deposit at a deposition rate of 0.01 nm/sec to 0.1 nm/sec so that the film thickness became 1nm, and aluminum was heated to deposit at a film thickness of 100nm to form a cathode, thereby obtaining an organic EL element. In this case, the deposition rate of aluminum is adjusted to 1 nm/sec to 10 nm/sec.
When a dc voltage was applied to the ITO electrode as an anode and the aluminum electrode as a cathode, deep blue (deep blue) light emission was observed.
< evaluation as TADF Compound >
Subsequently, the structure of the light emitting material having TADF activity was designed using density functional reliability (DFT) calculation. After the ground state structure is optimized by the B3LYP/6-31G (d) method, the Time-dependent DFT method is used to calculate the vertical excitation energy from the ground state, and the singlet excitation energy (E) is usedS) The emission wavelength is predicted. All calculations were performed using the quantum chemical calculation program Firefly (Firefly) (a.a. glanorvsky, Firefly (Firefly) version (version) 8).
< calculation reference example 1 >
The singlet excitation energy of reference compound 1 was 2.9040eV, and 427nm as converted into a wavelength. The reference compound 1 was synthesized by the method described in Japanese patent application No. 2017-562549, and the luminescence wavelength in the 1% PSt dispersion film was measured to be 448 nm. By calculation, the emission wavelength was 21nm, which is on the long wavelength side, compared with the wavelength expected from the singlet excitation energy.
[ 393]
Figure BDA0002815937380003191
In the case of a molecule having the structure of the present invention, the emission wavelength of the compound was determined on the basis of the assumption that the calculated reference example 1 has the same tendency as the measured value. Specifically, assume that: the actual emission wavelength may be longer by about 21nm as compared with the calculation result of the excited singlet energy.
< calculation example 1 >
Since the singlet excitation energy of the compound (BOCzb-3b30) was 2.7943eV and 444nm in terms of wavelength, the expected light emission wavelength was 465 nm. From the calculation results, the compound (BOCzb-3b30) was expected to obtain blue light emission.
[ 394]
Figure BDA0002815937380003201
< calculation example 2 >
Since the singlet excitation energy of the compound (BOCzb-0211S/3b30) was 2.8048eV and 442nm in terms of wavelength, the expected emission wavelength was 463 nm. From the calculation results, it is expected that the compound (BOCzb-0211S/3b30) obtains blue light emission.
[ Hua 395]
Figure BDA0002815937380003202
< calculation example 3 >
The singlet excitation energy of the compound (BOCza-0530) was 2.8146eV, and 441nm in terms of wavelength, and thus the expected emission wavelength was 462 nm. From the calculation results, it is expected that the compound (BOCza-0530) obtains blue luminescence.
[ 396]
Figure BDA0002815937380003203
< calculation example 4 >
Since the singlet excitation energy of the compound (BOCza-0530/0911S) was 2.8122eV and 441nm in terms of wavelength, the expected emission wavelength was 462 nm. From the calculation results, it is expected that the compound (BOCza-0530/0911S) obtains blue light emission.
[ solution 397]
Figure BDA0002815937380003211
Industrial applicability
In the present invention, by providing a novel polycyclic aromatic compound, the material for organic EL elements can be increased in the options. Further, by using a novel polycyclic aromatic compound as a material for an organic electroluminescent element, an excellent organic EL element, a display device provided with the same, an illumination device provided with the same, and the like can be provided.
Description of the symbols
100: organic electroluminescent 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

Claims (27)

1. A polycyclic aromatic compound represented by the following general formula (1) or a polymer of a polycyclic aromatic compound having a plurality of structures represented by the following general formula (1),
[ solution 1]
Figure FDA0002815937370000011
(in the above-mentioned formula (1),
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13and R14Each independently hydrogen, aryl, heteroaryl, diarylamino, diarylboron (two aryl groups may be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, or aryloxy, at least one of which may be further substituted with aryl, heteroaryl, alkyl, or cycloalkyl, and R1～R3、R4～R7、R8～R10And R11～R14Wherein adjacent groups may be bonded to each other and form an aryl or heteroaryl ring together with at least one of the a, b, c and d rings, at least one hydrogen in the formed ring may be substituted by an aryl, heteroaryl, diarylamino, diarylboron (two aryl groups may be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy or aryloxy group, at least one hydrogen of which may in turn be substituted by an aryl, heteroaryl, alkyl or cycloalkyl group,
X is > O, > N-R, > S or > Se, R > N-R being aryl, heteroaryl, alkyl or cycloalkyl, at least one of which may be substituted by aryl, heteroaryl, alkyl or cycloalkyl,
l is a single bond, > C (-R)2O, > S and > N-R, said > C (-R)2And R in N-R are each independently hydrogen, aryl, heteroaryl, diarylamino, diarylboryl (two aryl groups may be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, or aryloxy, at least one of which hydrogen may be further substituted by aryl, heteroaryl, alkyl, or cycloalkyl,
wherein, when X is > N-R, L is not > O,
in the case of multimers, R in the following formula (1)2Is hydrogen and, furthermore,
at least one hydrogen in the compound and the structure represented by the general formula (1) may be substituted with cyano, halogen, or deuterium).
2. The polycyclic aromatic compound or multimer thereof according to claim 1, wherein
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13And R14Independently represents hydrogen, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a diarylamino group (wherein each aryl group is an aryl group having 6 to 12 carbon atoms), a diarylboron group (wherein each aryl group is an aryl group having 6 to 12 carbon atoms, and two aryl groups may be bonded via a single bond or a linking group), an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryloxy group having 6 to 30 carbon atoms, at least one hydrogen of these groups may be further substituted by an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms, and R is 1～R3、R4～R7、R8～R10And R11～R14Wherein adjacent groups are 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 at least one of the a, b, c and d rings, at least one hydrogen in the formed 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 each aryl group is an aryl group having 6 to 12 carbon atoms), a diarylboron group (wherein each aryl group is an aryl group having 6 to 12 carbon atoms and both aryl groups may be bonded via a single bond or a linking group), an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or an aryloxy group having 6 to 30 carbon atoms, and at least one hydrogen in these groups is further substituted by an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms,
x is > O, > N-R, > S or > Se, wherein R > N-R is aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, alkyl having 1 to 12 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, and at least one hydrogen of these groups may be substituted by aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, alkyl having 1 to 12 carbon atoms or cycloalkyl having 5 to 10 carbon atoms,
l is a single bond, > C (-R)2O, > S and > N-R, said > C (-R) 2And R in the > N-R independently represents hydrogen, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a diarylamino group (wherein each aryl group is an aryl group having 6 to 12 carbon atoms), a diarylboron group (wherein each aryl group is an aryl group having 6 to 12 carbon atoms and both aryl groups may be bonded via a single bond or a linking group), an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or an aryloxy group having 6 to 30 carbon atoms, at least one hydrogen of these groups being further substituted by an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms,
wherein, when X is > N-R, L is not > O,
in the case of multimers, R in the following formula (1)2Is hydrogen and, furthermore,
at least one hydrogen in the compound and the structure represented by the general formula (1) may be substituted by cyano, halogen or deuterium.
3. The polycyclic aromatic compound or multimer thereof according to claim 1 or 2, wherein R4～R7Wherein the adjacent groups are bonded to each other and form an aryl ring or heteroaryl ring together with the b ring, selected from the group consisting of a naphthalene ring, a phenanthrene ring, an anthracene ring, a dibenzofuran ring, a carbazole ring, a dibenzothiophene ring, a silafluorene ring, a fluorene ring, and a ring in which benzene rings are condensed on these rings.
4. The polycyclic aromatic compound or multimer thereof according to claim 3, wherein R4～R7Wherein the aryl ring or heteroaryl ring, which is formed together with the b ring and to which adjacent groups are bonded, is a ring represented by the following partial structural formula (1a), formula (1b) or formula (1c),
[ solution 2]
Figure FDA0002815937370000021
In the following formulas, the first and second groups,
R4、R5、R7、R1b、R2b、R3b、R4b、R5band R6bIndependently of one another, hydrogen, aryl, heteroaryl, diarylamino, diarylboron (two aryl groups may be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, or aryloxy, at least one of which hydrogen may in turn be substituted by aryl, heteroaryl, alkyl, or cycloalkyl,
x is > O, > N-R, > S or > Se, R > N-R being aryl, heteroaryl, alkyl or cycloalkyl, at least one of which may be substituted by aryl, heteroaryl, alkyl or cycloalkyl,
z is > O, > N-R, > S, > Si (-R)2And > C (-R)2The > N-R, > Si (-R)2And > C (-R)2Wherein R is independently hydrogen, aryl, heteroaryl, diarylamino, diarylboron (two aryl groups may be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, or aryloxy, at least one of which may be further substituted with aryl, heteroaryl, alkyl, or cycloalkyl.
5. The polycyclic aromatic compound or multimer thereof according to any one of claims 1 to 4, wherein R > N-R as said X is aryl or heteroaryl, at least one hydrogen of which is substituted with fluorine.
6. The polycyclic aromatic compound or the multimer thereof according to any one of claims 1 to 4, wherein R > N-R as said X is an aryl or heteroaryl group, at least one hydrogen in the ortho position with respect to the N in said aryl or heteroaryl group being substituted with fluorine.
7. The polycyclic aromatic compound or the multimer thereof according to any one of claims 1 to 6, wherein L is a single bond, > O, or > N-R.
8. The polycyclic aromatic compound or the multimer thereof according to any one of claims 1 to 6, wherein L is a single bond.
9. The polycyclic aromatic compound or the multimer thereof according to any one of claims 1 to 4, wherein X is > O and L is a single bond.
10. The polycyclic aromatic compound or the multimer thereof according to any one of claims 1 to 6, wherein X is > N-R, L is a single bond.
11. The polycyclic aromatic compound or multimer thereof according to any one of claims 1 to 10, wherein R7And R8One of them is halogen, alkyl group having 1 to 6 carbon atoms, cycloalkyl group having 3 to 14 carbon atoms, aryl group having 6 to 10 carbon atoms or heteroaryl group having 2 to 10 carbon atoms, and the other is hydrogen, alkyl group having 1 to 6 carbon atoms, cycloalkyl group having 3 to 14 carbon atoms, aryl group having 6 to 10 carbon atoms or heteroaryl group having 2 to 10 carbon atoms.
12. The polycyclic aromatic compound or multimer thereof according to any one of claims 1 to 10, wherein R7And R8Wherein one is halogen, alkyl group having 1 to 4 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms or phenyl group, and the other is hydrogen, alkyl group having 1 to 4 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms or phenyl group.
13. The polycyclic aromatic compound or multimer thereof according to any one of claims 1 to 10, wherein R7And R8One is methyl, tert-butyl or phenyl and the other is hydrogen, methyl, tert-butyl or phenyl.
14. The polycyclic aromatic compound or multimer thereof according to any one of claims 1 to 10, wherein R7And R8One is methyl or tert-butyl and the other is hydrogen or methyl.
15. The polycyclic aromatic compound or multimer thereof according to any one of claims 1 to 10, whichIn R7And R8Wherein one is methyl and the other is hydrogen, and when X is > N-R, R > N-R is phenyl, and at least one hydrogen in the phenyl is substituted by aryl having 6 to 12 carbon atoms, heteroaryl having 2 to 10 carbon atoms, alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 14 carbon atoms, or fluorine.
16. The polycyclic aromatic compound or the multimer thereof according to claim 1, which is represented by any one of the following formulae,
[ solution 3]
Figure FDA0002815937370000041
[ solution 4]
Figure FDA0002815937370000042
[ solution 5]
Figure FDA0002815937370000043
[ solution 6]
Figure FDA0002815937370000051
[ solution 7]
Figure FDA0002815937370000052
[ solution 8]
Figure FDA0002815937370000061
(Me in each of the formulae mentioned is methyl and tBu is tert-butyl).
17. The polycyclic aromatic compound according to claim 1, which is represented by any one of the following formulae,
[ solution 9]
Figure FDA0002815937370000062
[ solution 10]
Figure FDA0002815937370000063
[ solution 11]
Figure FDA0002815937370000071
[ solution 12]
Figure FDA0002815937370000072
[ solution 13]
Figure FDA0002815937370000081
[ solution 14]
Figure FDA0002815937370000082
(Me in each of the formulae mentioned is methyl and tBu is tert-butyl).
18. The polycyclic aromatic compound according to claim 1, which is represented by any one of the following formulae,
[ solution 15]
Figure FDA0002815937370000091
[ solution 16]
Figure FDA0002815937370000092
[ solution 17]
Figure FDA0002815937370000093
(Me in each of the formulae mentioned is methyl and tBu is tert-butyl).
19. A material for organic devices, comprising the polycyclic aromatic compound according to any one of claims 1 to 18 or a multimer thereof.
20. The material for organic devices according to claim 19, wherein the material for organic devices is a material for organic electroluminescent elements, a material for organic field effect transistors, or a material for organic thin film solar cells.
21. The material for an organic device according to claim 20, wherein the material for an organic electroluminescent element is a material for a light-emitting layer.
22. An organic electroluminescent element comprising: a pair of electrodes including an anode and a cathode; and a light-emitting layer which is arranged between the pair of electrodes and contains the material for a light-emitting layer according to claim 21.
23. The organic electroluminescent element according to claim 22, wherein the light-emitting layer further contains a compound represented by the following general formula (3) and/or a compound represented by the following general formula (4),
[ solution 18]
Figure FDA0002815937370000101
(in the general formula (3), L1Is an arylene group having 6 to 30 carbon atoms or a heteroarylene group having 2 to 30 carbon atoms,
in the general formula (4), L2And L3Each independently an aryl group having 6 to 30 carbon atoms or a heteroaryl group having 2 to 30 carbon atoms,
at least one hydrogen in the compound represented by each formula is substituted by 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).
24. The organic electroluminescent element according to claim 22 or 23, wherein the light-emitting layer further contains a compound represented by the following general formula (5),
[ solution 19]
Figure FDA0002815937370000102
(in the general formula (5) mentioned above,
R1～R11each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboron (two aryl groups may be bonded via a single bond or a linking group), alkyl, or cycloalkyl, at least one of which hydrogen may in turn be substituted by aryl, heteroaryl, diarylamino, diarylboron (two aryl groups may be bonded via a single bond or a linking group), alkyl, or cycloalkyl,
R1～R11Wherein adjacent groups may be bonded to each other and form an aryl or heteroaryl ring together with the a, b or c ring, at least one hydrogen in the formed ring may be substituted by an aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboronyl (two aryl groups may be bonded via a single bond or a linking group), alkyl or cycloalkyl group, at least one hydrogen of which may in turn be substituted by an aryl, heteroaryl, diarylamino, diarylboronyl groupArylboronyl (two aryl groups may be bonded via a single bond or a linking group), alkyl or cycloalkyl,
at least one hydrogen in the compound represented by the general formula (5) may be independently substituted with halogen or deuterium, respectively).
25. The organic electroluminescent element according to any one of claims 22 to 24, which has an electron transport layer and/or an electron injection layer disposed between the cathode and the light-emitting layer, and at least one of the electron transport layer and the electron injection layer contains at least one selected from the group consisting of borane derivatives, pyridine derivatives, fluoranthene derivatives, BO-based derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, and hydroxyquinoline-based metal complexes.
26. The organic electroluminescent element according to claim 25, wherein the electron transport layer and/or the electron injection layer further contains 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.
27. A display device or a lighting device comprising the organic electroluminescent element according to any one of claims 22 to 26.
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