CN114989199A - Polycyclic aromatic compound, and compound, crosslinked product, material, composition and device each containing or using same - Google Patents

Polycyclic aromatic compound, and compound, crosslinked product, material, composition and device each containing or using same Download PDF

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CN114989199A
CN114989199A CN202210202191.4A CN202210202191A CN114989199A CN 114989199 A CN114989199 A CN 114989199A CN 202210202191 A CN202210202191 A CN 202210202191A CN 114989199 A CN114989199 A CN 114989199A
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畠山琢次
小田晋
川角亮介
马场大辅
近藤靖宏
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Kwansei Gakuin Educational Foundation
SK Materials JNC Co Ltd
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SK Materials JNC Co Ltd
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Abstract

The invention provides a polycyclic aromatic compound and a compound containing or usingCompounds, cross-linked bodies, materials, compositions and devices thereof. An organic EL element having a narrow half-value width of the emission spectrum and excellent color purity, and an organic EL element having excellent quantum efficiency and element life are provided by manufacturing an organic EL element using a novel polycyclic aromatic compound represented by the formula (1A) and the formula (1B) as a dopant material, for example. In the formula (1A) and the formula (1B), ring B, ring C, ring D, ring E, ring F and ring G are aryl or heteroaryl, and Y is 1 、Y 2 And Y 3 Each independently > B-, etc. < X 1 And X 2 Each independently is > N-R, > O, etc., and L each independently is a single bond or a linking group.
Figure DDA0003527825400000011

Description

Polycyclic aromatic compound, and compound, crosslinked product, material, composition and device containing or using same
Technical Field
The present invention relates to a 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 each using the polycyclic aromatic compound. In addition, in this specification, an "organic electroluminescent element" may be referred to as an "organic EL (Electroluminescence) element" or simply as an "element".
Background
Conventionally, various studies have been made on display devices using light emitting elements that emit light by an electric field, because they can achieve power saving and reduction in thickness, and further, organic electroluminescent elements including organic materials have been actively studied because they are easy to reduce the weight and increase the size. In particular, active research has been conducted on the development of organic materials having light-emitting characteristics such as blue or green, which are one of the three primary colors of light, and the development of organic materials having charge transport capabilities (having the possibility of becoming semiconductors or superconductors) including holes, electrons, and the like, both of high molecular compounds and low molecular compounds.
The organic EL element has a structure including: a pair of electrodes including an anode and a cathode, and one or more layers which are disposed between the pair of electrodes and include an organic compound. Among the layers containing an organic compound, there are a light-emitting layer, a charge transport/injection layer for transporting or injecting charges such as holes and electrons, and various organic materials suitable for these layers have been developed.
As the material for the light-emitting layer, three kinds of fluorescent materials, phosphorescent materials, and Thermally Activated Delayed Fluorescence (TADF) materials have been conventionally used. For example, a benzofluorene compound and the like have been developed as a fluorescent material (international publication No. 2004/061047), and a noble metal complex having a multidentate ligand and the like have been developed as a phosphorescent material (japanese patent laid-open No. 2014-239225).
In recent years, there has been reported a material obtained by improving an azaboronate derivative (International publication No. 2015/102118). Has a narrow half-value width of light emission in a single peak and has singlet energy (S) 1 ) And triplet energy (T) 1 ) Energy difference (Δ S) 1 T 1 ) The compound having a small conjugated structure is useful as a material for a blue or green light-emitting layer because it can achieve high color purity and high efficiency due to Thermally Activated Delayed Fluorescence (TADF). Further, triplet energy (T) is also required as an electron-transporting material or a hole-transporting material sandwiching the light-emitting layer 1 ) Large compounds with novel conjugated structures.
However, the fluorescent material has a problem of low emission efficiency, the phosphorescent material and the TADF material have problems of wide half-value width of emission spectrum and low color purity of emission although they have high emission efficiency, and the phosphorescent material contains a noble metal, which causes a problem of high price (natural (Nature) vol.492132012 12 th and Applied Physics Letters 75,4 (1999)).
[ Prior art documents ]
[ patent document ]
[ patent document 1] International publication No. 2004/061047
[ patent document 2] Japanese patent laid-open No. 2014-239225
[ patent document 3] International publication No. 2015/102118
[ non-patent document ]
[ non-patent document 1] Natural (Nature) vol.492132012, 12 th month
[ non-patent document 2] Ready-to-use Physics Letters 75,4(1999)
Disclosure of Invention
[ problems to be solved by the invention ]
As described above, various materials have been developed as materials used for organic EL devices, and in order to increase the options for materials for organic EL devices, it is desired to develop materials containing compounds different from conventional compounds. Patent document 3 reports a polycyclic aromatic compound containing boron and an organic EL element using the compound, but in order to further improve element characteristics, a material for a light-emitting layer, particularly a dopant material, which can improve color purity, light-emitting efficiency, and element lifetime is required. As shown in non-patent document 1 or non-patent document 2, the thermally activated delayed fluorescent material or the phosphorescent material that effectively utilizes the heavy atom effect has a problem in that the half-value width of the emission spectrum is wide and the color purity is improved.
Further, since a wet film formation method is currently used as a method for forming an organic layer constituting an organic EL element in addition to a vacuum deposition method, development of an ink material for wet film formation for forming a hole injection layer, a hole transport layer, and a light emitting layer has been actively carried out particularly, and it is also advantageous to search for such an ink material.
[ means for solving problems ]
The present inventors have made extensive studies to solve the above problems, and as a result, have succeeded in producing a novel polycyclic aromatic compound, and have found that the compound is effective as a material having a small difference between singlet energy and triplet energy required for thermally activated delayed fluorescence. Further, the present inventors have found that an excellent thermal activation delayed fluorescence type organic EL element can be obtained by, for example, configuring an organic EL element by disposing a light-emitting layer, which uses such a polycyclic aromatic compound as a dopant material and a compound having a triplet energy larger than that as a host material, between a pair of electrodes, and have completed the present invention.
In the present specification, the chemical structure or the substituent is sometimes represented by a carbon number, but the carbon number in the case of substituting a substituent in the chemical structure or in the case of substituting a substituent on the substituent and the like means the carbon number of each of the chemical structure or the substituent, and does not mean the total carbon number of the chemical structure and the substituent or the total carbon number of the substituent and the substituent. For example, the "substituent B having a carbon number Y substituted with the substituent a having a carbon number X" means that the "substituent a having a carbon number X" is substituted with the "substituent B having a carbon number Y, and the carbon number Y is not the total carbon number of the substituent a and the substituent B. For example, the "substituent B having a carbon number Y substituted with the substituent a" means that the substituent a "(not limited to a carbon number) is substituted with the" substituent B having a carbon number Y "and the carbon number Y is not the total carbon number of the substituent a and the substituent B.
Since the chemical structural formula described in the present specification (including a general formula represented by a markush structural formula) is a planar structural formula, various isomer structures such as an enantiomer (enantiomer), a diastereomer, or a rotamer may actually exist. In the present specification, unless otherwise specified, the compound described may have any isomeric structure that can be considered from its planar structural formula, and may be a mixture of possible isomers in any ratio.
In the present specification, structural formulae of a plurality of aromatic compounds are described. An aromatic compound is described by combining a double bond and a single bond, but actually, since pi electron resonance occurs, there is an equivalent resonance structure such that a plurality of double bonds and single bonds are alternately replaced with each other for a single substance. In the present specification, only one resonance structure is described for one substance unless otherwise specifiedThe description also includes other resonance structural formulas which are equivalent in organic chemistry. The above-mentioned case is referred to in the description of "optional" — C (-R) ═ optionally substituted "— N ═ or" the like to be described later (R is defined as R at that time a 、R b 、R c 、R d 、R e 、R f Or R g Etc.). That is, for example, "-C (-R) —" in formula (2A) described later is as follows, as an example. However, the present invention is not limited to the above, and it is needless to say that the present invention is applicable to not only one resonance structural formula described but also other equivalent resonance structural formulas.
[ solution 1]
Figure BDA0003527825380000031
Unless otherwise specified, the description that "any" — C (-R) ═ "may be substituted with" — N ═ "is applicable to all structural formulae in the present specification. In addition, R of the above-mentioned-C (-R) ═ is a substituent which is defined by its ring structure at that time.
In the present specification, the expression "may" and the expression "do not mean" or "do" are used, but both expressions have the same meaning.
< 1 > a polycyclic aromatic compound represented by the following general formula (1A) or general formula (1B).
[ solution 2]
Figure BDA0003527825380000032
In the formula (1A) or the formula (1B),
R a is hydrogen or a substituent, -C (-R) in the a ring a ) Either unsubstituted or substituted with "-N ═ N",
ring B, ring C, ring D, ring E, ring F, and ring G are each independently an aryl or heteroaryl ring, at least one hydrogen in these rings being unsubstituted or substituted,
Y 1 、Y 2 and Y 3 Each independently is > B-, > P (═ O) -, > P (═ S) -, > Al-, > Ga-, > As-, > C (-R) -, > Si (-R) -, or > Ge (-R) -, R of > C (-R) -, > R of Si (-R) -, and R of > Ge (-R) -are each independently substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl,
In the formula (1A), the compound (A),
X 1 and X 2 Independently from each other > N-R, > O, > S, > C (-R) 2 、＞Si(-R) 2 Or > Se, R, > C (-R) of > N-R 2 R, and > Si (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > C (-R) 2 And > Si (-R) 2 At least one of two R is not bonded by a single bond or a linking group, or is bonded by a single bond or a linking group,
as X 1 R of > N-R, > C (-R) 2 R or > Si (-R) 2 R of (A) is bonded to at least one of the a ring and the B ring as X through a single bond or a linking group 2 R of > N-R, > C (-R) 2 R or > Si (-R) 2 Wherein R of (A) is bonded to at least one of the a-ring and the E-ring via a single bond or a linking group, and the linking groups are the same or different,
in the formula (1A) or the formula (1B),
l is each independently a single bond or a linking group, wherein at least one of L is a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkynylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group, and at least one of the B ring, C ring, D ring, E ring, F ring, G ring, aryl group, and heteroaryl group in the compound represented by the formula (1A) or the formula (1B) is not condensed with or has been condensed with at least one cycloalkane At least one hydrogen in the hydrocarbon being unsubstituted or substituted, at least one-CH in said cycloalkane 2 -unsubstituted or substituted by-O-,
at least one hydrogen in the compound represented by the formula (1A) or the formula (1B) is unsubstituted or substituted by deuterium, cyano or halogen.
< 2 > the polycyclic aromatic compound according to < 1 > wherein in the formula (1A) or the formula (1B),
R a is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboryl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted arylthio, or substituted silyl, the two aryl groups of the diarylamino being not bonded to each other or to a linking group, the two heteroaryl groups of the diheteroarylamino being not bonded to each other or to a linking group, the aryl and heteroaryl groups of the arylheteroarylamino not being bonded to each other, or bonded via a linking group, the two aryl groups of the diarylboron group being not bonded to each other, or bonded via a single bond or a linking group,
-C (-R) in the a-ring a ) Either unsubstituted or substituted with "-N ═ N",
ring B, ring C, ring D, ring E, ring F, and ring G are each independently an aryl or heteroaryl ring, at least one of which rings may be substituted with a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted diarylamino, a substituted or unsubstituted diheteroarylamino, a substituted or unsubstituted arylheteroarylamino, a substituted or unsubstituted diarylboryl, a substituted or unsubstituted alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryloxy, a substituted or unsubstituted arylthio, or a substituted silyl, the two aryl groups of the diarylamino group not being bonded to each other, or being bonded via a linking group, the two heteroaryl groups of the diheteroarylamino group not being bonded to each other, or bonded via a linking group, the aryl and heteroaryl groups of the arylheteroarylamino group being not bonded to each other, or bonded via a linking group, the two aryl groups of the diarylboron group being not bonded to each other, or bonded via a single bond or a linking group,
Y 1 、Y 2 And Y 3 Each independently > B-, > P (═ O) -, > P (═ S) -, > Al-, > Ga-, > As-, > C (-R) -, > Si (-R) -, or > Ge (-R) -, R of > C (-R) -, > R of Si (-R) -, and R of > Ge (-R) -are each independently aryl, heteroaryl, alkyl, or cycloalkyl, at least one of these hydrogens being substituted with alkyl or cycloalkyl,
in the formula (1A), the compound (A),
X 1 and X 2 Independently from each other > N-R, > O, > S, > C (-R) 2 、＞Si(-R) 2 Or > Se, said > N-R, said > C (-R) 2 R of (b), and said > Si (-R) 2 Each R of (A) is independently hydrogen, aryl, heteroaryl, alkyl, or cycloalkyl, at least one of these hydrogens being unsubstituted or substituted with alkyl or cycloalkyl, said > C (-R) 2 Two R of (A) are each other and > Si (-R) 2 Wherein the two R groups are not bonded to each other by a single bond or a linking group, or bonded to each other by a single bond or a linking group, and wherein the linking groups are the same or different,
as X 1 R of > N-R, > C (-R) 2 R of (A), or > Si (-R) 2 R of (A) is bonded to at least one of the a ring and the B ring as X through a single bond or a linking group 2 R of > N-R, > C (-R) 2 R or > Si (-R) 2 Wherein R of (A) is bonded to at least one of the a-ring and the E-ring via a single bond or a linking group, wherein the linking groups are the same or different,
In the formula (1A) or the formula (1B),
l are each independently a single bond or a linking group, wherein at least one L is substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene, substituted or unsubstituted alkenylene, substituted or unsubstituted alkynylene, substituted or unsubstituted arylene, and substituted or unsubstituted heteroarylene,
the linking group is-N (-R) -, -O-, -S-, -C (-R) 2 -、-Si(-R) 2 -, -Se-, substituted or unsubstituted cycloalkylene, substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, substituted or unsubstituted alkynylene, substituted or unsubstituted arylene, or substituted or unsubstituted heteroarylene, R of the-N (-R) -, the-C (-R) 2 R of (A) and said-Si (-R) 2 Each R of-is independently hydrogen, aryl, heteroaryl, alkyl, or cycloalkyl, at least one of which is hydrogen unsubstituted or substituted with alkyl or cycloalkyl,
at least one of the ring B, ring C, ring D, ring E, ring F, ring G, aryl, and heteroaryl in the compound represented by the formula (1A) or formula (1B) is not condensed or condensed with at least one cycloalkane in which at least one hydrogen is unsubstituted or substituted, at least one-CH in the cycloalkane is unsubstituted or substituted 2 -unsubstituted or substituted by-O-,
at least one hydrogen in the compound represented by the formula (1A) or the formula (1B) is unsubstituted or substituted by deuterium, cyano or halogen.
< 3 > the polycyclic aromatic compound according to < 1 > represented by the following general formula (2A) or the following general formula (2B).
[ solution 3]
Figure BDA0003527825380000051
In the formula (2A) or the formula (2B),
R a is hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylAlkylamino, diarylboryl, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, or alkylbicycloalkylsilyl, at least one hydrogen of which is unsubstituted or substituted by aryl, heteroaryl, alkyl, or cycloalkyl, the two aryl groups of the diarylamino groups are not bonded to each other or are bonded via a linking group, the two heteroaryl groups of the diheteroarylamino groups are not bonded to each other or are bonded via a linking group, the aryl and heteroaryl groups of the arylheteroarylamino groups are not bonded to each other or are bonded via a linking group, the two aryl groups of the diarylboryl groups are not bonded to each other or are bonded via a single bond or a linking group,
-C (-R) in the a-ring a ) May be substituted with "-N ═ N",
R b 、R c 、R d 、R e 、R f and R g Independently of one another, hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, or alkylbicycloalkylsilyl, at least one of which is unsubstituted or substituted by aryl, heteroaryl, alkyl, or cycloalkyl, the two aryl groups of the diarylamino groups not being bonded to one another or being bonded via a linking group, the two heteroaryl groups of the diheteroarylamino groups not being bonded to one another or being bonded via a linking group, the aryl and heteroaryl groups of the arylheteroarylamino groups not being bonded to one another or being bonded via a linking group, the two aryl groups of the diarylboryl groups not being bonded to one another or being bonded via a single bond or a linking group,
in addition, R b 、R c 、R d 、R e 、R f And R g Wherein adjacent radicals are bonded to each other and form, together with ring b, ring c, ring d, ring e, ring f, and ring g, an aryl or heteroaryl ring, respectively, with at least one hydrogen in the ring formed being aryl or heteroaryl A group, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboramino, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, or alkylbicycloalkylsilyl, or substituted, at least one hydrogen of which is unsubstituted or substituted for aryl, heteroaryl, alkyl, or cycloalkyl, the two aryl groups of the diarylamino group being not bonded to each other or bonded via a linking group, the two heteroaryl groups of the diheteroarylamino group being not bonded to each other or bonded via a linking group, the aryl and heteroaryl groups of the arylheteroarylamino group being not bonded to each other or bonded via a linking group, the two aryl groups of the diarylboramino group being not bonded to each other or bonded via a single bond or a linking group,
any of the "C (-R) ═ rings in ring b, ring C, ring d, ring e, ring f, and ring g (where R is R) b 、R c 、R d 、R e 、R f Or R g ) Unsubstituted or substituted with "-N ═ and optionally" -C (-R) ═ C (-R) - "(where R is R) b 、R c 、R d 、R e 、R f Or R g ) Unsubstituted, or substituted "-N (-R) -", "-O-", "-S-", "-C (-R) 2 -”、“-Si(-R) 2 - ", or" -Se- ", the R of" -N (-R) - ", the" -C (-R) 2 - "R, and" -Si (-R) 2 R of- "is hydrogen, aryl, heteroaryl, alkyl, or cycloalkyl, at least one hydrogen of which is unsubstituted or substituted by alkyl or cycloalkyl, said" -C (-R) 2 - "two R of each other and" -Si (-R) 2 Two R's of- "may be bonded to each other by a single bond or a linking group,
l are each independently a single bond or a linking group, wherein at least one L is alkylene, cycloalkylene, alkenylene, alkynylene, arylene, heteroarylene, at least one hydrogen of the cycloalkylene, alkenylene, alkynylene, arylene, and heteroarylene is unsubstituted or substituted with one or more hydrogen of aryl, heteroaryl, diarylamino, diheteroarylamino, diarylboron, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, or alkylbicycloalkylsilyl, at least one of which is unsubstituted or substituted with one or more hydrogen of aryl, heteroaryl, alkyl, or cycloalkyl, two aryl groups of the diarylamino groups being not bonded to each other or bonded via a linking group, the two heteroaryl groups of the diheteroarylamino are not bonded to one another or via a linking group, the aryl and heteroaryl groups of the arylheteroarylamino are not bonded to one another or via a linking group, the two aryl groups of the diarylboron group are not bonded to one another or are bonded via a single bond or a linking group,
The linking group is-N (-R) -, -O-, -S-, -C (-R) 2 -、-Si(-R) 2 -, -Se-, cycloalkylene, alkylene, alkenylene, alkynylene, arylene, heteroarylene, R of said-N (-R) -, said-C (-R) 2 R of (A) and said-Si (-R) 2 -R is each independently hydrogen, aryl, heteroaryl, alkyl, or cycloalkyl, at least one of these hydrogens being unsubstituted or substituted with alkyl or cycloalkyl, at least one of the hydrogens of the cycloalkylene, the alkylene, the alkenylene, the alkynylene, the arylene, and the heteroarylene being unsubstituted or substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, or alkylbicycloalkylsilyl, at least one of these hydrogens being unsubstituted or substituted with aryl, heteroaryl, alkyl, or cycloalkyl, two aryl groups of the diarylamino groups not being bonded to each other, or bonded via a linking group, the two heteroaryl groups of the diheteroarylamino group not being bonded to one another, or bonded via a linking group, the aryl and heteroaryl groups of the arylheteroarylamino group not being bonded to one another, or bonded via a linking group, the diarylboron The two aryl radicals of the radical are not bonded to one another or are bonded via a single bond or a linking group,
Y 1 、Y 2 and Y 3 Each independently > B-, > P (═ O) -, > P (═ S) -, > Al-, > Ga-, > As-, > C (-R) -, > Si (-R) -, or > Ge (-R) -, R of said > C (-R) -, R of said > Si (-R) -, and R of said > Ge (-R) -each independently being aryl, heteroaryl, alkyl, or cycloalkyl, at least one of these hydrogens being substituted with alkyl or cycloalkyl,
in the formula (2A), the reaction mixture is,
X 1 and X 2 Are each independently > N-R, > O, > S, > C (-R) 2 、＞Si(-R) 2 Or > Se, R of > N-R, > C (-R) 2 R, and > Si (-R) 2 Each R of (a) is independently hydrogen, aryl, heteroaryl, alkyl, or cycloalkyl, at least one of these hydrogens being unsubstituted or substituted with alkyl or cycloalkyl, said > C (-R) 2 Two R of (A) are each other and > Si (-R) 2 Are not bonded to each other by a single bond, a linking group, or are bonded by a single bond, a linking group, wherein a plurality of the linking groups are different or the same,
as X 1 R of > N-R, > C (-R) 2 R of (A), or > Si (-R) 2 R of (2) is bonded to at least one of the ring a and the ring b as X through a single bond or a linking group 2 R of > N-R, > C (-R) 2 R or > Si (-R) 2 R of (2) is bonded to at least one of the a-ring and the e-ring by a single bond or a linking group, and the linking groups are different from or the same as each other,
at least one of the B-ring, the c-ring, the d-ring, the e-ring, the f-ring, the g-ring, the formed ring, the aryl group and the heteroaryl group in the compound represented by the formula (2A) or (2B) is not condensed or condensed with at least one cycloalkane having 3 to 24 carbon atoms, at least one hydrogen in the cycloalkane is not substituted with or substituted with an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, an alkyl group having 1 to 24 carbon atoms or a cycloalkyl group having 3 to 24 carbon atoms, and at least one-CH in the cycloalkane is substituted 2 -has not yetby-O-substitution, or by substitution,
at least one hydrogen in the compound represented by the formula (2A) or the formula (2B) is unsubstituted or substituted by deuterium, cyano or halogen.
< 4 > the polycyclic aromatic compound according to any one of < 1 > to < 3 > represented by any one of the following structural formulae.
[ solution 4]
Figure BDA0003527825380000081
In the following formulas, the first and second groups,
r is independently hydrogen, an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a diarylamino group (wherein the aryl group is an aryl group having 6 to 10 carbon atoms), a diarylboron group (wherein the aryl group is an aryl group having 6 to 10 carbon atoms), an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 16 carbon atoms, at least one of which is substituted with an alkyl group having 1 to 5 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms, two aryl groups of the diarylamino group are not bonded to each other or are bonded through a linking group, two aryl groups of the diarylboron group are not bonded to each other or are hydrogen-bonded through a single bond or a linking group,
o is an integer of 1 to 3,
p is independently an integer of 1 to 4,
q is an integer of 1 to 5,
at least one hydrogen in the compounds of each formula may be substituted with deuterium, cyano, or halogen.
< 5 > the polycyclic aromatic compound according to < 1 > represented by any one of the following structural formulae.
[ solution 5]
Figure BDA0003527825380000091
< 6 > a reactive compound obtained by substituting a reactive substituent in the polycyclic aromatic compound according to any one of < 1 > to < 5 >.
< 7 > a high molecular compound obtained by polymerizing the reactive compound of < 6 > as a monomer or a crosslinked high molecular compound obtained by further crosslinking the high molecular compound.
< 8 > a pendant type polymer compound obtained by substituting the reactive compound of < 6 > in a main chain type polymer or a pendant type polymer crosslinked body obtained by further crosslinking the pendant type polymer compound.
< 9 > a material for organic devices, comprising the polycyclic aromatic compound according to any one of < 1 > to < 5 >.
< 10 > a material for organic devices comprising the reactive compound according to < 6 >.
< 11 > a material for organic devices comprising the polymer compound or the polymer cross-linked body according to < 7 >.
< 12 > a material for organic devices comprising the pendant type high molecular compound or the pendant type crosslinked polymer according to < 8 >.
< 13 > the material for an organic device according to any one of < 9 > to < 12 >, 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.
< 14 > the material for organic devices according to < 13 > wherein the material for organic electroluminescent elements is a material for light-emitting layers.
< 15 > an ink composition comprising the polycyclic aromatic compound according to any one of < 1 > to < 5 > and an organic solvent.
< 16 > an ink composition comprising the reactive compound according to < 6 > and an organic vehicle.
< 17 > an ink composition comprising a main chain type polymer, the reactive compound according to < 6 > and an organic solvent.
< 18 > an ink composition comprising the polymer compound or the polymer crosslinked body according to < 7 > and an organic solvent.
< 19 > an ink composition comprising the pendant type polymer compound or the pendant type polymer crosslinked body according to < 8 > and an organic solvent.
< 20 > an organic electroluminescent element comprising: a pair of electrodes including an anode and a cathode; and an organic layer disposed between the pair of electrodes, and containing a polycyclic aromatic compound according to any one of < 1 > to < 5 >, a reactive compound according to < 6 >, a polymer compound or a crosslinked polymer according to < 7 >, or a pendant polymer compound or a crosslinked polymer according to < 8 >.
< 21 > the organic electroluminescent element according to < 20 > wherein the organic layer is a light-emitting layer.
< 22 > the organic electroluminescent element according to < 21 > wherein the light-emitting layer comprises a host and the polycyclic aromatic compound, the reactive compound, the polymeric compound, the crosslinked polymer, the pendant polymeric compound or the crosslinked pendant polymer as a dopant.
< 23 > the organic electroluminescent element according to < 22 > wherein the light-emitting layer further contains at least one selected from the group consisting of a compound represented by the following general formula (H1), a compound represented by the following general formula (H2), a compound represented by the following general formula (H3), a compound having a structure represented by the following general formula (H4), a compound represented by the following general formula (H5), a compound represented by the following general formula (H6), and a TADF material.
[ solution 6]
Figure BDA0003527825380000101
In the general formula (H1), L 1 Is an arylene group having 6 to 30 carbon atoms or a heteroarylene group having 2 to 30 carbon atoms，
In the general formula (H2), L 2 And L 3 Each independently an aryl group having 6 to 30 carbon atoms or a heteroaryl group having 2 to 30 carbon atoms,
in the general formula (H3), MU is a divalent group represented by removing any two hydrogen atoms from an aromatic compound, EC is a monovalent group represented by removing any one hydrogen atom from an aromatic compound, two hydrogens in MU are replaced by EC or MU, k is an integer of 2-50000,
in the general formula (H4), G is independently ═ C (-H) -or ═ N-, and H in the ═ C (-H) -may be substituted with a substituent or with a structure represented by another formula (H4),
in the general formula (H5), in the formula,
R 1 ～R 11 independently of one another, hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl or cycloalkyl, at least one of which may be further substituted by aryl, heteroaryl, diarylamino, alkyl or cycloalkyl, the two aryl groups of the diarylamino group not being bonded to one another or being bonded via a linking group, the two heteroaryl groups of the diheteroarylamino group not being bonded to one another or being bonded via a linking group, the aryl and heteroaryl groups of the arylheteroarylamino group not being bonded to one another or being bonded via a linking group,
R 1 ～R 11 Wherein adjacent groups can 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 can be substituted by aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl or cycloalkyl, at least one of which can be further substituted by aryl, heteroaryl, diarylamino, alkyl or cycloalkyl, the two aryl groups of the diarylamino are not bonded to each other or are bonded via a linking group, the two heteroaryl groups of the diheteroarylamino are not bonded to each other or are bonded via a linking group, the aryl and heteroaryl groups of the arylheteroarylamino are not bonded to each other or are bonded via a linking group,
in rings a, b, and cAny of "-C (-R) ═" (where R is R) 1 ～R 11 ) May be substituted with "-N ═ N",
in the general formula (H6), in the formula,
R 1 ～R 16 independently of one another, hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl or cycloalkyl, at least one of which may be further substituted by aryl, heteroaryl, diarylamino, alkyl or cycloalkyl, the two aryl groups of the diarylamino group not being bonded to one another or being bonded via a linking group, the two heteroaryl groups of the diheteroarylamino group not being bonded to one another or being bonded via a linking group, the aryl and heteroaryl groups of the arylheteroarylamino group not being bonded to one another or being bonded via a linking group,
R 1 ～R 16 Wherein adjacent radicals may be bonded to each other and together with the a-, b-, c-or d-ring form an aryl or heteroaryl ring, at least one hydrogen in the ring formed may be substituted by aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl or cycloalkyl, at least one hydrogen of these may be further substituted by aryl, heteroaryl, diarylamino, alkyl or cycloalkyl, the two aryl groups of the diarylamino groups are not bonded to each other or are bonded via a linking group, the two heteroaryl groups of the diheteroarylamino groups are not bonded to each other or are bonded via a linking group, the aryl and heteroaryl groups of the arylheteroarylamino groups are not bonded to each other or are bonded via a linking group, and the aryl and heteroaryl groups of the arylheteroarylamino groups are bonded to each other or are bonded via a linking group, and
at least one hydrogen in the compound or structure represented by each formula can be substituted by alkyl with 1-6 carbon atoms, cycloalkyl with 3-14 carbon atoms, cyano, halogen or deuterium.
< 24 > a display device or a lighting device comprising the organic electroluminescent element according to any one of < 20 > to < 23 >.
[ Effect of the invention ]
According to a preferred embodiment of the present invention, an organic EL device having a narrow half-value width of an emission spectrum and excellent color purity, and further an organic EL device having excellent quantum efficiency and device lifetime can be provided by manufacturing an organic EL device using a novel polycyclic aromatic compound, for example, as a dopant material. In addition, in terms of having a rigid structure, many of the novel polycyclic aromatic compounds of the present invention have a sharper emission spectrum, a narrow half-value width of the emission spectrum, and provide light emission with high color purity.
Specifically, the present inventors have found that a polycyclic aromatic compound in which aromatic rings are linked by heterogeneous elements such as boron, phosphorus, oxygen, nitrogen, and sulfur has a large Highest Occupied Molecular Orbital (HOMO) -Lowest Unoccupied Molecular Orbital (LUMO) gap (band gap Eg in a thin film) and a high triplet energy. The reason is considered to be that: since the 6-membered ring containing a hetero element has low aromaticity, the decrease of HOMO-LUMO gap accompanying the expansion of the conjugated system is suppressed, and single-occupied molecular orbital (SOMO) 1 and SOMO2 in the triplet excited state are localized by electron perturbation of the hetero element.
Further, the hetero element-containing polycyclic aromatic compound of the present invention can be effectively used as a fluorescent material for an organic EL device because it exhibits thermally active delayed fluorescence by reducing the energy difference between the triplet excited state and the singlet excited state and further increasing the spin-orbit interaction. In addition, a material having high triplet energy can also be effectively used as an electron transport layer or a hole transport layer of a phosphorescent organic EL device or an organic EL device utilizing thermally active delayed fluorescence. Further, since the energy of HOMO and LUMO can be varied arbitrarily by introducing a substituent into these polycyclic aromatic compounds, the ionization potential and electron affinity can be optimized according to the surrounding materials.
Drawings
Fig. 1 is a schematic sectional view showing an organic EL element according to the present embodiment.
[ description of symbols ]
100: organic electroluminescent element
101: substrate
102: anode
103: hole injection layer
104: hole transport layer
105: luminescent layer
106: electron transport layer
107: electron injection layer
108: and a cathode.
Detailed Description
[ polycyclic aromatic Compound of the present invention ]
< description of the overall Structure of the Compound >
The present invention is a polycyclic aromatic compound represented by the following general formula (1A) or (1B), and preferably a polycyclic aromatic compound represented by the following general formula (2A) or (2B). In the above formulas, "B" to "G" in the circle are symbols representing ring structures represented by circles, "a" to "G" in the 6-membered aromatic ring are benzene rings or rings (6-or 5-membered heteroaromatic rings and the like) in which the benzene rings are changed depending on the case, and the other symbols are the same as the above definitions. Further, the symbols in all structural formulae shown later in the paragraph are also defined as described above.
[ solution 7]
Figure BDA0003527825380000121
[ solution 8]
Figure BDA0003527825380000131
The compound of the present invention is characterized by having a linking group Q as L or X in the molecule 1 Or X 2 At least one linking group Q of R in (1) is alkylene, cycloalkylene, alkenylene, alkynylene, arylene, or heteroarylene. At least one hydrogen in the linking group Q is unsubstituted or substituted.
The linking group Q may be independently formed as L selected from a single bond and a linking group Q, and is bonded to X 1 Or X 2 The case of the linking group Q of R in (1) and the case of referring to other linking groups. For example, as will be described in detail later, the linking group Q in the formula (1A) is, for example, L linking the C ring and the D ring, and X 1 Or X 2 R > N-R is formed as a linking group when linked to the B ring or the E ring, respectively. In the formula (2A), for example, L connecting the c-ring and the d-ring, and X 1 Or X 2 R in the case of > N-R is a linking group which links the b ring or the e ring, respectively. In the formula (1B), the same applies to L connecting the ring C and the ring D, L connecting the ring G and the ring B, and L connecting the ring F and the ring E. In the formula (2B), similarly, for example, L is a linking group which links the c-ring and the d-ring, g-ring and B-ring, and L is a linking group which links the f-ring and the e-ring.
< description of the Ring Structure and substituents therefor >
R a Is hydrogen or a substituent. As said substituent, preferred are a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted diarylamino group (two aryl groups are not bonded to each other or bonded via a linking group), a substituted or unsubstituted diheteroarylamino group (two heteroaryl groups of a diheteroarylamino group are not bonded to each other or bonded via a linking group), a substituted or unsubstituted arylheteroarylamino group (an aryl group and a heteroaryl group are not bonded to each other or bonded via a linking group), a substituted or unsubstituted diarylboron group (two aryl groups are not bonded via a single bond or a linking group or bonded via a single bond or a linking group), a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, A substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylthio group, or a substituted silyl group. Examples of the substituent in the case where these groups have a substituent include: aryl, heteroaryl, alkyl, or cycloalkyl. The details of the substituents listed here will be described later.
Ring B, ring C, ring D, ring E, ring F, and ring G are each independently aryl or heteroaryl rings, at least one hydrogen in these rings being unsubstituted or substituted. As said substituent, preferred are a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted diarylamino group (two aryl groups are not bonded to each other or bonded via a linking group), a substituted or unsubstituted diheteroarylamino group (two heteroaryl groups of a diheteroarylamino group are not bonded to each other or bonded via a linking group), a substituted or unsubstituted arylheteroarylamino group (an aryl group and a heteroaryl group are not bonded to each other or bonded via a linking group), a substituted or unsubstituted diarylboron group (two aryl groups are not bonded via a single bond or a linking group or bonded via a single bond or a linking group), a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, A substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylthio group, or a substituted silyl group. Examples of the substituent in the case where these groups have a substituent include: aryl, heteroaryl, alkyl, or cycloalkyl. The details of the rings and substituents listed here will be described later.
R b 、R c 、R d 、R e 、R f And R g Each independently hydrogen, aryl, heteroaryl, diarylamino (two aryl groups are not bonded to each other or are bonded via a linking group), diheteroarylamino (two heteroaryl groups of diheteroarylamino are not bonded to each other or are bonded via a linking group), arylheteroarylamino (aryl groups and heteroaryl groups are not bonded to each other or are bonded via a linking group), diarylboron (two aryl groups are not bonded via a single bond or a linking group or are bonded via a single bond or a linking group), alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, or alkylbicycloalkylsilyl, at least one of which may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl. Further, with respect to the substituents listed hereinThe details of which will be described later.
The aryl ring or heteroaryl ring (i.e., B ring to G ring) in the formula (1A) and the formula (1B) is preferably a 5-or 6-membered ring having a bond in common with the condensed bicyclic structure included in each formula.
Here, the "condensed bicyclic structure" means that Y is contained in the formula (1A) 1 、X 1 And N (the first condensed bicyclic structure on the left side in the formula), and a compound containing Y 2 、X 2 And N (the second condensed bicyclic structure on the right side in the formula). In addition, in the same manner, in formula (1B), Y is included 1 And two saturated hydrocarbon rings of two N (the first condensed bicyclic structure on the left side in the formula), and Y 2 And two saturated hydrocarbon rings of two N (the second condensed bicyclic structure on the right side in the formula), and a compound containing Y 3 And two saturated hydrocarbon rings composed of two N atoms (the lower third condensed bicyclic structure in the formula). Although not shown in the formulae (2A) and (2B), a condensed bicyclic structure is present at the same site.
The "6-membered ring bonded in common to the condensed bicyclic structure" means, for example, a B-ring (benzene ring (6-membered ring)) condensed in the condensed bicyclic structure as shown in formula (2A) or formula (2B). The expression "aryl ring or heteroaryl ring having the 6-membered ring" (as the B ring) "means that the B ring is formed by only the 6-membered ring or by further condensing another ring with the 6-membered ring so as to include the 6-membered ring. In other words, the "aryl or heteroaryl ring having 6-membered rings (as B ring)" as used herein means that 6-membered rings constituting all or part of the B ring are condensed in a condensed bicyclic structure. The same description applies to "C ring (C ring)", "D ring (D ring)", "E ring (E ring)", "F ring (F ring)", "G ring (G ring)", and the same description applies to "5-membered ring".
The ring B, ring C, ring D and ring E in the formula (1A) correspond to the ring B in the formula (2A) and the substituent R thereof, respectively b C ring and its substituent R c D ring and its substituent R d And ring e and its substituent R e . That is, the formula (2A) corresponds to a structure in which "B to E rings having 6-membered rings" are selected as the B to E rings of the formula (1A). "having" a 6-membered ring is due to: as described later, for example, in the case of ring b which is a 6-membered ring, four substituents R thereof b The adjacent groups in (1) may be bonded to each other to form a ring, and a ring B which is a 6-membered ring may be further condensed with another ring to form a ring corresponding to the ring B. In this sense, the capital letters B to E represent the rings of formula (1A), while the lowercase letters B to E represent the rings of formula (2A).
The ring B, ring C, ring D, ring E, ring F and ring G in the formula (1B) correspond to the ring B in the formula (2B) and the substituent R thereof, respectively b C ring and its substituent R c D ring and its substituent R d E ring and substituents R thereof e F ring and its substituent R f And g ring and its substituent R g . That is, the formula (2B) corresponds to a structure in which "B ring to G ring having 6-membered ring" are selected as the B ring to G ring of the formula (1B). The "having" 6 membered ring is due to: as described later, for example, in the case of ring b which is a 6-membered ring, four substituents R thereof b The adjacent groups in (1) may be bonded to each other to form a ring, and a ring B which is a 6-membered ring may be further condensed with another ring to form a ring B. In this sense, the capital letters B to G represent the rings of formula (1B), while the lowercase letters B to G represent the rings of formula (2B).
< description of the Change in Ring Structure caused by the bond of substituents to each other >
Substituents R for ring b, ring c, ring d, ring e, ring f and ring g b 、R c 、R d 、R e 、R f And R g Wherein adjacent groups may be bonded to each other and form, together with ring b, ring c, ring d, ring e, ring f, and ring g, respectively, an aryl or heteroaryl ring, at least one hydrogen in the formed ring may be bonded to each other through an aryl, heteroaryl, diarylamino group (where two aryl groups are not bonded to each other or are bonded through a linking group), a diheteroarylamino group (where two heteroaryl groups of the diheteroarylamino group are not bonded to each other or are bonded through a linking group)Group bonded), arylheteroarylamino (aryl and heteroaryl are not bonded to each other or are bonded via a linking group), diarylboryl (two aryl groups are not bonded via a single bond or a linking group or are bonded via a single bond or a linking group), alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, or alkylbicycloalkylsilyl, at least one of which may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl. The details of the rings and substituents listed here will be described later.
Therefore, the polycyclic aromatic compound of the formula (2A) or (2B) has a change in the ring structure of the compound depending on the bonding form of the substituents in the B-ring to g-ring, as shown in the following formula (2A-fr) and formula (2B-fr), for example. The B 'ring and the C' ring in the following formulae correspond to the B ring and the C ring in formulae (1A) and (1B), respectively. The d-g ring may be similarly changed.
[ solution 9]
Figure BDA0003527825380000151
When the formulae (2A) and (2B) are given, the B 'ring and the C' ring in the formulae (2A-fr) and (2B-fr) represent a plurality of substituents R b And R c Wherein adjacent groups are bonded to each other and form an aryl ring or a heteroaryl ring together with the b-ring and the c-ring, respectively (may also be referred to as a condensed ring formed by condensing another ring structure in the b-ring or the c-ring). Also, according to the above formula, R in ring b is shown, for example b R with ring c c That is, substituents in different rings do not correspond to "adjacent groups" with each other, and these are not substantially bonded. That is, the term "adjacent group" refers to a group adjacent to the same ring.
The above-mentioned formulae (2A-fr) and (2B-fr) have a B 'ring or a C' ring formed by condensation of, for example, a benzene ring, an indole ring, a pyrrole ring, a benzofuran ring, a benzothiophene ring or the like with respect to a benzene ring as a B ring or a C ring, and the formed condensed ring B 'or condensed ring C' is a naphthalene ring, a carbazole ring, an indole ring, a dibenzofuran ring, a dibenzothiophene ring or the like, respectively.
More specific examples of the formulae (2A-fr) and (2B-fr) are shown below.
[ solution 10]
Figure BDA0003527825380000161
The above-mentioned formulas (2A-fr-ex) and (2B-fr-ex) are specific examples of the formulas (2A-fr) and (2B-fr), respectively, and are as follows: two adjacent R's in the B-ring of the formula (2A) and the formula (2B) b Bonded and taken together with the B ring (benzene ring) to form an aryl ring (naphthalene ring) represented by B ', two adjacent R's in the c ring c Bonded to and taken together with the b ring (benzene ring) to form an aryl ring (dibenzofuran ring) represented by C'. The aryl ring formed has a 6-membered ring (benzene ring b or c) bonded in common with the condensed bicyclic structure. Optional substituents on aryl rings B 'and C' (rings B and C of formulae (1A) and (1B)) other than R b And R c In addition, n is used to represent R, and the upper limit of n is the maximum number that can be substituted. These descriptions can be similarly applied to all forms other than the specific examples, for example, when the d-ring to g-ring are changed or when another aryl ring or heteroaryl ring is formed.
< center element Y in Compound 1 Central element Y 3 Description of (1) >
Y 1 、Y 2 And Y 3 Each independently is > B-, > P (═ O) -, > P (═ S) -, > Al-, > Ga-, > As-, > C (-R) -, > Si (-R) -, or > Ge (-R) -, R of > C (-R) -, > R of Si (-R) -, and R of > Ge (-R) -are each independently optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkyl, or optionally substituted cycloalkyl. As Y 1 、Y 2 And Y 3 Preferably > B-, > P (═ O) -, or > P (═ S) -, more preferably > B-. The details of the substituents listed here will be described later.
< description of the Change in Ring Structure caused by the linking group L between the rings >
The C ring and the D ring in the formula (1A) and the formula (1B) are bonded through L. In addition, the G ring and B ring and the F ring and E ring in formula (1B) are also independently bonded via L. The bond via the C ring and D ring of L is also referred to as CLD bond, the bond via the G ring and B ring of L is also referred to as GLB bond, and the bond via the F ring and E ring of L is also referred to as FLE bond.
< description of linking group >
The linking group is an atom, or a functional group, that links two carbon atoms. Preferably, a linking group Q is included.
The linking group Q is-N (-R) -, -O-, -S-, -C (-R) 2 -、-Si(-R) 2 -, -Se-, substituted or unsubstituted cycloalkylene, substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, substituted or unsubstituted alkynylene, substituted or unsubstituted arylene, or substituted or unsubstituted heteroarylene, R of the-N (-R) -, the-C (-R) 2 R of (A) and said-Si (-R) 2 R in (a) is independently hydrogen, aryl, heteroaryl, alkyl, or cycloalkyl, preferably hydrogen, aryl having 6 to 12 carbon atoms, heteroaryl having 2 to 15 carbon atoms, alkyl having 1 to 6 carbon atoms, or cycloalkyl having 3 to 14 carbon atoms. At least one hydrogen in the above is not substituted by an alkyl group (preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 2 to 4 carbon atoms) or a cycloalkyl group (preferably a cycloalkyl group having 3 to 14 carbon atoms, more preferably a cycloalkyl group having 3 to 10 carbon atoms), or substituted.
The cycloalkylene, alkenylene, alkynylene, arylene, and heteroarylene groups are preferably alkenylene groups having 2 to 6 carbon atoms, alkylene groups having 2 to 6 carbon atoms, cycloalkylene groups having 3 to 14 carbon atoms, arylene groups having 6 to 12 carbon atoms, or heteroarylene groups having 2 to 15 carbon atoms, and more preferably alkenylene groups having 2 to 6 carbon atoms, alkylene groups having 2 to 4 carbon atoms, cycloalkylene groups having 3 to 10 carbon atoms, arylene groups having 6 to 10 carbon atoms, or heteroarylene groups having 2 to 12 carbon atoms. At least one hydrogen in the above is not substituted by an alkyl group (preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 2 to 4 carbon atoms) or a cycloalkyl group (preferably a cycloalkyl group having 3 to 14 carbon atoms, more preferably a cycloalkyl group having 3 to 10 carbon atoms), or substituted.
The alkenylene group is most preferably in the form of-CR ═ CR-, and the alkylene group is most preferably-CR- 2 -CR 2 The morphology of (1). Where R is hydrogen or a substituent, the preferred ranges for the substituents can be found in the above description of alkenylene and alkylene groups.
The details of the substituents listed here will be described later.
L is a single bond or a linking group Q, and more preferably a single bond, -N (-R) -, -O-, -S-, -C (-R) 2 -, alkenylene, arylene, heteroarylene, and further preferably a single bond, arylene, -N (-R) -, -O-, and-S-, and most preferably a single bond and arylene. Reference is made to the above description for preferred ranges. As the arylene group, a phenylene group is most preferable. At least one hydrogen of these is unsubstituted or substituted, but reference is also made to the above description for preferred ranges of substituents.
In addition, at least one L is alkylene, cycloalkylene, alkenylene, alkynylene, arylene, or heteroarylene, preferably alkenylene, arylene, and most preferably phenylene. The preferable ranges of these can be referred to the above description. At least one hydrogen of these is unsubstituted or substituted, but reference is also made to the above description for preferred ranges of these.
The position at which two rings are bonded via a bonding group is not particularly limited as long as it is a position capable of bonding, but it is preferable that the two rings are bonded at the most adjacent position, and for example, it is preferable that the two rings are bonded to each other at the position adjacent to the "N" bonding position (1-position) in each ring (see the structural formulae of formulae (1A) and (1B)).
The c-ring and d-ring in the formulae (2A) and (2B) of the lower formulae are also bonded via L in the same manner as in the above formulae. In addition, in the formula (2B) of the lower formula, g ring and B ring, and f ring and e ring are independently bonded to each other by L, as in the upper formula. May be bonded by a single bond or a linking group (these are also collectively referred to as a bonding group). The bond between the c-ring and the d-ring of L containing a single bond or a linking group Q is also referred to as an cLd bond, the bond between the g-ring and the b-ring is also referred to as a gLb bond, and the bond between the f-ring and the e-ring is also referred to as a fLe bond. The type or bonding position of the linking group Q can be referred to the description of the above formula.
< description of bond L (1) >)
In the compound of the present invention, as described above, since the C ring and the D ring (C ring and D ring), the G ring and the B ring (G ring and B ring), and the F ring and the E ring (F ring and E ring) may be bonded through L, the first crosslinked structure may be formed in the formulas (1A) and (2A), and the first crosslinked structure, the second crosslinked structure, and the third crosslinked structure may be formed in the formulas (1B) and (2B). L in the following structural formula means a bonding group (single bond and linking group). Among them, the compound of the present invention is characterized in that one or two of three crosslinked structures that can be formed within a molecule are formed.
[ solution 11]
Figure BDA0003527825380000171
[ solution 12]
Figure BDA0003527825380000181
As described above, L includes a single bond and a linking group as a bonding group, the bonding position between the rings is not limited, and the ring structure of each ring such as c ring is changed by bonding of adjacent substituents or the like as described above.
The position at which two rings are bonded via L is not particularly limited as long as it is a position capable of bonding, but it is preferable to bond at the most adjacent position, and for example, it is preferable to bond at the position adjacent to the position (2 position) based on the bonding position (1 position) of "N" in each ring (see the structural formulae of formulae (1A), (1B), (2A), and (2B)).
When L is formed, it is preferable that both bonded rings are benzene rings.
< connecting element X in Compound 1 And a linking element X 2 Description of (1) >
Formula (A), (B) and1A) and X in the formula (2A) 1 And X 2 Are each independently > N-R, > O, > S, > C (-R) 2 、＞Si(-R) 2 Or > Se, R of > N-R, > C (-R) 2 R, and > Si (-R) 2 Each R of (a) is independently hydrogen, aryl which may be substituted, heteroaryl which may be substituted, alkyl which may be substituted, or cycloalkyl which may be substituted. The details of the substituents listed here will be described later.
As X 1 And X 2 Preferably, > N-R, > O, > S, or > C (-R) 2 More preferably, > N-R or > O, and still more preferably, > N-R. From the viewpoint of good TADF properties, > N-R, > O and > S are preferable, more specifically, > N-R is preferable from the viewpoint of localization of orbitals by the multiple resonance effect, and > S is preferable from the viewpoint of the heavy atom effect. In addition, from the viewpoint of emission wavelength, it is preferable that > O be used for emission of short wavelength, and > N-R or > S be used for emission of long wavelength.
One of the preferable embodiments of the formula (1A) and the formula (1B) is a formula (1A-a), a formula (1A-B), a formula (1A-c), a formula (1B-a), a formula (1B-B), or a formula (1B-c) as described below. Based on "as X 1 R of > N-R, > C (-R) 2 R or > Si (-R) 2 R of (A) is bonded to at least one of the ring a and the ring B as X through a single bond or a linking group 2 R of > N-R, > C (-R) 2 R of (A), or > Si (-R) 2 The statement that R in (A) is bonded to at least one of the a ring and the E ring by a single bond or a linking group "corresponds to X in the formula (1A) and the formula (1B) 1 Or X 2 Is > N-R, R is via a single bond, or a linking group (L) Q ) And bonded to the B ring or the E ring (B ring or E ring). Each symbol and its preferred range can be referred to the description of formula (1A) and formula (1B), wherein X is represented by formula (1A-a), formula (1A-B), formula (1A-c), formula (1B-a), formula (1B-B) or formula (1B-c) 1 Or X 2 Not > N-R. In addition, regarding L Q Reference is made directly to the description of L.
[ solution 13]
Figure BDA0003527825380000191
＞C(-R) 2 And > Si (-R) 2 At least one of the two R groups of (A) may be bonded by a single bond or a linking group (these are also collectively referred to as bonding groups). The linking group may be a linking group Q. The details of the substituents listed here will be described later.
[ solution 14]
Figure BDA0003527825380000201
The bonding group is preferably a single bond, or an alkenylene group, -N (-R) -, -O-, -S-, -C (-R) as a bonding group 2 -、-Si(-R) 2 -, and-Se-, more preferably a single bond, alkenylene group (particularly-CR ═ CR-), -N (-R) -, -O-, -S-, and-C (-R) 2 Further, a single bond, and-CR ═ CR-, -N (-R) -, -O-, and-S-, which are linking groups, are preferable, and a single bond is most preferable.
The position at which two R are bonded via a bonding group is not particularly limited as long as it is a position capable of bonding, but it is preferably bonded at the most adjacent position, and for example, when two R are phenyl groups, they are preferably bonded to each other at the position adjacent to the position (2 position) based on the bonding position (1 position) of "C" or "Si" in the phenyl group (see the structural formula).
< by X 1 Or X 2 Description of modification of Ring Structure by bond to Ring
X in the formulae (1A) and (2A) 1 R, > N-R, > C (-R) 2 R or > Si (-R) 2 R of (a) is bonded to at least one of the a-ring and the B-ring (B-ring) not via a single bond or a linking group (preferably, a linking group Q, these are also collectively referred to as a bonding group), or bonded to at least one of the a-ring and the B-ring (B-ring) via a single bond or a linking group (preferably, a linking group Q, these are also collectively referred to as a bonding group).
X in the formulae (1A) and (2A) 2 Is > N-RR, > C (-R) 2 R or > Si (-R) 2 R of (a) is bonded to at least one of the a-ring and the E-ring (E-ring) not via a single bond or a linking group (these are also referred to collectively as a bonding group), or bonded to at least one of the a-ring and the E-ring (E-ring) via a single bond or a linking group (these are also referred to collectively as a bonding group).
X as a participating bond 1 Or X 2 Preferably > N-R and > C (-R) 2 More preferably, > N-R.
The bonding group is preferably a single bond, or-CR- ═ CR-, -N (-R) -, -O-, -S-, -C (-R) -which is the bonding group Q 2 -、-Si(-R) 2 -, and-Se-, more preferably a single bond, -CR-, -N (-R) -, -O-, -S-, and-C (-R) as the linking group Q 2 -.
As a ring bound to X 1 And is preferably B ring (B ring), for X 2 And preferably an E ring (E ring).
In the above formula (1A), "said > R of N-R, > C (-R) 2 R or > Si (-R) 2 The definition of "R is bonded to at least one of the a-ring and the B-ring (or the E-ring) by a single bond or a linking group Q" corresponds to "R of said > N-R, said > C (-R) in the formula (2A) of the following formula 2 R or > Si (-R) 2 Wherein R in (A) is-CR ═ CR-, -C ≡ C-, -N (-R) -, -O-, -S-, -C (-R) as a linking group Q, via a single bond 2 -、-Si(-R) 2 -, or-Se-, and at least one bond between the a ring and the b ring (or the e ring) ".
The specification can be expressed by the following structural formula, for example. In addition, the substituent R in the structural formula is a A substituent R b A substituent R c A substituent R d And a substituent R e The display is not performed, but actually exists.
[ solution 15]
Figure BDA0003527825380000211
In the structural formula on the left side, is X 1 And X 2 (iii) a selection of (2) (> N-R, > C (-R) 2 And > Si (-R) 2 ) Wherein R is bonded to the b-ring and the e-ring, respectively, and represents an example having another ring to introduce X 1 Or X 2 The mode (1) is a compound having a B 'ring and an E' ring formed by condensation of a B-ring (benzene ring) and an E-ring (benzene ring). The condensed rings B 'and E' formed are, for example, dihydrodibenzonitrogen
Figure BDA0003527825380000212
Cyclo, dibenzo nitrogen
Figure BDA0003527825380000213
Ring, triphenylene nitrogen
Figure BDA0003527825380000214
A ring, a phenoxazine ring, a phenothiazine ring, a carbazole ring, or an acridine ring, etc.
The central formula represents a more specific example of the formula on the left side, and is as follows: as X 1 And X 2 R (phenyl) of > N-R is bonded to the b ring (benzene ring) through an o-phenylene group as a linking group Q to form a tribenzonitrogene
Figure BDA0003527825380000215
Ring B 'is bonded to ring E (benzene ring) by a single bond to form a carbazole ring E' surrounded by a dotted line.
The structural formula on the right represents a more specific example of the structural formula on the left, and is as follows: as X 1 And X 2 R (phenyl) of > N-R is bonded to the B ring (benzene ring) through-O-as a linking group to form a phenoxazine ring B 'surrounded by a dotted line, and-S-as a linking group is bonded to the E ring (benzene ring) to form a phenothiazine ring E' surrounded by a dotted line.
X 1 And X 2 (iii) a selection of (2) (> N-R, > C (-R) 2 And > Si (-R) 2 ) The position at which R in (1) is bonded to the rings (B ring, E ring, B ring and E ring) via a bonding group is not particularly limited as long as it is a position capable of bonding, but is preferably the most adjacent positionThe bond, for example when R is phenyl, is preferably the bond between the ring to which it is bonded and the "X" in the phenyl 1 "or" X 2 "are bonded to each other at the position adjacent to (2-position) based on the bonding position (1-position) (see the structural formula).
The description of the specific examples can be similarly applied to all the forms other than the specific examples, for example, X 1 And X 2 Any one of them is bonded to a ring, bonded to an a-ring, bonded via another linking group, and the like.
< description on the number of crosslinked structures formed by single bonds or linking groups Q in carbazole-like structures >
As described above, in the formulas (1A) and (2A), the first crosslinked structure is derived from the C-ring and D-ring bonds crosslinked by a single bond or a linking group or the C-ring D-bond and D-ring crosslinked by L including a single bond and a linking group Q, and the second crosslinked structure is derived from the X 1 B bond, X 1 QB bond, or X 1 b bond or X 1 Qb bond, and the third cross-linked structure is derived from X 2 E bond, X 2 QE Key, X 2 e bond or X 2 Qe key. In addition, in formula (1B) and formula (2B), the first crosslinking analogous structure is formed from CLD bond or cLd bond, and the second structure is derived from GL Q B bond or gL Q b bond, the third structure is derived from FL Q E bond or fL Q e bond. The compound of the present invention is characterized in that at least one of these three crosslink-like structures which can be formed within the molecule is formed, and at least one of the linking groups Q is an alkylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, an arylene group, and a heteroarylene group.
< description of structural changes of ring a, ring b to ring g >
In the description so far, the a-ring, b-ring, c-ring, d-ring, e-ring, f-ring, and g-ring are illustrated and described as benzene rings, and examples of aryl rings or heteroaryl rings in which the a-ring, b-ring to g-ring structures are changed to 5-or 6-membered rings other than benzene rings are described below. The following structural changes of these rings are also understood in the same manner as described above.
< structural Change of Ring a >
-C (-R) in the a-ring in the formulae (1A) and (2A) a ) May be substituted by "-N ═ to" a pyridine ring. The following structural diagram is a diagram in which only a part of the a-ring and its surrounding structure is extracted.
[ solution 16]
Figure BDA0003527825380000221
Structural variation of ring b to ring g
Any of the rings "C (-R) — (where R is R) in the B, C, d, e, f, and g rings in the formulae (2A) and (2B) — C (-R) ═ in the formulae (2A) and (2B) b 、R c 、R d 、R e 、R f Or R g ) May be substituted with "-N ═ N".
[ solution 17]
Figure BDA0003527825380000222
As shown above, for example, "-C (-R) in the d-ring d ) The "position" may be substituted with "-N ═ so that the d ring represented by a benzene ring in each formula may be changed to a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, or another nitrogen-containing heteroaryl ring. In addition, as mentioned above, in the d ring on the adjacent base (in the formula, the remaining two adjacent R d ) These may be bonded and form together with the d ring a heteroaryl ring (in the formula, a quinoline ring), and the ring formed may be further substituted (represented by n R).
Further, there are variations as follows.
[ solution 18]
Figure BDA0003527825380000223
Preferably with respect to X 1 、X 2 Or > N-bonded carbonOrtho-or para-C (-R) d ) Substituted with "-N ═ N".
The same applies to the case where the other site is substituted with "-N", or the case where the b-, c-, e-, f-and g-rings other than the d-ring are changed.
Further, it is preferable that all of "— (C (-R) ═" (including R being R) a In the case of R b 、R c 、R d 、R e 、R f Or R g In the case of (b), and in the case of a substituent defined by another ring structure) is not in a form of "— N ═".
Any of the rings "C (-R) ═ C (-R) -" among the B, C, d, e, f, and g rings in the formulae (2A) and (2B) (where R is R b 、R c 、R d 、R e 、R f Or R g ) May be substituted by "-N (-R) -", "-O-", "-S-", "-C (-R) 2 -”、“-Si(-R) 2 - ", or" -Se- ", the R of" -N (-R) - ", the" -C (-R) 2 - "R, and" -Si (-R) 2 R of-is hydrogen, aryl, heteroaryl, alkyl, or cycloalkyl, at least one of which may be substituted with alkyl or cycloalkyl. The details of the substituents listed here will be described later.
[ solution 19]
Figure BDA0003527825380000231
As shown above, for example, "-C (-R) in the d-ring d )＝C(-R d ) The site of- "may be substituted with" -N (-R) - "," -O- "," -S- "," -C (-R) 2 -”、“-Si(-R) 2 - ", or" -Se- ", so that the ring d, represented as a benzene ring in each formula, may be changed to an R-substituted pyrrole ring, furan ring, thiophene ring, other nitrogen/oxygen/sulfur-containing heteroaryl ring (5-membered ring) or aryl ring (5-membered ring). In addition, as mentioned above, in the d ring on the adjacent base (in the formula, the remaining two adjacent R d ) These may be bonded and form, together with the d ring, a heteroaromatic A cyclic ring (in the formula, R-substituted indole, benzofuran, benzothiophene, or the like) or an aryl ring, and the formed ring may be further substituted (represented by n R's).
Further, there are variations as follows.
[ solution 20]
Figure BDA0003527825380000232
Other sites are substituted with "-N (-R) -", "-O-", "-S-", "-C (-R) 2 -”、“-Si(-R) 2 The same applies to the case of- ", or" -Se- ", or the case where the b-, c-, e-, f-and g-rings other than the d-ring are changed.
The "-C (-R) 2 Two R of- "are each other and" -Si (-R) 2 At least one of the two R groups of- "may be bonded via a single bond or a linking group (these are also referred to as a bonding group). Examples of the linking group include: -CH 2 -CH 2 -、-CHR-CHR-、-CR 2 -CR 2 -、-CH＝CH-、-CR＝CR-、-C≡C-、-N(-R)-、-O-、-S-、-C(-R) 2 -、-Si(-R) 2 Examples of-Se-or-Se-include the following structures. Furthermore, R, -CR of said-CHR- 2 -CR 2 R of-R, -CR, -R of-N (-R) -, -C (-R) 2 R of-and-Si (-R) 2 Each R of (A) is independently hydrogen, aryl, heteroaryl, alkyl, alkenyl, alkynyl, or cycloalkyl, at least one of which may be substituted with alkyl or cycloalkyl. In addition, two adjacent R groups may form a ring with each other, thereby forming a cycloalkylene group, an arylene group, and a heteroarylene group. The details of the substituents listed here will be described later.
[ solution 21]
Figure BDA0003527825380000241
The bonding group is preferably a single bond, or-CR-, -N- (-R)-、-O-、-S-、-C(-R) 2 -、-Si(-R) 2 -, and-Se-, more preferably a single bond, a linking group of-CR- (-CR-, -N (-R) -, -O-, -S-, and-C (-R) 2 Further, a single bond, or-CR ═ CR-, -N (-R) -, -O-, and-S-, which are linking groups, is preferable, and a single bond is most preferable.
The position at which two R are bonded via a bonding group is not particularly limited as long as it is a position capable of bonding, but it is preferably bonded at the most adjacent position, and for example, when two R are phenyl groups, they are preferably bonded to each other at the position adjacent to the position (2-position) with reference to the bonding position (1-position) of "C" or "Si" in the phenyl group (see the structural formula).
< description of the Ring Or substituent >
Next, details of the ring or the substituent (including the second substituent further substituted on the first substituent) listed in the description so far will be described together.
The "aryl ring" is, for example, an aryl ring having 6 to 30 carbon atoms, preferably an aryl ring having 6 to 20 carbon atoms, an aryl ring having 6 to 16 carbon atoms, an aryl ring having 6 to 12 carbon atoms, an aryl ring having 6 to 10 carbon atoms, or the like.
The "aryl ring" as the ring B to ring G in the formula (1A) and the formula (1B) corresponds to the "R" defined in the formula (2A) and the formula (2B) b 、R c 、R d 、R e 、R f And R g Wherein adjacent groups are bonded to each other and form an aryl ring together with the b-ring, c-ring, d-ring, e-ring, f-ring, and g-ring, respectively, and the "formed aryl ring" includes a benzene ring having 6 carbon atoms in the b-ring to g-ring, and therefore the total carbon number of the condensed rings in which the smallest 5-membered ring is condensed on the benzene ring is 9 carbon atoms having the lower limit.
Among them, the b-g rings as the benzene rings may be changed to nitrogen-containing heteroaryl rings (6-or 5-membered rings), oxygen/sulfur-containing heteroaryl rings (5-membered rings), etc. as described above, the number of carbons at the lower limit is changed accordingly in the above case.
Specific "aryl ring" includes, for example, a benzene ring as a monocyclic system, a naphthalene ring as a condensed bicyclic system, an acenaphthylene ring (acenaphthylene ring), a fluorene ring (fluorene ring), a phenalene ring (phenalene ring), or a phenanthrene ring (phenanthrene ring) as a condensed tricyclic system, an anthracene ring, a triphenylene ring, a pyrene ring, or a tetracene ring as a condensed quaternary system, or a perylene ring or pentacene ring as a condensed quinary system.
The "heteroaryl ring" is, for example, a heteroaryl ring having 2 to 30 carbon atoms, preferably a heteroaryl ring having 2 to 25 carbon atoms, a heteroaryl ring having 2 to 20 carbon atoms, a heteroaryl ring having 2 to 15 carbon atoms, a heteroaryl ring having 2 to 10 carbon atoms, or the like. The "heteroaryl ring" is, for example, a heterocyclic ring containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen as ring-constituting atoms in addition to carbon, and the like.
Furthermore, the "heteroaryl ring" as the ring B to ring G in the formula (1A) and the formula (1B) corresponds to the "R" specified in the formula (2A) and the formula (2B) b 、R c 、R d 、R e 、R f And R g In (b) a heteroaryl ring in which adjacent groups are bonded to each other and are formed together with the b-ring, c-ring, d-ring, e-ring, f-ring, and g-ring, respectively, the "formed heteroaryl ring" already includes a benzene ring having 6 carbon atoms in the b-ring to g-ring, and therefore the total carbon number of 6 carbon atoms of a condensed ring in which the smallest 5-membered ring is condensed on the benzene ring becomes the lower limit.
Among them, the b-g rings as the benzene rings may be changed to nitrogen-containing heteroaryl rings (6-or 5-membered rings), oxygen/sulfur-containing heteroaryl rings (5-membered rings), etc., as described above, and therefore, in the above case, the number of carbons at the lower limit is changed accordingly.
Specific "heteroaryl rings" are for example: a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an oxadiazole ring, a thiadiazole ring, a triazole ring, a tetrazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring, an indole ring, an isoindole ring, a 1H-indazole ring, a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, a 1H-benzotriazole ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinazoline ring, a quinoxaline ring, a phenanthroline ring, a phthalazine ring, a naphthyridine ring, a purine ring, a pteridine ring, a carbazole ring, an acridine ring, a phenoxazine ring, a phenothiazine ring, a phenazine ring, a phenazasillene (phenazasiline) ring, an indolizine ring, a furan ring, a benzofuran ring, an isobenzofuran ring, a dibenzofuran ring, a naphthobenzofuran ring, a thiophene ring, an isobenzothiophene ring, a thiophene ring, a benzothiophene ring, a naphtho ring, a 1H-indazole ring, a, A benzo-phosphacyclopentadiene ring, a dibenzophosphacyclopentadiene ring, a benzo-phosphacyclopentadiene oxide ring, a dibenzophosphacyclopentadiene oxide ring, a furazan ring, a thianthracene ring, an indolocarbazole ring, a benzindolocarbazole ring, a dibenzoindolocarbazole ring, an imidazoline ring, or an oxazoline ring, and the like.
In addition, the following formula (BO) is also included in the heteroaryl ring.
[ solution 22]
Figure BDA0003527825380000251
The "aryl group" is, for example, an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 20 carbon atoms, an aryl group having 6 to 16 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
Specific "aryl" groups are for example: phenyl as a monocyclic system, biphenyl (2-biphenyl, 3-biphenyl, or 4-biphenyl) as a bicyclic system, naphthyl (1-naphthyl or 2-naphthyl) as a condensed bicyclic system, terphenyl (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, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, o-terphenyl-3-yl, P-terphenyl-3-yl, or p-terphenyl-4-yl), acenaphthene- (1-, 3-, 4-, or 5-) yl, fluorene- (1-, 2-, 3-, 4-, or 9-) yl, phenalene- (1-or 2-) yl, phenanthrene- (1-, 2-, 3-, 4-, or 9-) yl, or anthracene- (1-, 2-, or 9-) yl as a condensed tricyclic system, and tetraphenyl (5 '-phenyl-m-terphenyl-2-yl, 5' -phenyl-m-terphenyl-3-yl, 5 '-phenyl-m-terphenyl-4-yl, 5' -terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-1-or p-2-phenanthrene- (1-, 2-, 3-, or 9-) yl as a tetracyclic system, Or m-quaterphenyl), a triphenylene- (1-or 2-) group, a pyrene- (1-, 2-, or 4-) group, or a tetracene- (1-, 2-, or 5-) group as a condensed quaternary ring system, a perylene- (1-, 2-, or 3-) group, or a pentacene- (1-, 2-, 5-, or 6-) group as a condensed quinary ring system, and the like.
In addition, in the aryl group as the second substituent, that is, in the aryl group as the substituent (second substituent) which is further substituted on the substituent (first substituent), a structure in which at least one hydrogen in the aryl group is substituted with an aryl group such as a phenyl group (specifically, the group described above), an alkyl group such as a methyl group (specifically, the group described below), or a cycloalkyl group such as a cyclohexyl group or an adamantyl group (specifically, the group described below) is also included in the aryl group as the second substituent.
For example, when the second substituent is a fluorenyl group, the fluorenyl group may be one in which at least one hydrogen at the 9-position is substituted with an aryl group such as a phenyl group, an alkyl group such as a methyl group, or a cycloalkyl group such as a cyclohexyl group or an adamantyl group, and such a group is also included in the aryl group as the second substituent.
The "arylene group" is, for example, an arylene group having 6 to 30 carbon atoms, preferably an arylene group having 6 to 20 carbon atoms, an arylene group having 6 to 16 carbon atoms, an arylene group having 6 to 12 carbon atoms, an arylene group having 6 to 10 carbon atoms, or the like.
Specific examples of the "arylene group" include a structure in which one hydrogen is removed from the above-mentioned "aryl group" (monovalent group) to form a divalent group.
The "heteroaryl group" is, for example, a heteroaryl group having 2 to 30 carbon atoms, preferably a heteroaryl group having 2 to 25 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, or a heteroaryl group having 2 to 10 carbon atoms. The "heteroaryl group" is, for example, a monovalent group such as a heterocyclic ring containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen as ring-constituting atoms in addition to carbon.
As specific "heteroaryl", for example: 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, phenanthrolinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, carbolinyl, acridinyl, phenoxathiyl, phenoxazinyl, phenothiazinyl, phenazinyl silyl (phenazailinyl), indolizinyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, naphthobenzofuryl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, benzoxazolyl, cinnolinyl, naphthyridinyl, cinnolinyl, naphthobenzofuryl, cinnolinyl, naphthobenzofuryl, cinnolinyl, dibenzofuryl, naphthofuryl, cinnolinyl, naphthofuryl, cinnolinyl, naphthofuryl, dibenzofuryl, cinnolinyl, dibenzofuryl, naphthofuryl, dibenzofuryl, cinnolinyl, dibenzofuryl, naphthofuryl, dibenzofuryl, naphthofuryl, dibenzofuryl, cinnolinyl, naphthofuryl, cinnolinyl, naphthobenzothienyl, benzophosphoryl, dibenzophosphoryl, a monovalent radical of a benzophosphole oxide ring, a monovalent radical of a dibenzophosphole oxide ring, a furazanyl, thianthrenyl, indolocarbazolyl, benzindolocarbazolyl, dibenzoindolocarbazolyl, imidazolinyl, oxazolinyl, and the like.
In addition, a monovalent group obtained by removing one hydrogen from the following formula (BO) is also included in the heteroaryl group.
[ solution 23]
Figure BDA0003527825380000261
In addition, in the heteroaryl group as the second substituent, that is, the heteroaryl group as the substituent (second substituent) which is further substituted on the substituent (first substituent), a structure in which at least one hydrogen in the heteroaryl group is substituted with an aryl group such as a phenyl group (specifically, the group described above), an alkyl group such as a methyl group (specifically, the group described below), or a cycloalkyl group such as a cyclohexyl group or an adamantyl group (specifically, the group described below) is also included in the heteroaryl group as the second substituent.
For example, when the second substituent is a carbazolyl group, the carbazolyl group may be one in which at least one hydrogen atom at the 9-position is substituted with an aryl group such as a phenyl group, an alkyl group such as a methyl group, or a cycloalkyl group such as a cyclohexyl group or an adamantyl group, and such a group is also included in the heteroaryl group as the second substituent.
The "heteroarylene group" is, for example, a heteroarylene group having 2 to 30 carbon atoms, preferably a heteroarylene group having 2 to 25 carbon atoms, a heteroarylene group having 2 to 20 carbon atoms, a heteroarylene group having 2 to 15 carbon atoms, or a heteroarylene group having 2 to 10 carbon atoms. The "heteroarylene group" is, for example, a divalent group such as a heterocyclic ring containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen as ring-constituting atoms in addition to carbon.
Specific examples of the "heteroarylene group" include structures in which one hydrogen is removed from the "heteroaryl group" (monovalent group) to form a divalent group.
"diarylamino" is an amino group substituted with two aryl groups, and details of the aryl groups can be found in the description of the "aryl groups".
"Diheteroarylamino" is an amino group substituted with two heteroaryl groups, and reference is made to the description of "heteroaryl" for details of such heteroaryl groups.
"Arylheteroarylamino" is an amino group substituted with aryl and heteroaryl groups, and the details of the aryl and heteroaryl groups can be found in the description of the "aryl" and "heteroaryl".
The description that "two heteroaryl groups are bonded via a linking group" or not "in diarylamino groups (two aryl groups are bonded via a linking group or not), diheteroarylamino groups (two heteroaryl groups are bonded via a linking group or not), arylheteroarylamino groups (aryl groups and heteroaryl groups are bonded via a linking group or not) is as follows, for example, two phenyl groups representing diphenylamino groups are bonded via a linking group. In addition, the description also applies to diheteroarylamino and arylheteroarylamino groups formed from aryl or heteroaryl groups. The linking group is preferably a linking group Q, and its preferable range (including preferable ranges of substituents) can be referred to in the specification.
[ solution 24]
Figure BDA0003527825380000271
In addition, in the case where only "diarylamino", "diheteroarylamino", or "arylheteroarylamino" is described in the present specification, unless otherwise specified, descriptions are provided such that "two aryl groups are bonded via a linking group, or are not bonded", "two heteroaryl groups are bonded via a linking group, or are not bonded", and "aryl and heteroaryl groups are bonded via a linking group, or are not bonded", respectively.
"Diarylboron group" is a boron group in which two aryl groups are substituted, and the details of the aryl groups can be referred to the description of the "aryl groups". The two aryl groups are not bonded via a single bond or a linking group (preferably, a linking group Q), or are bonded via a single bond or a linking group (preferably, a linking group Q). The definition of the linking group Q and its preferred range are described in the present specification.
The "alkyl group" may be a straight chain or branched chain, and is, for example, a straight-chain alkyl group having 1 to 24 carbon atoms or a branched chain alkyl group having 3 to 24 carbon atoms, preferably an alkyl group having 1 to 18 carbon atoms (branched chain alkyl group having 3 to 18 carbon atoms), an alkyl group having 1 to 12 carbon atoms (branched chain alkyl group having 3 to 12 carbon atoms), an alkyl group having 1 to 6 carbon atoms (branched chain alkyl group having 3 to 6 carbon atoms), an alkyl group having 1 to 5 carbon atoms (branched chain alkyl group having 3 to 5 carbon atoms), an alkyl group having 1 to 4 carbon atoms (branched chain alkyl group having 3 to 4 carbon atoms), and the like.
Specific "alkyl" groups are for example: methyl, ethyl, n-propyl, isopropyl, 1-ethyl-1-methylpropyl, 1-diethylpropyl, 1, 2-trimethylpropyl, 1,2, 2-tetramethylpropyl, 1-ethyl-1, 2, 2-trimethylpropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-ethylbutyl, 1-dimethylbutyl, 3-dimethylbutyl, 1-diethylbutyl, 1-ethyl-1-methylbutyl, 1-propyl-1-methylbutyl, 1, 3-trimethylbutyl, 1-ethyl-1, 3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl (t-amyl), or a mixture thereof, 1-methylpentyl, 2-propylpentyl, 1-dimethylpentyl, 1-ethyl-1-methylpentyl, 1-propyl-1-methylpentyl, 1-butyl-1-methylpentyl, 1, 4-trimethylpentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 1-dimethylhexyl, 1-ethyl-1-methylhexyl, 1, 5-trimethylhexyl, 3,5, 5-trimethylhexyl, n-heptyl, 1-methylheptyl, 1-hexylheptyl, 1-dimethylheptyl, 2-dimethylheptyl, 2, 6-dimethyl-4-heptyl, n-octyl, tert-octyl (1,1,3, 3-tetramethylbutyl), 1-dimethyloctyl, n-nonyl, n-decyl, 1-methyldecyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, or n-eicosyl, and the like.
As the "alkylene group", a divalent group obtained by removing one hydrogen from the "alkyl group" can be cited. Examples thereof include a linear alkylene group having 1 to 24 carbon atoms and a branched alkylene group having 3 to 24 carbon atoms, and preferably an alkylene group having 1 to 18 carbon atoms (branched alkylene group having 3 to 18 carbon atoms), an alkylene group having 1 to 12 carbon atoms (branched alkylene group having 3 to 12 carbon atoms), an alkylene group having 1 to 6 carbon atoms (branched alkylene group having 3 to 6 carbon atoms), an alkylene group having 1 to 5 carbon atoms (branched alkylene group having 3 to 5 carbon atoms), an alkylene group having 1 to 4 carbon atoms (branched alkylene group having 3 to 4 carbon atoms) and the like.
As for the "alkenyl group", reference is made to the description of the "alkyl group" which is a group having a C — C single bond substituted by a C ═ C double bond in the structure of the "alkyl group", and which also includes a group having not only one but two or more single bonds substituted by a double bond (also referred to as an alkadienyl group or alkatrienyl group). Examples of the "alkenyl group" include a linear alkenyl group having 2 to 24 carbon atoms and a branched alkenyl group having 4 to 24 carbon atoms. Preferably C2-18 alkenyl, more preferably C2-12 alkenyl, further preferably C2-6 alkenyl, especially preferably C2-4 alkenyl. Specific "alkenyl" may include: vinyl, allyl, butadienyl, and the like.
As the "alkenylene group", a divalent group obtained by removing one hydrogen from the "alkenyl group" can be cited.
As the "alkynyl group", there may be mentioned a group in which a C-C single bond is substituted by a C.ident.C triple bond in the structure of the "alkyl group", and a group in which not only one but two or more single bonds are substituted by a triple bond (also referred to as a diacetylenic hydrocarbon-yl group or a trialkynic hydrocarbon-yl group) is also included.
As the "alkynylene group", a divalent group obtained by removing one hydrogen from the "alkynyl group" can be exemplified.
The "cycloalkyl group" is, for example, a cycloalkyl group having 3 to 24 carbon atoms, preferably a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 16 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, or a cycloalkyl group having 5 carbon atoms.
Specific "cycloalkyl" are for example: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, or a 1 to 5 or 1 to 4 carbon alkyl (particularly methyl) substituent thereof, bicyclo [1.1.0] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.1.0] pentyl, bicyclo [2.1.1] hexyl, bicyclo [3.1.0] hexyl, bicyclo [2.2.1] heptyl (norbornyl), bicyclo [2.2.2] octyl, adamantyl, diamantane (diamantane) group, decahydronaphthyl, or decahydroazulenyl.
The "cycloalkylene group" is, for example, a cycloalkylene group having 3 to 24 carbon atoms, preferably a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkylene group having 3 to 16 carbon atoms, a cycloalkylene group having 3 to 14 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, a cycloalkylene group having 5 to 10 carbon atoms, a cycloalkylene group having 5 to 8 carbon atoms, a cycloalkylene group having 5 to 6 carbon atoms, or a cycloalkylene group having 5 carbon atoms.
Specific examples of the "cycloalkylene group" include a structure in which one hydrogen is removed from the "cycloalkyl group" (monovalent group) to form a divalent group.
The "alkoxy group" may be any of a linear or branched chain, and is, for example, a linear alkoxy group having 1 to 24 carbon atoms or a branched alkoxy group having 3 to 24 carbon atoms, preferably an alkoxy group having 1 to 18 carbon atoms (a branched alkoxy group having 3 to 18 carbon atoms), an alkoxy group having 1 to 12 carbon atoms (a branched alkoxy group having 3 to 12 carbon atoms), an alkoxy group having 1 to 6 carbon atoms (a branched alkoxy group having 3 to 6 carbon atoms), an alkoxy group having 1 to 5 carbon atoms (a branched alkoxy group having 3 to 5 carbon atoms), an alkoxy group having 1 to 4 carbon atoms (a branched alkoxy group having 3 to 4 carbon atoms), and the like.
Specific "alkoxy" groups are for example: methoxy, ethoxy, n-propoxy, isopropoxy, 1-ethyl-1-methylpropoxy, 1-diethylpropoxy, 1, 2-trimethylpropoxy, 1,2, 2-tetramethylpropoxy, 1-ethyl-1, 2, 2-trimethylpropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, 2-ethylbutoxy, 1-dimethylbutoxy, 3-dimethylbutoxy, 1-diethylbutoxy, 1-ethyl-1-methylbutoxy, 1-propyl-1-methylbutoxy, 1, 3-trimethylbutoxy, 1-ethyl-1, 3-dimethylbutoxy, n-pentyloxy, isopentyloxy, n-pentyloxy, isopentyloxy, n-butyloxy, isobutyoxy, sec-butyloxy, tert-butyloxy, 2-ethylbutyloxy, 1-dimethylbutoxy, 3-dimethylbutoxy, 1, 2-ethylbutyloxy, 3-dimethylbutoxy, 3-butyloxy, 1, 2-dimethylbutoxy, 1, 2-ethylbutyloxy, 1, 2-dimethylbutoxy, 1, 2-dimethylbutoxy, 1, 2-dimethylbutoxy, 2, 1, 2-di-methylbutoxy, or a, Neopentyloxy, t-pentyloxy (t-amyloxy), 1-methylpentyloxy, 2-propylpentyloxy, 1-dimethylpentyloxy, 1-ethyl-1-methylpentyloxy, 1-propyl-1-methylpentyloxy, 1-butyl-1-methylpentyloxy, 1, 4-trimethylpentyloxy, n-hexyloxy, 1-methylhexyloxy, 2-ethylhexyloxy, 1-dimethylhexyloxy, 1-ethyl-1-methylhexyloxy, 1, 5-trimethylhexyloxy, 3,5, 5-trimethylhexyloxy, n-heptyloxy, 1-methylheptyloxy, 1-hexylheptyloxy, 1-dimethylheptyloxy, 2-dimethylheptyloxy, 2, 6-dimethyl-4-heptyloxy, n-octyloxy, tert-octyloxy (1,1,3, 3-tetramethylbutyloxy), 1-dimethyloctyloxy, n-nonyloxy, n-decyloxy, 1-methyldecyloxy, n-undecyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy, or n-eicosyloxy, and the like.
"aryloxy" is a group represented by "Ar-O- (Ar is aryl)", and as for details of the aryl group, a description of the "aryl group" can be cited.
"arylthio" is a group represented by "Ar-S- (Ar is an aryl)", and as for details of the aryl group, a description of the "aryl group" can be cited.
The "substituted silyl group" is, for example, a silyl group substituted with at least one of an aryl group, an alkyl group, and a cycloalkyl group, and is preferably a triarylsilyl group, a trialkylsilyl group, a tricycloalkylsilyl group, a dialkylcycloalkylsilyl group, or an alkylbicycloalkylsilyl group.
"Triarylsilyl" is a silyl group substituted with three aryl groups, and with respect to the details of the aryl groups, reference is made to the description of the "aryl group".
Specific "triarylsilyl group" is, for example, triphenylsilyl group, diphenylmononaphthylsilyl group, monophenyldinaphthylsilyl group, or trinaphthylsilyl group, etc.
"Trialkylsilyl" is a silyl group substituted with three alkyl groups, and for details of the alkyl groups, reference may be made to the description of the "alkyl groups".
Specific "trialkylsilyl groups" are, for example: trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, triisobutylsilyl group, tri-sec-butylsilyl group, tri-tert-butylsilyl group, ethyldimethylsilyl group, n-propyldimethylsilyl group, isopropyldimethylsilyl group, n-butyldimethylsilyl group, isobutyldimethylsilyl group, sec-butyldimethylsilyl group, tert-butyldimethylsilyl group, methyldiethylsilyl group, isopropyldiethylsilyl group, n-butyldiethylsilyl group, sec-butyldiethylsilyl group, methyldi-n-propylsilyl group, ethyldi-n-propylsilyl group, n-butyldi-n-propylsilyl group, sec-butyldi-n-propylsilyl group, tert-butyldi-n-propylsilyl group, methyldiisopropylsilyl group, ethyldiisopropylsilyl group, isopropylsilyl group, n-butylsilyl group, n-butylsilyl group, and butylsilyl group, N-butyldiisopropyl silane, sec-butyldiisopropyl silane, tert-butyldiisopropyl silane, or the like.
"Tricycloalkylsilyl" is a silyl group substituted with three cycloalkyl groups, and for the details of the cycloalkyl groups, reference may be made to the description of the "cycloalkyl groups".
Specific examples of the "tricycloalkylsilyl group" include tricyclopentylsilyl group, tricyclohexylsilyl group and the like.
"Dialkylcycloalkylsilyl" is a silyl group substituted with two alkyl groups and one cycloalkyl group, and for a detailed description of the alkyl and cycloalkyl groups, reference may be made to the descriptions of the "alkyl" and "cycloalkyl" groups.
"Alkylbicycloalkylsilyl" is a silyl group substituted with one alkyl group and two cycloalkyl groups, and for details of the alkyl and cycloalkyl groups, reference may be made to descriptions of the "alkyl" and "cycloalkyl" groups.
Specifically, the emission wavelength can be adjusted by the steric hindrance, electron donating property, and electron withdrawing property of the structure of the first substituent or the second substituent, but the group represented by the following structural formula is preferable, and methyl group, tert-butyl group, tert-pentyl group, tert-octyl group, neopentyl group, adamantyl group, phenyl group, o-tolyl group, p-tolyl group, 2, 4-xylyl group, 2, 5-xylyl group, 2, 6-xylyl group, 2,4, 6-mesityl group, diphenylamino group, di-p-tolylamino group, bis (p-tert-butyl) phenyl group, carbazolyl group, 3, 6-dimethylcarbazolyl group, 3, 6-di-tert-butylcarbazolyl group, and phenoxy group are more preferable, and methyl group, tert-butyl group, tert-pentyl group, tert-octyl group, neopentyl group, adamantyl group, phenyl group, o-tolyl group, 2, 6-xylyl group, 2,4, 6-mesitylene, 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, a group having a large steric hindrance is preferable for selective synthesis, and specifically, t-butyl group, t-amyl group, t-octyl group, adamantyl group, o-tolyl group, p-tolyl group, 2, 4-xylyl group, 2, 5-xylyl group, 2, 6-xylyl group, 2,4, 6-mesityl group, di-p-tolylamino group, bis (p- (t-butyl) phenyl) amino group, 3, 6-dimethylcarbazolyl group, and 3, 6-di-t-butylcarbazolyl group are preferable.
In the following structural formulae, "Me" represents a methyl group, "tBu" represents a tert-butyl group, "tAm" represents a tert-pentyl group, "thoct" represents a tert-octyl group, and a bond site.
[ solution 25]
Figure BDA0003527825380000301
[ solution 26]
Figure BDA0003527825380000302
[ solution 27]
Figure BDA0003527825380000311
[ solution 28]
Figure BDA0003527825380000321
[ solution 29]
Figure BDA0003527825380000331
[ solution 30]
Figure BDA0003527825380000332
[ solution 31]
Figure BDA0003527825380000341
[ solution 32]
Figure BDA0003527825380000342
[ solution 33]
Figure BDA0003527825380000351
[ chemical 34]
Figure BDA0003527825380000352
[ solution 35]
Figure BDA0003527825380000361
[ solution 36]
Figure BDA0003527825380000362
[ solution 37]
Figure BDA0003527825380000371
[ solution 38]
Figure BDA0003527825380000372
[ solution 39]
Figure BDA0003527825380000381
[ solution 40]
Figure BDA0003527825380000391
[ solution 41]
Figure BDA0003527825380000392
[ solution 42]
Figure BDA0003527825380000401
< description of Cycloalkane condensation >
In addition, at least one of the aromatic ring and the heteroaromatic ring in the chemical structure of the polycyclic aromatic compound of the present invention may be condensed with at least one cycloalkane.
For example, at least one of the ring B, ring C, ring D, ring E, ring F, ring G, aryl, and heteroaryl in the compound represented by formula (1A) or formula (1B), the ring B, ring C, ring D, ring E, ring F, ring G, the "formed ring", aryl, and heteroaryl in the compound represented by formula (2A) or formula (2B) (including aryl and heteroaryl as part of each substituent listed above) may be condensed with at least one cycloalkane.
Examples of the "cycloalkane" include: a C3-24 cycloalkane, a C3-20 cycloalkane, a C3-16 cycloalkane, a C3-14 cycloalkane, a C5-10 cycloalkane, a C5-8 cycloalkane, a C5-6 cycloalkane, a C5 cycloalkane, and the like.
Specific cycloalkanes include: cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, bicyclo [1.1.0] butane, bicyclo [1.1.1] pentane, bicyclo [2.1.0] pentane, bicyclo [2.1.1] hexane, bicyclo [3.1.0] hexane, bicyclo [2.2.1] heptane (norbornane), bicyclo [2.2.2] octane, adamantane, bisadamantane, decahydronaphthalene, decahydroazulene, and carbon number-1 to 5 alkyl (particularly methyl) substituents, halogen (particularly fluorine) substituents, and carbon number-1 to 5 substituents thereof.
Among these, for example, a structure in which at least one hydrogen on the carbon at the α -position of a cycloalkane (a carbon at a position adjacent to the carbon at the condensation site in a cycloalkyl group condensed in an aromatic ring or a heteroaromatic ring) is substituted as shown in the following structural formula is preferable, a structure in which two hydrogens on the carbon at the α -position are substituted is more preferable, and a structure in which a total of four hydrogens on the two carbon at the α -position are substituted is even more preferable. Examples of the substituent include an alkyl (particularly methyl) substituent having 1 to 5 carbon atoms, a halogen (particularly fluorine) substituent, and a deuterium substituent.
[ solution 43]
Figure BDA0003527825380000411
The number of cycloalkanes condensed in one aromatic ring or heteroaromatic ring is preferably one to three, more preferably one or two, and still more preferably one. For example, examples in which one or more cycloalkanes are condensed in one benzene ring (phenyl group) are shown below. In the respective structural formulae, when the compound is a benzene ring, the compound refers to a benzene ring included in the skeleton structure of the compound, and when the compound is a phenyl group, the compound refers to a bond substituted in the skeleton structure of the compound. Cycloalkanes condensed as shown in the formula (Cy-1-4) and the formula (Cy-2-4) may be condensed with each other. The same applies to the case where the ring (group) to be condensed is an aromatic or heteroaromatic ring other than a benzene ring (phenyl group), and the case where the cycloalkane to be condensed is cyclopentane or a cycloalkane other than cyclohexane.
[ solution 44]
Figure BDA0003527825380000412
At least one-CH in cycloalkanes 2 -may be substituted by-O-. In which a plurality of-CH 2 -when substituted by-O-, the adjacent-CH 2 -is not substituted by-O-. For example, one or more-CH groups in cycloalkane condensed with one benzene ring (phenyl group) are shown below 2 Examples of-O-substitution. In the respective structural formulae, when the compound is a benzene ring, the compound refers to a benzene ring included in the skeleton structure of the compound, and when the compound is a phenyl group, the compound refers to a bond substituted in the skeleton structure of the compound. The same applies to the case where the condensed ring (group) is an aromatic ring or a heteroaromatic ring other than a benzene ring (phenyl group), and the case where the cycloalkane to be condensed is cyclopentane or a cycloalkane other than cyclohexane.
[ solution 45]
Figure BDA0003527825380000413
At least one hydrogen in the cycloalkane may be substituted, and as the substituent, for example: aryl, heteroaryl, diarylamino (two aryl groups are not bonded to each other or via a linking group), diheteroarylamino (two heteroaryl groups of diheteroarylamino are not bonded to each other or via a linking group), arylheteroarylamino (aryl and heteroaryl groups are not bonded to each other or via a linking group), diarylboron (two aryl groups are not bonded via a single bond or a linking group or are bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, aryloxy, substituted silyl, deuterium, cyano, or halogen, details of which can be cited in the description of the first substituent. Among these substituents, preferred are alkyl groups (e.g., alkyl groups having 1 to 6 carbon atoms), cycloalkyl groups (e.g., cycloalkyl groups having 3 to 14 carbon atoms), halogens (e.g., fluorine), and deuterium. In addition, when the cycloalkyl group is substituted, the substitution form may be a spiro structure, and for example, an example in which a spiro structure is formed on a cycloalkane condensed on one benzene ring (phenyl group) is shown below. In the respective structural formulae, when the compound is a benzene ring, the compound refers to a benzene ring included in the skeleton structure of the compound, and when the compound is a phenyl group, the compound refers to a bond substituted in the skeleton structure of the compound.
[ solution 46]
Figure BDA0003527825380000421
As another form of the cycloalkane condensation, examples of the polycyclic aromatic compound of the present invention include the following: substituted with diarylamino groups condensed with cycloalkanes (condensed to the aryl portion thereof), carbazolyl groups condensed with cycloalkanes (condensed to the benzene ring portion thereof), or benzocarbazolyl groups condensed with cycloalkanes (condensed to the benzene ring portion thereof). With regard to the "diarylamino group", the description may be cited.
Further, as more specific examples, the following may be mentioned: r in the polycyclic aromatic compound represented by the formula (1A) or (2A) a Is a diarylamino group (condensed to its aryl moiety) condensed with a cycloalkane or a carbazolyl group (condensed to its benzene ring moiety) condensed with a cycloalkane.
< description of substitution with deuterium, cyano, or halogen >
At least one hydrogen in the polycyclic aromatic compound of the present invention may be substituted with deuterium, cyano, or halogen. Halogen is fluorine, chlorine, bromine, or iodine, preferably fluorine, chlorine, or bromine, more preferably fluorine or chlorine.
< description of specific examples of polycyclic aromatic Compounds of the present invention >
For example, a compound represented by any one of the following structural formulae is preferable.
[ solution 47]
Figure BDA0003527825380000431
In the following formulas, the first and second groups,
r is independently hydrogen, an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a diarylamino group (wherein the aryl group is an aryl group having 6 to 10 carbon atoms), a diarylboron group (wherein the aryl group is an aryl group having 6 to 10 carbon atoms, and both aryl groups may be bonded by 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, at least one hydrogen of which may be substituted by an alkyl group having 1 to 5 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms,
o is an integer of 1 to 3,
p is an integer of 1 to 4,
q is an integer of 1 to 5,
at least one hydrogen in the compounds of each formula may be substituted with deuterium, cyano, or halogen.
More specific description of R may refer to the description of said aryl group and the like. O, p, and q are preferably 1 or 2, more preferably 1, and still more preferably 0.
< utilization as a Thermally Active Delayed Fluorescence (TADF) material >
The compounds of the present invention may also be used as TADF materials. In particular, the compounds represented by the formulae (1A) and (2A) are preferable to the compounds represented by the formulae (1B) and (2B), and the ring bonded in common to the condensed bicyclic structure in the B ring to the G ring or the B ring to the G ring is preferably a 6-membered ring, and more preferably a 6-membered aryl ring including the a ring.
< description of specific examples of polycyclic aromatic Compounds of the present invention >
More specific examples of the polycyclic aromatic compound include compounds represented by the following structural formulae. In the following structural formulae, "Me" represents a methyl group, "tBu" represents a tert-butyl group, and "D" represents deuterium.
[ solution 48]
Figure BDA0003527825380000441
[ solution 49]
Figure BDA0003527825380000451
[ solution 50]
Figure BDA0003527825380000461
[ solution 51]
Figure BDA0003527825380000471
[ chemical formula 52]
Figure BDA0003527825380000481
[ chemical formula 53]
Figure BDA0003527825380000491
[ solution 54]
Figure BDA0003527825380000501
[ solution 55]
Figure BDA0003527825380000502
[ solution 56]
Figure BDA0003527825380000503
[ solution 57]
Figure BDA0003527825380000511
[ solution 58]
Figure BDA0003527825380000521
[ chemical 59]
Figure BDA0003527825380000531
[ solution 60]
Figure BDA0003527825380000541
[ solution 61]
Figure BDA0003527825380000551
[ chemical formula 62]
Figure BDA0003527825380000561
[ solution 63]
Figure BDA0003527825380000571
[ chemical formula 64]
Figure BDA0003527825380000581
[ chemical 65]
Figure BDA0003527825380000591
[ chemical formula 66]
Figure BDA0003527825380000601
The polycyclic aromatic compound of the present invention can be used as a polymer compound obtained by polymerizing a reactive compound having a reactive substituent substituted in the polycyclic aromatic compound as a monomer, a crosslinked polymer compound obtained by polymerizing a monomer having a polymerizable substituent, or a suspended polymer compound obtained by polymerizing a reactive compound having a crosslinkable substituent in the suspended polymer compound, or a suspended polymer compound obtained by polymerizing a reactive compound having a reactive substituent in the polycyclic aromatic compound as a monomer, the polymer crosslinked material is obtained by further crosslinking the polymer compound, the pendant polymer compound is obtained by reacting a main chain polymer with the reactive compound, and the pendant polymer crosslinked material is obtained by further crosslinking the pendant polymer compound.
The reactive substituent (including the polymerizable substituent, the crosslinkable substituent, and the reactive substituent for obtaining a pendant polymer, hereinafter also simply referred to as "reactive substituent") is not particularly limited as long as it is a substituent capable of imparting a high molecular weight to the polycyclic aromatic compound, a substituent capable of further crosslinking the polymer compound obtained in this manner, and a substituent capable of imparting a pendant reaction to a main chain polymer. Each structural formula represents a bonding site.
[ solution 67]
Figure BDA0003527825380000611
L is independently a single bond, -O-, -S-, > C ═ O, -O-C (═ O) -, C1-12 alkylene, C1-12 oxyalkylene, or C1-12 polyoxyalkylene. Among the substituents, preferred is a group represented by formula (XLS-1), formula (XLS-2), formula (XLS-3), formula (XLS-9), formula (XLS-10) or formula (XLS-17), and more preferred is a group represented by formula (XLS-1), formula (XLS-3) or formula (XLS-17).
Such a polymer compound, a polymer crosslinked body, a pendant polymer compound, and a pendant polymer crosslinked body may contain, in addition to the repeating unit of the polycyclic aromatic compound of the present invention, at least one selected from the group of compounds consisting of substituted or unsubstituted triarylamine, substituted or unsubstituted fluorene, substituted or unsubstituted anthracene, substituted or unsubstituted tetracene, substituted or unsubstituted triazine, substituted or unsubstituted carbazole, substituted or unsubstituted tetraphenylsilane, substituted or unsubstituted spirofluorene, substituted or unsubstituted triphenylphosphine, substituted or unsubstituted dibenzothiophene, and substituted or unsubstituted dibenzofuran, as a repeating unit.
Examples of the substituent in these repeating units include: aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryl groups may be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, aryloxy, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, or alkylbicycloalkylsilyl groups, and the like. The description of the polycyclic aromatic compounds of the present invention can be cited with respect to the details of the "aryl group" of the triarylamine or the substituents.
The use of such a polymer compound, crosslinked polymer, pendant polymer compound and crosslinked pendant polymer (hereinafter, also simply referred to as "polymer compound and crosslinked polymer") will be described in detail later.
2. Method for producing polycyclic aromatic compound of the present invention
The polycyclic aromatic compounds of the invention are basically prepared by first using a bonding group ("N" ", or containing X 1 Or X 2 A group) to bond the a ring and the B ring to the G ring or the B ring to the G ring, thereby producing an intermediate (first reaction), and then, using a bonding group (including Y) 1 ～Y 3 The group (B) bonds the a ring to the B ring to the G ring or the B ring to the G ring, thereby producing the final product (second reaction). Reference is made to the production method described in International publication No. 2015/102118.
In the first Reaction, for example, in the case of etherification, a nucleophilic substitution Reaction, Ullmann Reaction (Ullmann Reaction) or the like can be used, and in the case of amination, a Buchwald-Hartwig Reaction or the like can be used. In addition, in the second Reaction, a Tandem Hetero-Friedel-Crafts Reaction (consecutive aromatic electrophilic substitution Reaction, the same applies hereinafter) can be used.
As shown in the following schemes (1) and (2), the second reaction is to introduce Y bonding the a ring and the B to G rings or the B to G rings 1 ～Y 3 The reaction of (1). First, N and X are each coupled with N-butyllithium, sec-butyllithium, tert-butyllithium or the like 1 And X 2 The hydrogen atoms in between, or "N" hydrogen atoms in between, are ortho-metalated. Then, Y such as boron trichloride or boron tribromide is added 1 ～Y 3 The halide of (2) is subjected to a lithium-boron metal exchange, and then a Bronsted base such as N, N-diisopropylethylamine is added thereto to thereby carry out a Tandem borofriedel-Crafts Reaction (Tandem Bora-Friedel-Crafts Reaction), whereby the target compound can be obtained. In the second reaction, a Lewis acid (Lewis acid) such as aluminum trichloride may be added to accelerate the reaction. Note that the definitions of symbols in each structural formula in the following schemes (1) and (2) and the following schemes are the same as those described above. In addition, The chemical Journal of The American Chemistry, 2018,140 1195-1198, omitting the step of metalating the hydrogen atom (H) with an organic basic compound and reacting with Y 1 A method of directly reacting a halide (boron tribromide, etc.).
[ solution 68]
Figure BDA0003527825380000621
[ solution 69]
Figure BDA0003527825380000631
In the above-mentioned scheme, lithium is introduced to a desired position by ortho-metalation, but lithium may be introduced to a desired position by halogen-metal exchange as well as introduction of a bromine atom or the like to a position to which lithium is to be introduced as in the following scheme (3). According to the above method, even when ortho-metalation is not possible due to the influence of a substituent, a target product can be produced, and this method is useful.
[ solution 70]
Figure BDA0003527825380000632
The above-mentioned schemes (1) to (3) are Y 1 ～Y 3 A typical production method of a compound that is a boron (B) atom.
Next, Y is put 1 ～Y 3 The case of a phosphine sulfide, phosphine oxide or phosphorus atom is shown as an example in the following schemes (4) and (5). As described above, first, N and X are paired with N-butyllithium or the like 1 And X 2 The hydrogen atoms in between, or "N" hydrogen atoms in between, are ortho-metalated. Then, phosphorus trichloride and sulfur are added in this order, and finally, a Lewis acid such as aluminum trichloride and a Bronsted base such as N, N-diisopropylethylamine are added to carry out a Tandem phosphofriedel-Crafts Reaction (Tandem Phospho-Friedel-Crafts Reaction), whereby Y can be obtained 1 ～Y 3 Is a phosphine sulfide compound. Y can be obtained by treating the obtained phosphine sulfide compound with m-Chloroperoxybenzoic acid (m-CPBA) 1 ～Y 3 Y being a compound of a phosphine oxide, by treatment with triethylphosphine 1 ～Y 3 Is a compound of phosphorus atom.
[ solution 71]
Figure BDA0003527825380000641
[ chemical 72]
Figure BDA0003527825380000651
In the above-mentioned flow, Y is mainly described 1 ～Y 3 Examples of the compound include B, P, P ═ O and P ═ S, but other compounds can be produced by appropriately changing the raw materials.
The following example is shown in the flow: adding Y such as boron trichloride or boron tribromide 1 ～Y 3 Before the halide of (2), the pair of "N" and X is made of butyllithium or the like 1 And X 2 While the tandem hetero Friedel-crafts reaction is carried out by subjecting hydrogen atoms (or halogen atoms) between them or hydrogen atoms (or halogen atoms) between "N" to ortho-metallation, it is also possible to add Y such as boron trichloride or boron tribromide without subjecting to ortho-metallation using butyllithium or the like 1 ～Y 3 To carry out the reaction.
The solvent used in the above-mentioned process may be, for example, tert-butyl benzene or xylene.
Examples of the ortho-metallation reagent used in the above-mentioned scheme include: an alkyllithium such as methyllithium, n-butyllithium, sec-butyllithium or tert-butyllithium, an organic basic compound such as lithium diisopropylamide, lithium tetramethylpiperidide, lithium hexamethyldisilazide or potassium hexamethyldisilazide, and an alkali metal such as Na dispersed in an organic solvent.
As described aboveMetal- (Y) used in the procedure 1 ～Y 3 ) The metal exchange reagent of (2) includes: y is 1 ～Y 3 Of (b) a trifluoride, Y 1 ～Y 3 Trichloride of (a) and Y 1 ～Y 3 Tribromide of (5), Y 1 ～Y 3 Y being triiodide or the like 1 ～Y 3 Halide of (4), CIPN (NEt) 2 ) 2 Equal Y 1 ～Y 3 Of an aminated halide of, Y 1 ～Y 3 Alkoxylates of (B), Y 1 ～Y 3 And aryloxy compounds of (4).
Examples of the bronsted base used in the above scheme include: n, N-diisopropylethylamine, triethylamine, 2,2,6, 6-tetramethylpiperidine, 1,2,2,6, 6-pentamethylpiperidine, N-dimethylaniline, N-dimethyltoluidine, 2, 6-lutidine, sodium tetraphenylborate, potassium tetraphenylborate, triphenylborane, tetraphenylsilane, Ar, N-diisopropylethylamine, N-tetramethylpiperidine, N-dimethyltoluidine, N-dimethylpyridine, N-tetramethylpiperidine, N-dimethylborane, N-diisopropylethylamine, N-tetramethylpiperidine, N-dimethylpiperidine, N-dimethylborane, N-dimethylborane, N-tetramethylsilane, N-diisopropylethylamine, 2,2, 2, 6-tetramethylpiperidine, 2-diisopropylethylamine, 2-tetramethylborane, and a 4 BNa、Ar 4 BK、Ar 3 B、Ar 4 Si (Ar represents an aryl group such as a phenyl group), and the like.
As lewis acids used in the above-mentioned scheme, there can be mentioned: AlCl 3 、AlBr 3 、AlF 3 、BF 3 ·OEt 2 、BCl 3 、BBr 3 、GaCl 3 、GaBr 3 、InCl 3 、InBr 3 、In(OTf) 3 、SnCl 4 、SnBr 4 、AgOTf、ScCl 3 、Sc(OTf) 3 、ZnCl 2 、ZnBr 2 、Zn(OTf) 2 、MgCl 2 、MgBr 2 、Mg(OTf) 2 、LiOTf、NaOTf、KOTf、Me 3 SiOTf、Cu(OTf) 2 、CuCl 2 、YCl 3 、Y(OTf) 3 、TiCl 4 、TiBr 4 、ZrCl 4 、ZrBr 4 、FeCl 3 、FeBr 3 、CoCl 3 、CoBr 3 And so on.
In the scheme, in order to promote the cascade of hybrid Friedel-crafts reaction, a Bransted base or Lewis acid can also be used. Wherein, Y is used 1 ～Y 3 Of (b) a trifluoride, Y 1 ～Y 3 Trichloride of (a) and Y 1 ～Y 3 Tribromide of (5), Y 1 ～Y 3 Y being triiodide or the like 1 ～Y 3 In the case of the halide of (3), an acid such as hydrogen fluoride, hydrogen chloride, hydrogen bromide, or hydrogen iodide is generated as the aromatic electrophilic substitution reaction proceeds, and therefore, it is effective to use a Bronsted base which traps an acid. On the other hand, in the use of Y 1 ～Y 3 Of an aminated halide of, Y 1 ～Y 3 In the case of the alkoxylate (b), since an amine or an alcohol is produced as the aromatic electrophilic substitution reaction proceeds, it is often effective to use a lewis acid which accelerates the elimination of the amino group or alkoxy group because the bronsted base is not required to be used.
The polycyclic aromatic compound of the present invention also includes a compound in which at least a part of hydrogen is substituted with deuterium, cyano group, or halogen, and such a compound can be produced in the same manner as described above by using a raw material in which a desired position is halogenated with deuteration, cyanation, fluorination, chlorination, or the like.
3. Organic device
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
Hereinafter, the organic EL device of the present embodiment will be described in detail with reference to the drawings. Fig. 1 is a schematic sectional view showing an organic EL element according to the present embodiment.
< Structure of organic electroluminescent element >
The organic EL element 100 shown in fig. 1 includes: the light-emitting device comprises a substrate 101, an anode 102 disposed on the substrate 101, a hole injection layer 103 disposed on the anode 102, a hole transport layer 104 disposed on the hole injection layer 103, a light-emitting layer 105 disposed on the hole transport layer 104, an electron transport layer 106 disposed on the light-emitting layer 105, an electron injection layer 107 disposed on the electron transport layer 106, and a cathode 108 disposed on the electron injection layer 107.
In addition, the organic EL device 100 may have a structure in which the order of production is reversed, for example, the structure including: the organic light emitting diode comprises a substrate 101, a cathode 108 arranged on the substrate 101, an electron injection layer 107 arranged on the cathode 108, an electron transport layer 106 arranged on the electron injection layer 107, a light emitting layer 105 arranged on the electron transport layer 106, a hole transport layer 104 arranged on the light emitting layer 105, a hole injection layer 103 arranged on the hole transport layer 104, and an anode 102 arranged on the hole injection layer 103.
All of the layers are not indispensable, and the minimum constituent unit is constituted by the anode 102, the light-emitting layer 105, and the cathode 108, and the hole injection layer 103, the hole transport layer 104, the electron transport layer 106, and the electron injection layer 107 are layers that can be arbitrarily provided. In addition, each of the layers may include a single layer, or may include a plurality of layers.
As the form of the layers constituting the organic EL element, in addition to the above-mentioned "substrate/anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode" form, there may be mentioned "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 EL element 100, and quartz, glass, metal, plastic, or the like is generally used. The substrate 101 is shaped according to the purposeThe sheet-like, film-like, or sheet-like shape may be formed, and for example, a glass plate, a metal foil, a plastic film, a plastic sheet, or the like may 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 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, it is preferable that the amount of eluted ions from the glass is as small as possible, and therefore, it is preferable to use an alkali-free glass, and SiO is added 2 Etc. 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 at least one of the hole injection layer 103 and the hole transport layer 104 is provided between the anode 102 and the light-emitting layer 105, holes are injected into the light-emitting layer 105 through these layers.
As a material for forming the anode 102, an inorganic compound and an organic compound can be cited. Examples of the inorganic compound include: metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (Indium Oxide, Tin Oxide, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), etc.), metal halides (copper iodide, etc.), copper sulfide, carbon black, ITO glass, or Nesa glass), and the like. Examples of the organic compound include: polythiophene such as poly (3-methylthiophene), and conductive polymers such as polypyrrole and polyaniline. Further, it can be suitably selected from substances used as an anode of an organic EL element.
The resistance of the transparent electrode is not limited as long as it can supply a sufficient current for light emission of the light-emitting element, and 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, a low-resistance product of, for example, 100 Ω/γ to 5 Ω/γ, preferably 50 Ω/γ to 5 Ω/γ is particularly preferably used. The thickness of ITO can be arbitrarily selected depending on the resistance value, and is usually used in a range of 50nm to 300nm in many cases.
< hole injection layer and hole transport layer in organic electroluminescent element >
The hole injection layer 103 functions to efficiently inject holes transferred from the anode 102 into the light-emitting layer 105 or the hole transport layer 104. The hole transport layer 104 functions to efficiently transport holes injected from the anode 102 or holes injected from the anode 102 through the hole injection layer 103 to the light-emitting layer 105. The hole injection layer 103 and the hole transport layer 104 are formed by laminating and mixing one or more kinds of hole injection/transport materials, or are formed by mixing a hole injection/transport material and a polymer binder. Further, an inorganic salt such as iron (III) chloride may be added to the hole injection/transport material to form a layer.
The hole injecting/transporting substance needs to efficiently inject/transport holes from the positive electrode between electrodes to which an electric field is applied, and it is desirable that the hole injecting efficiency is high and the injected holes are efficiently transported. Therefore, a substance having a small ionization potential, a large hole mobility, and excellent stability, and in which impurities serving as traps are not easily generated during production and use, is preferable. In the present invention, as the material for the hole injection layer and the hole transport layer, a polycyclic aromatic compound represented by the above general formula (1A) or general formula (1B) can be used.
As the material for forming the hole injection layer 103 and the hole transport layer 104, any compound can be selected from compounds conventionally used as charge transport materials for holes in photoconductive materials, p-type semiconductors, and known compounds used in hole injection layers and hole transport layers of organic EL devices. Specific examples of the CompoundA biscarbazole derivative such as a carbazole derivative (e.g., N-phenylcarbazole, polyvinylcarbazole, etc.), bis (N-arylcarbazole) or bis (N-alkylcarbazole), a triarylamine derivative (a polymer 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, N, n '-dinaphthyl-N, N' -diphenyl-4, 4 '-diphenyl-1, 1' -diamine, N 4 ,N 4 ' -Diphenyl-N 4 ,N 4 '-bis (9-phenyl-9H-carbazol-3-yl) - [1,1' -biphenyl]4,4' -diamine, N 4 ,N 4 ,N 4 ',N 4 '-tetrakis [1,1' -biphenyl]-4-yl- [1,1' -biphenyl]Triphenylamine derivatives such as-4, 4 '-diamine, 4',4 ″ -tris (3-methylphenyl (phenyl) amino) triphenylamine, starburst amine derivatives, etc.), stilbene derivatives, phthalocyanine derivatives (metal-free, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone 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, etc.), heterocyclic compounds such as porphyrin derivatives, polysilanes, etc. In the polymer system, a polycarbonate or a styrene derivative, polyvinylcarbazole, polysilane, or the like having the monomer in the side chain is preferable, but there is no particular limitation as long as it is a compound which forms a thin film necessary for manufacturing a light-emitting element, can inject holes from an anode, and can transport holes.
Further, it is also known that the conductivity of an organic semiconductor is strongly affected by doping. Such an organic semiconductor matrix material contains a compound having a good electron donating property or a compound having a good electron accepting property. For the doping of electron-donating substances, strong electron acceptors such as Tetracyanoquinodimethane (TCNQ) or 2,3,5, 6-tetrafluorotetracyanoquinodimethane (2,3,5, 6-tetrafluorolotetracynano-1, 4-benzoquinodimethane (2,3,5, 6-tetrafluoro-1, 4-benzoquinodimethane, F4TCNQ) are known (see, for example, documents "m. faffy, a. bayer, t. friez, k. rio (m. pfeiffer, a. beyer, t.fritz, k.leo)," applied physics article (pff. lett.), (73), (22), 3202. quiz 3204(1998) "and documents" j. buloevez, m. faffy, t. friez, k. litt., "applied physics article j. blowwit, p. wo.731, t. lett.," applied physics article (t.), "applied electronics article (t. fti., t.)," applied electronics article (t. fti.73, t.), "applied electronics article (r, t.)," applied electronics article (p. fti). 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 the matrix material having a hole transporting property, for example, a benzidine derivative (N, N ' -bis (3-methylphenyl) -N, N ' -bis (phenyl) benzidine (N, N ' -bis (3-methylphenenyl) -N, N ' -bis (phenyl) benzidine, TPD) or the like) or a starburst amine derivative (4,4',4 ″ -tris (N, N-diphenylamino) triphenylamine, TDATA, or the like), or a specific metal phthalocyanine (particularly zinc phthalocyanine (ZnPc) or the like) is known (japanese patent laid-open No. 2005-167175).
The material for a hole injection layer and the material for a hole transport layer can be used as a material for a hole layer as a polymer compound or a crosslinked polymer thereof, or as a pendant-type polymer compound or a crosslinked pendant-type polymer thereof: the polymer compound is obtained by polymerizing a reactive compound, as a monomer, substituted with a reactive substituent in the material for the hole injection layer and the material for the hole transport layer, and the pendant polymer compound is obtained by reacting a main chain polymer with the reactive compound. As the reactive substituent in such a case, the description of the polycyclic aromatic compound represented by the above general formula (1A) or general formula (1B) can be cited.
The use of such a polymer compound and a crosslinked polymer will be described in detail later.
< light-emitting layer in organic electroluminescent element >
The light-emitting layer 105 emits light by recombination of holes injected from the anode 102 and electrons injected from the cathode 108 between electrodes to which an electric field is applied. The material for forming the light-emitting layer 105 may be a compound that emits light by being excited by recombination of holes and electrons (light-emitting compound), and is preferably a compound that can be formed into a stable thin film shape and that exhibits strong light emission (fluorescence) efficiency in a solid state. In the present invention, as a material for the light-emitting layer, a host material and, for example, a polycyclic aromatic compound represented by the above general formula (1A) or general formula (1B) as a dopant material 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 contained within the bulk of the host material, or may be contained within a portion of the host material, either. The doping method may be a co-evaporation method with the host material, a simultaneous evaporation method in which the host material is mixed in advance, or a wet film formation method in which the host material is mixed in advance with an organic solvent 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 material used is preferably 0.001 to 50 wt%, more preferably 0.05 to 20 wt%, and still more preferably 0.1 to 10 wt% of the total material for the light-emitting layer. In the above range, for example, concentration quenching is preferably prevented. In addition, from the viewpoint of durability, it is also preferable that a part or all of hydrogen atoms of the dopant material be deuterated.
On the other hand, in the organic electroluminescent element using the thermally activated delayed fluorescence dopant material, the amount of the dopant material used is preferably low in terms of preventing the concentration quenching phenomenon, but is preferably high in terms of the efficiency of the thermally 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 40 to 99.999 wt%, 59 to 1 wt%, and 20 to 0.001 wt%, preferably 60 to 99.99 wt%, 39 to 5 wt%, and 10 to 0.01 wt%, more preferably 70 to 99.95 wt%, 29 to 10 wt%, and 5 to 0.05 wt%, respectively, of the total material for the light-emitting layer. The compound represented by the general formula (1A) or the general formula (1B) and a polymer compound thereof can also be used as an auxiliary dopant material.
As the host material, there can be mentioned: 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-emitting bodies.
From the viewpoint of promoting but not inhibiting the generation of TADF in the light-emitting layer, the triplet energy of the host material is preferably higher than the triplet energy of the dopant or the assist dopant having the highest triplet energy in the light-emitting layer, and specifically, the triplet energy of the host material is preferably 0.01eV or more, more preferably 0.03eV or more, and further preferably 0.1eV or more. In addition, a compound having TADF activity may also be used in the host material.
Examples of host materials include: a compound represented by the following general formula (H1), a compound represented by the following general formula (H2), a compound represented by the following general formula (H3), a compound having a structure represented by the following general formula (H4), a compound represented by the following general formula (H5), a compound represented by the following general formula (H6), and a TADF material. Preferred is a compound represented by the general formula (H1).
[ solution 73]
Figure BDA0003527825380000701
< Compound represented by the general formula (H1) >)
[ chemical formula 74]
Figure BDA0003527825380000702
In the formula (H1), L 1 Is 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, more preferably a heteroarylene group having 2 to 20 carbon atoms, further preferably a heteroarylene group having 2 to 15 carbon atoms, and particularly preferably a heteroarylene group having 2 to 10 carbon atoms. Specific examples of the arylene group include: a divalent group such as a benzene ring, a biphenyl ring, a naphthalene ring, a tribiphenyl ring, an acenaphthene ring, a fluorene ring, a phenalene ring, a phenanthrene ring, a triphenylene ring, a pyrene ring, a tetracene ring, a perylene ring, and a pentacene ring. Specific examples of the heteroarylene group include: a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an oxadiazole ring, a thiadiazole ring, a triazole ring, a tetrazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring, an indole ring, an isoindole ring, a 1H-indazole ring, a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, a 1H-benzotriazole ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinazoline ring, a quinoxaline ring, an oxazine ring, a naphthyridine ring, a purine ring, a pteridine ring, a carbazole ring, an acridine ring, a phenoxathiin ring, a phenoxazine ring, a phenothiazine ring, a phenazine ring, an indolizine ring, a furan ring, a benzofuran ring, an isobenzofuran ring, a dibenzofuran ring, a thiophene ring, a benzothiophene ring, a dibenzothiophene ring, a oxadiazole ring, an anthracene ring, an indolocarbazole ring, a benzindole ring, a carbazole ring, II A benzindolocarbazole ring, a naphthobenzofuran ring, and the like.
At least one hydrogen in the compound represented by the formula (H1) 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.
< Compound represented by the general formula (H2) >
[ solution 75]
Figure BDA0003527825380000711
In the formula (H2), L 2 And L 3 Each independently an aryl group having 6 to 30 carbon atoms or a heteroaryl group having 2 to 30 carbon atoms. 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 monovalent group such as a benzene ring, a biphenyl ring, a naphthalene ring, a terphenyl ring, an acenaphthene ring, a fluorene ring, a phenalene ring, a phenanthrene ring, a triphenylene ring, a pyrene ring, a tetracene ring, a perylene ring, and a pentacene ring. The heteroaryl group is preferably a heteroaryl group having 2 to 25 carbon atoms, more preferably a heteroaryl group having 2 to 20 carbon atoms, still more preferably a heteroaryl group having 2 to 15 carbon atoms, particularly preferably a heteroaryl group having 2 to 10 carbon atoms, and specifically, there can be mentioned: 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, phenoxathiin ring, phenoxazine ring, phenothiazine ring, phenazine azine ring, indolizine ring, furan ring, benzofuran ring, isobenzofuran ring, dibenzofuran ring, thiophene ring, dibenzothiophene ring, furazan ring, oxadiazole ring, anthracene ring, indolocarbazole ring, benzindolizarbazole ring, benzindolizazolocarbazole ring, indole ring, thiadiazole ring, and indole-carbazole ring, Dibenzoindolocarbazole ring and naphthobenzene And a furan ring, and the like.
At least one hydrogen in the compound represented by the formula (H2) 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.
< Compound (one example of Polymer host Material) > < represented by the general formula (H3)
[ 76]
Figure BDA0003527825380000712
In the formula (H3), the reaction mixture,
the MU is independently a divalent group represented by removing any two hydrogen atoms from the aromatic compound, EC is independently a monovalent group represented by removing any one hydrogen atom from the aromatic compound, two hydrogens in the MU are replaced by EC or MU, k is an integer of 2-50000.
More specifically, it is a method for producing,
MU is independently arylene, heteroarylene, diarylenearylamino, diarylenearylboranyl, oxahydrocarbyl-boron-diyl, azahydrocarbyl boron-diyl,
EC are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, or aryloxy,
at least one hydrogen of MU and EC may be further substituted with aryl, heteroaryl, diarylamino, alkyl, and cycloalkyl groups,
k is an integer of 2 to 50000.
k is preferably an integer of 20 to 50000, more preferably an integer of 100 to 50000.
At least one hydrogen of MU and EC in the formula (H3) may be substituted by an alkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms, a halogen or deuterium, and further, any-CH in the alkyl group 2 May be-O-or-Si (CH) 3 ) 2 -substitution in the alkyl group except-CH directly bonded to EC in formula (H3) 2 Any other than-CH 2 The alkyl group may be substituted with an arylene group having 6 to 24 carbon atoms, and any hydrogen in the alkyl group may be substituted with fluorine.
Examples of the MU include divalent groups represented by removing any two hydrogen atoms from any of the following compounds.
[ chemical 77]
Figure BDA0003527825380000721
More specifically, divalent groups represented by any of the following structures are included. Of these, MUs are bonded at one star to other MUs or ECs.
[ solution 78]
Figure BDA0003527825380000722
[ solution 79]
Figure BDA0003527825380000731
[ solution 80]
Figure BDA0003527825380000741
[ solution 81]
Figure BDA0003527825380000742
[ chemical 82]
Figure BDA0003527825380000751
[ solution 83]
Figure BDA0003527825380000752
[ solution 84]
Figure BDA0003527825380000753
[ solution 85]
Figure BDA0003527825380000761
[ solution 86]
Figure BDA0003527825380000762
Examples of EC include monovalent groups represented by any of the following structures. In these, EC is bound to MU at x.
[ solution 87]
Figure BDA0003527825380000763
[ solution 88]
Figure BDA0003527825380000771
From the viewpoint of solubility and coating film formation properties, the compound represented by the formula (H3) is preferably one in which 10 to 100% of the MUs in the total number (k) of MUs in the molecule have alkyl groups having 1 to 24 carbon atoms, more preferably 30 to 100% of the MUs in the total number (k) of MUs in the molecule have alkyl groups having 1 to 18 carbon atoms (branched chain alkyl groups having 3 to 18 carbon atoms), and still more preferably 50 to 100% of the MUs in the total number (k) of MUs in the molecule have alkyl groups having 1 to 12 carbon atoms (branched chain alkyl groups having 3 to 12 carbon atoms). On the other hand, from the viewpoint of in-plane orientation and charge transport, it is preferable that 10% to 100% of the MUs of the total number of MUs (k) in a molecule have an alkyl group having 7 to 24 carbon atoms, and more preferably 30% to 100% of the MUs of the total number of MUs (k) in a molecule have an alkyl group having 7 to 24 carbon atoms (branched chain alkyl group having 7 to 24 carbon atoms).
< Compound having a structure represented by the general formula (H4) >
The compound is a compound including a structure represented by the following formula (H4), and includes a plurality of the structures, preferably one to five, more preferably one to three, further preferably one to two, most preferably one, and in the case of including a plurality of the structures, the structures are bonded to each other directly by a single bond or by a specific linking group.
[ solution 89]
Figure BDA0003527825380000772
In the general formula (H4), G is each independently "═ C (-H) -" or "═ N-", and H in the "═ C (-H) -" may be substituted with a substituent or with a structure represented by another formula (H4).
Compounds having a structure represented by general formula (H4) can be produced, for example, by using the compounds described in international publication No. 2012/153780, international publication No. 2013/038650, and the like, and by the methods described in these documents.
Examples of the substituent in which H in "═ C (-H) -" of G is substituted are as follows, but not limited thereto.
Specific examples of the "aryl" as the substituent include: phenyl, tolyl, xylyl, naphthyl, phenanthryl, pyrenyl,
Figure BDA0003527825380000773
Radical, benzo [ c ] ]Phenanthryl, benzo [ g ]]
Figure BDA0003527825380000774
Examples of the group include a phenyl group, a biphenyl group, a terphenyl group, a fluorenyl group, a 9, 9-dimethylfluorenyl group, a benzofluorenyl group, a dibenzofluorenyl group, a biphenyl group, a terphenyl group, a tetraphenyl group, a fluoranthenyl group and the like, and preferred examples thereof include a phenyl group, a biphenyl group, a terphenyl group, a tetraphenyl group, a naphthyl group, a triphenylene group, a fluorenyl group and the like. As the aryl group having a substituent, there may be mentioned: tolyl, xylyl, and 9, 9-dimethylfluorenyl. As shown in the specific examples, aryl includes both condensed aryl and non-condensed aryl.
Specific examples of the "heteroaryl" as the substituent include: pyrrolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyridyl, triazinyl, indolyl, isoindolyl, imidazolyl, benzimidazolyl, indazolyl, imidazo [1,2-a ] pyridyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, azabenzofuryl, thienyl, benzothienyl, dibenzothienyl, azabenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, naphthyridinyl, carbazolyl, azacarbazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxazinyl, oxazinyl, oxazolyl, oxadiazolyl, furazanyl, benzoxazolyl, thienyl, thiazolyl, thiadiazolyl, benzothiazolyl, triazolyl, tetrazolyl and the like, preferably, a group such as benzofuryl, dibenzothienyl, dibenzooxazolyl, carbazolyl, Pyridyl, pyrimidyl, triazinyl, azabenzofuranyl, and azabenzothiophenyl, and the like. Further preferred is a dibenzofuranyl group, a dibenzothienyl group, an azabicyclofuranyl group or an azabicyclofuranyl group.
The "substituted silyl group" as the substituent is also preferably a group selected from the group consisting of a substituted or unsubstituted trialkylsilyl group, a substituted or unsubstituted arylalkylsilyl group, and a substituted or unsubstituted triarylsilyl group.
Specific examples of the substituted or unsubstituted trialkylsilyl group include a trimethylsilyl group and a triethylsilyl group. Specific examples of the substituted or unsubstituted arylalkylsilyl group include: diphenylmethylsilyl, ditolymethylsilyl, phenyldimethylsilyl and the like. Specific examples of the substituted or unsubstituted triarylsilyl group include a triphenylsilyl group and a tritolylsilyl group.
The "substituted phosphinoxide group" as a substituent is also preferably a substituted or unsubstituted diarylphosphinoxide group. Specific examples of the substituted or unsubstituted diarylphosphinoxide group include diphenylphosphine oxide and xylylphosphine oxide.
Examples of the "substituted carboxyl group" as a substituent include a benzoyloxy group and the like.
Examples of the linking group to which a plurality of structures represented by the formula (H4) are bonded include divalent to tetravalent, divalent to trivalent, or divalent derivatives of the above aryl or heteroaryl group.
Specific examples of the compounds having a structure represented by general formula (H4) are shown below.
[ solution 90]
Figure BDA0003527825380000781
[ solution 91]
Figure BDA0003527825380000791
< Compound represented by the general formula (H5) >)
[ solution 92]
Figure BDA0003527825380000792
In the formula (H5), in the formula,
R 1 ～R 11 independently of one another, hydrogen, aryl, heteroaryl, diarylamino (two aryl groups are not bonded to one another or are bonded via a linking group), diheteroarylamino (two heteroaryl groups of diheteroarylamino are not bonded to one another or are bonded via a linking group), arylheteroarylamino (aryl groups and heteroaryl groups are not bonded to one another or are bonded via a linking group), alkyl or cycloalkyl (above, the first substituent), at least one of which may be further substituted by aryl, heteroaryl, diarylamino, alkyl or cycloalkyl (above, the second substituent),
R 1 ～R 11 wherein adjacent radicals may 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 being aryl, heteroaryl, biarylArylamino (two aryl groups are not bonded to each other or bonded via a linking group), diheteroarylamino (two heteroaryl groups of diheteroarylamino are not bonded to each other or bonded via a linking group), arylheteroarylamino (aryl groups and heteroaryl groups are not bonded to each other or bonded via a linking group), alkyl or cycloalkyl (above, a first substituent), at least one of which may be further substituted with aryl, heteroaryl, diarylamino, alkyl or cycloalkyl (above, a second substituent),
any of the rings a, b and C "— (C (-R) ═ where R is R 1 ～R 11 ) May be substituted with "-N ═ N",
at least one hydrogen in the compound represented by formula (H5) may be independently substituted with halogen or deuterium, respectively.
Any of the a-ring, b-ring and C-ring in the formula (H5) — (where R is R ═ C (-R) ═ C (where R is R) 1 ～R 11 ) Substituted with "-N ═ can also be varied to pyridine, pyrimidine, pyridazine, pyrazine and other nitrogen-containing heteroaryl rings. The details of the description may refer to the descriptions in the general formula (2A) and the formula (2B).
Preferably in said formula (H5),
R 1 ～R 11 independently of each other, hydrogen, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a diarylamino group (two aryl groups are not bonded to each other or bonded via a linking group, wherein the aryl group is an aryl group having 6 to 12 carbon atoms), an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 16 carbon atoms, at least one of which 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), an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 16 carbon atoms,
R 1 ～R 11 wherein adjacent groups are bonded to each other and form an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms together with the a, b or c ring, at least one hydrogen in the formed ring may be substituted by an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, or a diarylamino group (two aryl groups are not bonded to each other or are bonded via a linking group, wherein the aryl group is a group having 6 to 1 carbon atoms 2 aryl group), 1-12 carbon alkyl group or 3-16 carbon cycloalkyl group, wherein at least one hydrogen of the above groups may be further substituted by 6-30 carbon aryl group, 2-30 carbon heteroaryl group, diarylamino group (wherein aryl group is 6-12 carbon aryl group), 1-12 carbon alkyl group or 3-16 carbon cycloalkyl group.
Still more preferably, in the formula (H5),
R 1 ～R 11 independently of each other, hydrogen, an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, a diarylamino group (two aryl groups are not bonded to each other or bonded via a linking group, wherein the aryl group is an aryl group having 6 to 10 carbon atoms), an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 14 carbon atoms, at least one of which 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 (two aryl groups are not bonded to each other or bonded via a linking group, wherein the aryl group is an aryl group having 6 to 10 carbon atoms), an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 14 carbon atoms,
R 1 ～R 11 wherein adjacent groups are bonded to each other and form an aryl ring having 9 to 12 carbon atoms or a heteroaryl ring having 6 to 12 carbon atoms together with the a, b or c ring, at least one hydrogen in the formed ring is substituted by an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, a diarylamino group (both aryl groups are not bonded to each other or are bonded via a linking group, and the aryl group is an aryl group having 6 to 10 carbon atoms), an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 14 carbon atoms), and at least one hydrogen in these groups is further substituted by an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, a diarylamino group (two aryl groups are not bonded to each other or are bonded via a linking group, and the aryl group is an aryl group having 6 to 10 carbon atoms), an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 14 carbon atoms.
In the first substituent and the second substituent, the "aryl" or the "heteroaryl" in the aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino may be exemplified as follows.
Specific examples of the "aryl group" include aryl groups having 6 to 30 carbon atoms, preferably aryl groups having 6 to 24 carbon atoms, more preferably aryl groups having 6 to 20 carbon atoms, further 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 a monocyclic aromatic group, (2-, 3-, 4-) biphenyl as a bicyclic aromatic group, (1-, 2-) naphthyl as a condensed bicyclic aromatic group, (m-terphenyl-2 '-yl, m-terphenyl-4' -yl, m-terphenyl-5 '-yl, o-terphenyl-3' -yl, o-terphenyl-4 '-yl, p-terphenyl-2' -yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl-2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, P-terphenyl-3-yl, p-terphenyl-4-yl), acenaphthylene- (1-, 3-, 4-, 5-) as condensed tricyclic aryl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalene- (1-, 2-) yl, (1-, 2-, 3-, 4-, 9-) phenanthryl, tetraphenyl (5' -phenyl-m-terphenyl-2-yl, 5' -phenyl-m-terphenyl-3-yl, 5' -phenyl-m-terphenyl-4-yl, m-terphenyl) as tetracyclic aryl, triphenylene- (1-, p-terphenyl-4-yl as condensed tetracyclic aryl, triphenylene- (1-, p-terphenyl-2-yl, p-terphenyl-4-yl) as condensed tricyclic aryl, triphenylene- (1-, p-terphenyl-m-2-) as condensed tricyclic aryl, and the like, 2-) group, pyrene- (1-, 2-, 4-) group, tetracene- (1-, 2-, 5-) group, perylene- (1-, 2-, 3-) group as condensed pentacyclic aryl group, pentacene- (1-, 2-, 5-, 6-) group and the like.
Specific examples of the "heteroaryl group" include a heteroaryl group having 2 to 30 carbon atoms, preferably a heteroaryl group having 2 to 25 carbon atoms, more preferably a heteroaryl group having 2 to 20 carbon atoms, still more preferably a heteroaryl group having 2 to 15 carbon atoms, and particularly preferably a heteroaryl group having 2 to 10 carbon atoms. Examples thereof include: pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxathiyl, phenoxazinyl, phenothiazinyl, phenazinyl, indolizinyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, naphthobenzofuryl, thienyl, benzothienyl, dibenzothienyl, naphthobenzothienyl, dibenzothienyl, benzophosphoryl, tetrazolyl, benzoxazolyl, pyridazinyl, 1H-benzotriazolyl, quinolyl, pyrazinyl, cinnolinyl, carbazolyl, pyridyl, phenanthryl, naphthobenzofuryl, benzothienyl, dibenzothienyl, naphthobenzothienyl, benzoxazolyl, and benzoxazolyl, Dibenzophosphoryl group, a monovalent group of a benzo-phosphole oxide ring, a monovalent group of a dibenzophosphole oxide ring, a furazan group, a thianthryl group, an indolocarbazolyl group, a benzindolocarbazolyl group, and a dibenzoindolocarbazolyl group.
The "alkyl group" in the first substituent and the second substituent may be either a linear or branched chain, and examples thereof include a linear 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), further 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 5 carbon atoms (a branched chain alkyl group having 3 to 5 carbon atoms) or 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 (t-amyl), n-hexyl, 1-methylpentyl, 3, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, tert-octyl (1,1,3, 3-tetramethylbutyl), 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-tridecyl, N-heptadecyl, n-octadecyl, n-eicosyl, and the like. Further, examples of the method include: 1-ethyl-1-methylpropyl, 1-diethylpropyl, 1-dimethylbutyl, 1-ethyl-1-methylbutyl, 1, 4-trimethylpentyl, 1, 2-trimethylpropyl, 1-dimethyloctyl, 1-dimethylpentyl, 1-dimethylheptyl, 1, 5-trimethylhexyl, 1-ethyl-1-methylhexyl, 1-ethyl-1, 3-dimethylbutyl, 1,2, 2-tetramethylpropyl, 1-butyl-1-methylpentyl, 1-diethylbutyl, 1-ethyl-1-methylpentyl, 1, 3-trimethylbutyl, 1-propyl-1-methylpentyl, 1-dimethylbutyl, 1-ethyl-1-methylpentyl, 1, 3-trimethylbutyl, 1-propyl-1-methylpentyl, 1,1, 2-trimethylpropyl, 1-ethyl-1, 2, 2-trimethylpropyl, 1-propyl-1-methylbutyl, 1-dimethylhexyl 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. Examples thereof include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and alkyl (particularly methyl) substituents having 1 to 4 carbon atoms of these groups, bicyclo [1.1.0] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.1.0] pentyl, bicyclo [2.1.1] hexyl, bicyclo [3.1.0] hexyl, bicyclo [2.2.1] heptyl, bicyclo [2.2.2] octyl, adamantyl, decahydronaphthyl, decahydroazulenyl, and the like.
The substitution position when the first substituent is an aryl group is preferably R 1 、R 3 、R 4 、R 5 、R 10 And R 11 More preferably, for example, to R 1 And R 3 Substituted with respect to R 5 And R 10 Substituted with respect to R 4 And R 11 Aryl is preferably phenyl.
The substitution position when the first substituent is heteroaryl is preferably R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 9 、R 10 And R 11 More preferably, for example, to R 1 Substituted with respect to R 2 Substituted with respect to R 3 Substituted with respect to R 1 And R 3 Substituted with respect to R 4 And R 11 Substituted with respect to R 5 And R 10 Substituted with respect to R 6 And R 9 The heteroaryl group is preferably a carbazolyl group. The heteroaryl (e.g., carbazolyl) can be substituted at that position via a phenylene group.
Specific examples of the compound represented by formula (H5) include compounds represented by the following structural formulae. Further, "Me" in the formula is methyl.
[ solution 93]
Figure BDA0003527825380000821
[ chemical 94]
Figure BDA0003527825380000822
The compound represented by formula (H5) can be produced by first bonding the a-ring to the c-ring with a bonding group (-O-) to produce an intermediate (first reaction), and then 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 general etherification Reaction such as a nucleophilic substitution Reaction or Ullmann Reaction (Ullmann Reaction) can be used. In the second reaction, a cascade-type hetero-friedel-crafts reaction (a sequential aromatic electrophilic substitution reaction) can be used. The details of the first reaction and the second reaction can be found in the description of International publication No. 2015/102118.
< Compound represented by the general formula (H6) >)
[ solution 95]
Figure BDA0003527825380000831
In the formula (H6), in the formula,
R 1 ～R 16 each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, or cycloalkyl (above, the first substituent), at least one of which may be further substituted with aryl, heteroaryl, diarylamino, alkyl, or cycloalkyl (above, the second substituent),
R 1 ～R 16 Wherein adjacent radicals may be bonded to each other and together with the a-ring, b-ring, c-ring, or d-ring form an aryl or heteroaryl ring, at least one hydrogen in the formed ring being available via an aryl, heteroaryl, diarylamino groupDiheteroarylamino, arylheteroarylamino, alkyl or cycloalkyl (above, the first substituent), at least one of which may be further substituted with aryl, heteroaryl, diarylamino, alkyl or cycloalkyl (above, the second substituent),
at least one hydrogen in the compound represented by formula (H6) may be independently substituted with halogen or deuterium, respectively.
Preferably in said formula (H6),
R 1 ～R 16 independently hydrogen, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a diarylamino group (two aryl groups are not bonded to each other or bonded through a linking group), an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 16 carbon atoms, wherein at least one hydrogen of these groups is further substituted by an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a diarylamino group (two aryl groups are not bonded to each other or bonded through a linking group, wherein an aryl group is an aryl group having 6 to 12 carbon atoms), an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 16 carbon atoms,
R 1 ～R 16 Wherein adjacent groups are bonded to each other and form an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms together with the a, b, c, or d ring, at least one hydrogen in the formed ring may be substituted by an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a diarylamino group (two aryl groups are not bonded to each other or are bonded via a linking group, wherein the aryl group is an aryl group having 6 to 12 carbon atoms), an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 16 carbon atoms), and at least one hydrogen in these groups 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 (two aryl groups are not bonded to each other or are bonded via a linking group, wherein the aryl group is an aryl group having 6 to 12 carbon atoms), an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 16 carbon atoms.
Still more preferably, in the formula (H6),
R 1 ～R 16 independently represents hydrogen, aryl group having 6-16 carbon atoms, heteroaryl group having 2-15 carbon atoms, diarylamino group (two aryl groups are not bonded to each other or bonded via a linking group, wherein aryl group isAryl group having 6 to 10 carbon atoms), alkyl group having 1 to 6 carbon atoms or cycloalkyl group having 3 to 14 carbon atoms, wherein at least one hydrogen of these groups may be further substituted by aryl group having 6 to 16 carbon atoms, heteroaryl group having 2 to 15 carbon atoms, diarylamino group (wherein aryl group is aryl group having 6 to 10 carbon atoms), alkyl group having 1 to 6 carbon atoms or cycloalkyl group having 3 to 14 carbon atoms,
R 1 ～R 16 Wherein adjacent groups are bonded to each other and form an aryl ring having 9 to 12 carbon atoms or a heteroaryl ring having 6 to 12 carbon atoms together with the a, b, c, or d ring, at least one hydrogen in the formed ring is substituted by an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, a diarylamino group (two aryl groups are not bonded to each other or bonded via a linking group, wherein the aryl group is an aryl group having 6 to 10 carbon atoms), an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 14 carbon atoms), and at least one hydrogen in the formed ring is further substituted by an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, a diarylamino group (two aryl groups are not bonded to each other or bonded via a linking group, wherein the aryl group is an aryl group having 6 to 10 carbon atoms), an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 14 carbon atoms.
In the first substituent and the second substituent, the following examples are given as "aryl" or "heteroaryl" in aryl, heteroaryl, diarylamino (two aryl groups are not bonded to each other or bonded through a linking group), diheteroarylamino (two heteroaryl groups of diheteroarylamino are not bonded to each other or bonded through a linking group), arylheteroarylamino (aryl group and heteroaryl group are not bonded to each other or bonded through a linking group).
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, further 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 bicyclic aryl, (1-, 2-) naphthyl as condensed bicyclic aryl, terphenyl (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, o-terphenyl-5 '-yl, o-terphenyl-3' -yl, P-terphenyl-3-yl, p-terphenyl-4-yl), acenaphthylene- (1-, 3-, 4-, 5-) as condensed tricyclic aryl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalene- (1-, 2-) yl, (1-, 2-, 3-, 4-, 9-) phenanthryl, tetraphenyl (5' -phenyl-m-terphenyl-2-yl, 5' -phenyl-m-terphenyl-3-yl, 5' -phenyl-m-terphenyl-4-yl, m-terphenyl) as tetracyclic aryl, triphenylene- (1-, p-terphenyl-4-yl as condensed tetracyclic aryl, triphenylene- (1-, p-terphenyl-2-yl, p-terphenyl-4-yl) as condensed tricyclic aryl, triphenylene- (1-, p-terphenyl-m-2-) as condensed tricyclic aryl, and the like, 2-) group, pyrene- (1-, 2-, 4-) group, tetracene- (1-, 2-, 5-) group, perylene- (1-, 2-, 3-) group as condensed pentacyclic aryl group, pentacene- (1-, 2-, 5-, 6-) group and the like.
Specific examples of the "heteroaryl group" include a heteroaryl group having 2 to 30 carbon atoms, preferably a heteroaryl group having 2 to 25 carbon atoms, more preferably a heteroaryl group having 2 to 20 carbon atoms, still more preferably a heteroaryl group having 2 to 15 carbon atoms, and particularly preferably a heteroaryl group having 2 to 10 carbon atoms. Examples thereof include: pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxathiyl, phenoxazinyl, phenothiazinyl, phenazinyl, indolizinyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, naphthobenzofuryl, thienyl, benzothienyl, dibenzothienyl, naphthobenzothienyl, dibenzothienyl, benzophosphoryl, tetrazolyl, benzoxazolyl, pyridazinyl, 1H-benzotriazolyl, quinolyl, pyrazinyl, cinnolinyl, carbazolyl, pyridyl, phenanthryl, naphthobenzofuryl, benzothienyl, dibenzothienyl, naphthobenzothienyl, benzoxazolyl, and benzoxazolyl, Dibenzophosphoryl group, a monovalent group of a benzo-phosphole oxide ring, a monovalent group of a dibenzophosphole oxide ring, a furazan group, a thianthryl group, an indolocarbazolyl group, a benzindolocarbazolyl group, and a dibenzoindolocarbazolyl group.
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 5 carbon atoms (a branched chain alkyl group having 3 to 5 carbon atoms) or 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 (t-amyl), n-hexyl, 1-methylpentyl, 3, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, tert-octyl (1,1,3, 3-tetramethylbutyl), 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-tridecyl, N-heptadecyl, n-octadecyl, n-eicosyl, and the like. Further, examples thereof include: 1-ethyl-1-methylpropyl, 1-diethylpropyl, 1-dimethylbutyl, 1-ethyl-1-methylbutyl, 1, 4-trimethylpentyl, 1, 2-trimethylpropyl, 1-dimethyloctyl, 1-dimethylpentyl, 1-dimethylheptyl, 1, 5-trimethylhexyl, 1-ethyl-1-methylhexyl, 1-ethyl-1, 3-dimethylbutyl, 1,2, 2-tetramethylpropyl, 1-butyl-1-methylpentyl, 1-diethylbutyl, 1-ethyl-1-methylpentyl, 1, 3-trimethylbutyl, 1-propyl-1-methylpentyl, 1-ethylbutyl, 1-methylpentyl, 1,1, 2-trimethylpropyl, 1-ethyl-1, 2, 2-trimethylpropyl, 1-propyl-1-methylbutyl, 1-dimethylhexyl 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. Examples thereof include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and alkyl (particularly methyl) substituents having 1 to 4 carbon atoms of these groups, bicyclo [1.1.0] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.1.0] pentyl, bicyclo [2.1.1] hexyl, bicyclo [3.1.0] hexyl, bicyclo [2.2.1] heptyl, bicyclo [2.2.2] octyl, adamantyl, decahydronaphthyl, decahydroazulenyl, and the like.
The compound represented by the formula (H6) can be produced by referring to the description in International publication No. 2014/042197.
< TADF Material >
By reducing the energy difference between the excited singlet state and the excited triplet state, reverse energy transfer from the excited triplet state to the excited singlet state, which is generally low in transition probability, occurs with high efficiency, and light emission from the singlet state (thermally activated delayed fluorescence, TADF) appears. In normal fluorescence emission, 75% of triplet excitons generated by current excitation pass through a thermal deactivation path, and thus cannot be extracted as fluorescence. On the other hand, in TADF, all excitons can be used for fluorescence emission, and a highly efficient organic EL device can be realized.
As the TADF material that can be used for such a purpose, for example, a compound represented by the following general formula (H7) or a compound having the following general formula (H7) as a partial structure can be cited.
[ solution 96]
ED-Ln-EA (H7)
In the formula (H7), ED is an electron donating group, Ln is a bonding group, EA is an electron accepting group, and the singlet energy (S) of the compound represented by the formula (H7) 1 ) And triplet energy (T) 1 ) Energy difference (Δ S) 1 T 1 ) Is below 0.2eV (Hiroki Uoyama, Kenichi Goushi, Zhijin King, Katsuyuuki Shizu, Hiroko Hao Zi, Chihaya Adachi, Nature, 492,234-238 (2012)). Energy difference (Δ S) 1 T 1 ) Preferably 0.15eV or less, more preferably 0.10eV or less,more preferably 0.08eV or less.
The TADF material is preferably a donor-acceptor type TADF compound (a D-a type TADF compound) designed to locally present HOMO and LUMO in the molecule using an electron donating substituent called a donor and an electron accepting substituent called an acceptor to produce efficient reverse intersystem crossing.
Here, in the present specification, the "electron donating substituent" (donor) refers to a substituent and a partial structure locally existing in the LUMO orbital of a TADF compound molecule, and the "electron accepting substituent" (acceptor) refers to a substituent and a partial structure locally existing in the HOMO orbital of a TADF compound molecule.
In general, TADF compounds using a donor or acceptor have a large Spin Orbit Coupling (SOC) and a small exchange interaction between HOMO and LUMO due to structural reasons, and a small Δ E (ST), and thus can achieve a very fast reverse intersystem crossing speed. On the other hand, a TADF compound using a donor or an acceptor has a large structural relaxation in an excited state (in a molecule, since a stable structure is different between a ground state and an excited state, when a transition from the ground state to the excited state occurs by an external stimulus, the structure is changed to the stable structure in the excited state thereafter), and a wide emission spectrum is provided, and thus, when the TADF compound is used as a light-emitting material, color purity may be lowered.
When the color purity is lowered by the TADF material, a fluorescent compound may be added as another component to the light-emitting layer or a layer adjacent to the light-emitting layer. TADF materials function as auxiliary dopants, while the other components function as emissive dopants. As the other component, any compound may be used as long as the absorption spectrum of the compound and the emission peak of the auxiliary dopant at least partially overlap.
As the structure of the donor and acceptor used in the TADF material, for example, the structures described in Chemistry of Materials (2017, 29, 1946-1963) can be used. The ED may, for example, contain sp 3 The functional group of nitrogen, more specifically, there may be mentioned: groups derived from carbazole, dimethylcarbazole, di-tert-butylcarbazole, dimethoxycarbazole, tetramethylcarbazole, benzofluorocarbazole, benzothienocarbazole, phenylindolinocarbazole, phenyldicarbazole, bicarbazole, tercarbazole, diphenylcarbazolylamine, tetraphenylcarbazolylamine, phenoxazine, dihydrophenazine, phenothiazine, dimethylacridine, diphenylamine, bis (tert-butylphenyl) amine, N1- (4- (diphenylamino) phenyl) -N4, N4-diphenylbenzene-1, 4-diamine, dimethylanilinium dihydroacridine diamine, tetramethyl-dihydro-indenyl acridine, diphenyl-dihydrodibenzoazasilaline and the like. Further, the EA includes, for example, an sp-containing compound 2 Nitrogen aromatic ring, CN-substituted aromatic ring, ketone-containing ring, and cyano group, and more specifically, the following are included: from sulfonylbenzophenones, benzophenones, phenylenebis (phenylmethanone), benzonitrile, isonicotinonitrile, phthalonitrile, isophthalonitrile, terephthalonitrile, triazole, oxazole, thiadiazole, benzothiazole, benzobis (thiazole), benzoxazole, benzobis (oxazole), quinoline, benzimidazole, dibenzoquinoxaline, heptaazaphenalene, thioxanthone dioxide, dimethylanthrone, anthracenedione, pyridine, 5H-cyclopenta [1, 2-b: 5,4-b' ]Bipyridine, benzenetricarboxylic acid nitrile, fluorenyldicarbonitrile, pyrazindicarbonitrile, pyridinedicarbonitrile, dibenzoquinoxalinedicarbonitrile, pyrimidine, phenylpyrimidine, methylpyrimidine, triazine, triphenyltriazine, bis (phenylsulfonyl) benzene, dimethylthioxanthene dioxide, thianthrene tetraoxide, tris (dimethylphenyl) borane, and the like. Examples of Ln include a single bond and an arylene group, and more specifically, include: phenylene, biphenylene, naphthylene, and the like. In either structure, hydrogen may be substituted with alkyl, cycloalkyl, and aryl groups. Particularly preferred are compounds having at least one member selected from the group consisting of carbazole, phenoxazine, acridine, triazine, pyrimidine, pyrazine, thioxanthone, benzonitrile, phthalonitrile, isophthalonitrile, diphenylsulfone, triazole, oxadiazole, thiadiazole, and benzophenone as a partial structure.
More specifically, the compound represented by the general formula (H7) is a compound represented by any one of the following general formulae (H7-1), (H7-2) and (H7-3).
[ solution 97]
Figure BDA0003527825380000871
In the general formula (H7-1), the formula (H7-2) and the formula (H7-3),
m is each independently a single bond, -O-, > N-Ar or > C (-Ar) 2 From the viewpoint of the depth of the HOMO of the partial structure to be formed and the heights of the lowest excited singlet level and the lowest excited triplet level, a single bond, -O-, or > N-Ar is preferable,
J is a spacer structure separating a donor partial structure and a receptor partial structure, and is each independently an arylene group having 6 to 18 carbon atoms, and preferably an arylene group having 6 to 12 carbon atoms from the viewpoint of the size of a conjugate exuded from the donor partial structure and the receptor partial structure, and more specifically, there are: phenylene, methylphenylene and dimethylphenylene,
q is independently ═ C (-H) -or ═ N-, and in terms of the shallowness of the LUMO of the partial structure formed and the heights of the lowest excited singlet level and the lowest excited triplet level, it is preferably ═ N-,
ar is independently hydrogen, an aryl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 18 carbon atoms, and in terms of the depth of the HOMO of the partial structure formed and the heights of the lowest excited singlet level and the lowest excited triplet level, the preferred examples are hydrogen, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 14 carbon atoms, an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 6 to 10 carbon atoms, and the more preferred examples are hydrogen, phenyl, tolyl, xylyl, mesitylphenyl, biphenyl, pyridyl, bipyridyl, triazinyl, carbazolyl, dimethylcarbazolyl, di-tert-butylcarbazolyl, benzimidazole or phenylbenzimidazole, and the more preferred examples are hydrogen, phenyl or carbazolyl,
m is 1 or 2, and m is,
n is an integer of 2 to (6-m), and preferably an integer of 4 to (6-m) from the viewpoint of steric hindrance.
Further, at least one hydrogen in the compounds represented by each of the formulae may be substituted with halogen or deuterium.
Examples of the compound represented by the formula (H7) include compounds represented by the following structures. In the structural formula, ". indicates a bonding position,". Me "indicates a methyl group, and" tBu "indicates a tert-butyl group.
[ solution 98]
Figure BDA0003527825380000881
[ solution 99]
Figure BDA0003527825380000891
[ solution 100]
Figure BDA0003527825380000901
[ solution 101]
Figure BDA0003527825380000911
[ solution 102]
Figure BDA0003527825380000921
[ solution 103]
Figure BDA0003527825380000931
[ solution 104]
Figure BDA0003527825380000941
[ solution 105]
Figure BDA0003527825380000951
[ solution 106]
Figure BDA0003527825380000961
As the compounds represented by the general formula (H7), among the specific compounds mentioned above, particularly preferred are 4CzBN, 4CzBN-Ph, 5CzBN, 3Cz2DPhCzBN, 4CzIPN, 2PXZ-TAZ, Cz-TRZ3, BDPCC-TPTA, MA-TA, PA-TA, FA-TA, PXZ-TRZ, DMAC-TRZ, BCzT, DCzTrz, DDCzTrz, spiro AC-TRZ, Ac-HPM, Ac-PPM, Ac-MPM, TCzTrz, TmCzTrz and DCzmCZTrz.
In addition, as the dopant material, in addition to the polycyclic aromatic compound represented by the above general formula (1A) or general formula (1B), a known compound may be used, and may be selected from various materials according to a desired luminescent color. Specific examples thereof include: phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphthopyrene, dibenzopyrene, rubrene and
Figure BDA0003527825380000962
Condensed ring derivatives such as isocondensed ring derivatives, benzoxazole derivatives, benzothiazole derivatives, benzimidazole derivatives, benzotriazole derivatives, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, imidazole derivatives, thiadiazole derivatives, triazole derivatives, pyrazoline derivatives, stilbene derivatives, thiophene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, distyrylanthracene derivatives or distyrylbenzene derivatives (Japanese patent application laid-open No. 1-245087), distyrylarylene derivatives (Japanese patent application laid-open No. 2-247278), diazabenzodiindene derivatives, furan derivatives, benzofuran derivatives, phenylisobenzofuran, ditrimethylphenylisobenzofuran, bis (2-methylphenyl) isobenzofuran, bis (2-trifluoromethylphenyl) isobenzofuran, benz (I) anthracene derivatives, benz (I) butadiene derivatives, cyclopentadiene derivatives, bis (vinylanthracene derivatives, or benz (I) benzene derivatives, Isobenzofurans such as phenylisobenzofuransDerivatives, dibenzofuran derivatives, 7-dialkylaminocoumarin derivatives, 7-piperidylcoumarin derivatives, 7-hydroxycoumarin derivatives, 7-methoxycoumarin derivatives, 7-acetoxycoumarin derivatives, 3-benzothiazoleylcoumarin derivatives, 3-benzimidazolylcoumarin derivatives, coumarin derivatives such as 3-benzoxazolyl coumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, polymethine derivatives, cyanine derivatives, oxobenzanthracene derivatives, xanthene derivatives, rhodamine derivatives, fluorescein derivatives, pyrylium derivatives, quinolone derivatives, acridine derivatives, oxazine derivatives, phenylene ether derivatives, quinacridone derivatives, quinazoline derivatives, pyrrolopyridine derivatives, furopyridine derivatives, 1,2, 5-thiadiazolopyridine derivatives, pyrromethene derivatives, perinone derivatives, pyrrolopyrrole derivatives, squarylium salt derivatives, violanthrone derivatives, phenazine derivatives, acridone derivatives, deazaflavin derivatives, fluorene derivatives, and benzofluorene derivatives, and the like.
When the color-developing light is exemplified, examples of the blue dopant material to the blue-green dopant material include: naphthalene, anthracene, phenanthrene, pyrene, triphenylene, perylene, fluorene, indene,
Figure BDA0003527825380000971
And the like aromatic hydrocarbon compounds or derivatives thereof, furan, pyrrole, thiophene, silole, 9-silafluorene, 9' -spirodisilafluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, aromatic heterocyclic compounds such as phenanthroline, pyrazine, naphthyridine, quinoxaline, pyrrolopyridine, thioxanthene and the like or derivatives thereof, distyrylbenzene derivatives, tetraphenylbutadiene derivatives, distyryl derivatives, aldazine derivatives, coumarin derivatives, azole derivatives such as imidazole, thiazole, thiadiazole, carbazole, oxazole, oxadiazole, triazole and the like and metal complexes thereof, and aromatic amine derivatives represented by N, N '-diphenyl-N, N' -bis (3-methylphenyl) -4,4 '-diphenyl-1, 1' -diamine and the like.
Examples of the green to yellow dopant materials include: coumarin derivatives, phthalimide derivatives, naphthalimide derivatives, perinone derivatives, pyrrolopyrrole derivatives, cyclopentadiene derivatives, acridone derivatives, quinacridone derivatives, tetracene derivatives such as rubrene, and the like, and further, the following compounds are preferable examples: examples of the blue-green dopant material include compounds obtained by introducing a substituent capable of increasing the wavelength of light, such as an aryl group, a heteroaryl group, an arylvinyl group, an amino group, or a cyano group, into a compound exemplified as the blue-green dopant material.
Further, examples of the orange dopant material to the red dopant material include: naphthalimide derivatives such as bis (diisopropylphenyl) perylene tetracarboxylic 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-pyran or analogues thereof, magnesium phthalocyanine, metal phthalocyanine derivatives such as aluminum chlorophthalocyanine, rhodamine compounds, deazanol derivatives, coumarin derivatives, quinacridone derivatives, phenoxazine derivatives, oxazine derivatives, quinazoline derivatives, pyrrolopyridine derivatives, squarylium salt derivatives, violanthrone derivatives, phenazine derivatives, phenoxazone derivatives and thiadiazolopyripyrene derivatives, and the like, and further, the following compounds are exemplified as preferable examples: a compound obtained by introducing a substituent capable of increasing the wavelength of light, such as an aryl group, a heteroaryl group, an arylvinyl group, an amino group, or a cyano group, into the compounds exemplified as the blue dopant material to the cyan dopant material and the green dopant material to the yellow dopant material.
The dopant may be suitably selected from compounds described in 2004, 6/13 th page, references cited therein, and the like.
Among the dopant materials, amines having a stilbene structure, perylene derivatives, borane derivatives, aromatic amine derivatives, coumarin derivatives, pyran derivatives, or pyrene derivatives are particularly preferable.
The amine having a stilbene structure is represented by, for example, the following formula.
[ solution 107]
Figure BDA0003527825380000981
In the formula, Ar 1 Is an m-valent group derived from an aryl group having 6 to 30 carbon atoms, Ar 2 And Ar 3 Are each independently C6-30 aryl, Ar 1 ～Ar 3 At least one of (A) has a stilbene structure, Ar 1 ～Ar 3 May be substituted with an aryl group, a heteroaryl group, an alkyl group, a cycloalkyl group, a trisubstituted silyl group (a silyl group trisubstituted with at least one of an aryl group, an alkyl group and 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 108]
Figure BDA0003527825380000982
In the formula, Ar 2 And Ar 3 Each independently an aryl group having 6 to 30 carbon atoms, Ar 2 And Ar 3 May be substituted with aryl, heteroaryl, alkyl, cycloalkyl, trisubstituted silyl (silyl trisubstituted with at least one of aryl, alkyl and cycloalkyl), 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, phenanthrenyl, pyrenyl, phenanthrenyl, and phenanthrenyl, phenanthr,
Figure BDA0003527825380000983
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, and the like, 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 the borane derivatives include: 1, 8-diphenyl-10- (ditrimethylphenylboronyl) anthracene, 9-phenyl-10- (ditrimethylphenylboronyl) anthracene, 4- (9' -anthryl) ditrimethylphenylboronyl naphthalene, 4- (10' -phenyl-9 ' -anthryl) ditrimethylphenylboronyl naphthalene, 9- (ditrimethylphenylboronyl) anthracene, 9- (4' -biphenyl) -10- (ditrimethylphenylboronyl) anthracene, 9- (4' - (N-carbazolyl) phenyl) -10- (ditrimethylphenylboronyl) anthracene, and the like.
Further, borane derivatives described in International publication No. 2000/40586, for example, can also be used.
The aromatic amine derivative is represented by the following formula, for example.
[ solution 109]
Figure BDA0003527825380000991
In the formula, Ar 4 An n-valent group derived from an aryl group having 6 to 30 carbon atoms, Ar 5 And Ar 6 Are each independently C6-30 aryl, Ar 4 ～Ar 6 May be substituted with an aryl group, a heteroaryl group, an alkyl group, a cycloalkyl group, a trisubstituted silyl group (a silyl group trisubstituted with at least one of an aryl group, an alkyl group and a cycloalkyl group), or a cyano group, and n is an integer of 1 to 4.
Particularly, the following aromatic amine derivatives are more preferable: ar (Ar) 4 Is derived from anthracene,
Figure BDA0003527825380000992
Divalent radicals of fluorene, benzofluorene or pyrene, Ar 5 And Ar 6 Each independently an aryl group having 6 to 30 carbon atoms, Ar 4 ～Ar 6 May be substituted with aryl, heteroaryl, alkyl, cycloalkyl, trisubstituted silyl (silyl trisubstituted with at least one of aryl, alkyl and cycloalkyl) or cyano, and n is 2.
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, phenanthrenyl, pyrenyl, phenanthrenyl, and phenanthrenyl, phenanthr,
Figure BDA0003527825380000993
Mesityl, tetracenyl, perylenyl, pentacenyl, and the like.
As aromatic amine derivatives, as
Figure BDA0003527825380000994
Examples of the system include: n, N, N ', N' -tetraphenyl
Figure BDA0003527825380000995
6, 12-diamine, N, N, N ', N' -tetrakis (p-tolyl))
Figure BDA0003527825380000996
6, 12-diamine, N, N, N ', N' -tetrakis (m-tolyl)
Figure BDA0003527825380000997
6, 12-diamine, N, N, N ', N' -tetrakis (4-isopropylphenyl)
Figure BDA0003527825380000998
-6, 12-diamine, N, N, N ', N' -tetrakis (naphthalen-2-yl)
Figure BDA0003527825380000999
6, 12-diamine, N '-diphenyl-N, N' -di (p-tolyl)
Figure BDA00035278253800009910
-6, 12-diamine, N '-diphenyl-N, N' -bis (4-ethylphenyl)
Figure BDA00035278253800009911
6, 12-diamine, N '-diphenyl-N, N' -bis (4-isopropylphenyl)
Figure BDA00035278253800009912
-6, 12-diamine, N '-diphenyl-N, N' -bis (4-tert-butylphenyl)
Figure BDA00035278253800009913
6, 12-diamine, N '-bis (4-isopropylphenyl) -N, N' -di (p-tolyl)
Figure BDA00035278253800009914
6, 12-diamine, and the like.
Examples of pyrene-based compounds 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-diamine 1 ,N 6 -diphenyl-N 1 ,N 6 -bis- (4-trimethylsilyl-phenyl) -1H, 8H-pyrene-1, 6-diamine and the like.
Further, examples of anthracene series include: n, N, N, N-tetraphenylanthracene-9, 10-diamine, N, N, N ', N ' -tetra (p-tolyl) anthracene-9, 10-diamine, N, N, N ', N ' -tetra (m-tolyl) anthracene-9, 10-diamine, N, N, N ', N ' -tetra (4-isopropylphenyl) anthracene-9, 10-diamine, N, N ' -diphenyl-N, N ' -di (p-tolyl) anthracene-9, 10-diamine, N, N ' -diphenyl-N, N ' -di (m-tolyl) anthracene-9, 10-diamine, N, N ' -diphenyl-N, N ' -bis (4-ethylphenyl) anthracene-9, 10-diamine, N, N ' -diphenyl-N, n '-bis (4-isopropylphenyl) anthracene-9, 10-diamine, N, N' -diphenyl-N, N '-bis (4-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, 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 (1-naphthylamino) anthracene, 10-diphenylamino-9- (4-diphenylamino-1-naphthyl) anthracene, 10-diphenylamino-9- (6-diphenylamino-2-naphthyl) anthracene, and the like.
Further, 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.
Examples of the coumarin derivative include coumarin-6 and coumarin-334.
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 DCM and DCJTB described below.
[ solution 110]
Figure BDA0003527825380001001
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.
The material for the light-emitting layer (host material and dopant material) may be used as a material for the light-emitting layer as a polymer compound or a crosslinked polymer thereof as follows, or as a pendant-type polymer compound or a crosslinked pendant-type polymer thereof as follows: the polymer compound is obtained by polymerizing a reactive compound, which is obtained by substituting a reactive substituent in the material for the light-emitting layer (host material and dopant material), as a monomer, and the pendant polymer compound is obtained by reacting a main chain polymer with the reactive compound. As the reactive substituent in such a case, the description of the polycyclic aromatic compound represented by the above general formula (1A) or general formula (1B) can be cited.
The use of such a polymer compound and a crosslinked polymer will be described in detail later.
< Electron injection layer, Electron transport layer in organic electroluminescent element >
The electron injection layer 107 functions to efficiently inject electrons transferred from the cathode 108 into the light-emitting layer 105 or the electron transport layer 106. The electron transport layer 106 functions to efficiently transport electrons injected from the cathode 108 or electrons injected from the cathode 108 through the electron injection layer 107 to the light-emitting layer 105. The electron transporting layer 106 and the electron injecting layer 107 are formed by laminating and mixing one or two or more kinds of electron transporting/injecting materials, or are formed by mixing an electron transporting/injecting material and a polymer binder.
The electron injection/transport layer is a layer that is responsible for injecting electrons from the cathode and transporting the electrons, and is preferably a layer that has high electron injection efficiency and transports the injected electrons with good efficiency. Therefore, a substance having a high electron affinity, a high electron mobility, and excellent stability is preferable, and impurities that become traps are less likely to be generated during production and use. However, when the balance between the transport of holes and electrons is considered, if the function of efficiently preventing holes from the anode from flowing to the cathode side without being recombined 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 that can efficiently prevent hole transfer.
The material (electron transport material) for forming the electron transport layer 106 or the electron injection layer 107 can be selected and used arbitrarily from compounds conventionally used as electron transport compounds in photoconductive materials, and known compounds used in electron injection layers and electron transport layers of organic EL devices. In the present invention, as the electron transporting material, a polycyclic aromatic compound represented by the general formula (1A) or the general formula (1B) may be used.
The material used for the electron transport layer or the electron injection layer preferably contains at least one compound selected from the following compounds: a compound containing an aromatic ring or a heteroaromatic ring containing at least one atom selected from carbon, hydrogen, oxygen, sulfur, silicon, and phosphorus; pyrrole derivatives and condensed ring derivatives thereof; and a metal complex having electron-accepting nitrogen. Specifically, there may be mentioned: aromatic ring derivatives having condensed ring systems such as naphthalene and anthracene, styrene-based aromatic ring derivatives represented by 4,4' -bis (diphenylvinyl) biphenyl, perinone derivatives, coumarin derivatives, naphthalimide derivatives, quinone derivatives such as anthraquinone and diphenoquinone, phosphine oxide derivatives, carbazole derivatives, indole derivatives, and the like. Examples of the metal complex having electron-accepting nitrogen include: and hydroxyoxazole complexes such as hydroxyphenyl oxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. These materials may be used alone or in combination with different materials.
Specific examples of the other electron transport compound include: pyridine derivatives, naphthalene derivatives, anthracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone derivatives, perylene derivatives, oxadiazole derivatives (1, 3-bis [ (4-tert-butylphenyl) 1,3, 4-oxadiazolyl ] phenylene, etc.), thiophene derivatives, triazole derivatives (N-naphthyl-2, 5-diphenyl-1, 3, 4-triazole, etc.), thiadiazole derivatives, metal complexes of 8-hydroxyquinoline derivatives, hydroxyquinoline-based metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzoxazole compounds, gallium complexes, pyrazole derivatives, perfluorinated phenylene derivatives, triazine derivatives, pyrazine derivatives, perylene derivatives, anthraquinone derivatives, perylene derivatives, and the like, 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, oligomeric pyridine derivatives such as terpyridine, bipyridine derivatives, terpyridine derivatives (e.g., 1, 3-bis (2,2 ': 6',2 '-terpyridin-4' -yl) benzene), naphthyridine derivatives (e.g., bis (1-naphthyl) -4- (1, 8-naphthyridin-2-yl) phenylphosphine oxide), aldazine derivatives, carbazole derivatives, indole derivatives, phosphine oxide derivatives, and the like, Bisstyryl derivatives and the like.
In addition, a metal complex having electron-accepting nitrogen may also be used, and examples thereof include: hydroxyoxazole complexes such as hydroxyquinoline metal complexes and hydroxyphenyl oxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes.
The materials can be used alone or in admixture with different materials.
Among 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.
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 long as the reducing substance has a certain degree of reducibility, various substances can be used, and for example, at least one selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, oxides of alkali metals, halides of alkali metals, oxides of alkaline earth metals, halides of alkaline earth metals, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals, and organic complexes of rare earth metals can be preferably used.
Preferable reducing substances include alkali metals such as Na (work function 2.36eV), K (work function 2.28eV), Rb (work function 2.16eV), and Cs (work function 1.95eV), and alkaline earth metals such as Ca (work function 2.9eV), Sr (work function 2.0 to 2.5eV), and Ba (work function 2.52eV), and particularly preferable substances have 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 the alkali metals to a material forming the electron transporting layer or the electron injecting layer, improvement in light emission luminance or prolongation in the organic EL element can be achieved. In addition, as the reducing substance having a work function of 2.9eV or less, a combination of two or more of these alkali metals is also preferable, and a combination including Cs, for example, a combination of Cs and Na, Cs and K, Cs and Rb, or Cs and Na and K is particularly preferable. By including Cs, the reducing ability can be efficiently exerted, and by adding Cs to a material for forming an electron transporting layer or an electron injecting layer, improvement in light emission luminance or prolongation in life of the organic EL element can be achieved.
The material for an electron injection layer and the material for an electron transport layer can be used as a material for an electron layer as a polymer compound or a crosslinked polymer thereof, or as a pendant-type polymer compound or a crosslinked pendant-type polymer thereof: the polymer compound is obtained by polymerizing a reactive compound, as a monomer, substituted with a reactive substituent in the material for the electron injection layer and the material for the electron transport layer, and the pendant polymer compound is obtained by reacting a main chain polymer with the reactive compound. As the reactive substituent in such a case, the description of the polycyclic aromatic compound represented by the above general formula (1A) or general formula (1B) can be cited.
The use of such a polymer compound and a crosslinked polymer will be described in detail later.
< cathode in organic electroluminescent element >
The cathode 108 functions to inject electrons into the light-emitting layer 105 through the electron injection layer 107 and the electron transport layer 106.
The material forming the cathode 108 is not particularly limited as long as it can efficiently inject electrons into the organic layer, and the same material as the material forming the anode 102 can be used. Among them, metals such as tin, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, cesium, and magnesium, and alloys thereof (e.g., magnesium-silver alloys, magnesium-indium alloys, and aluminum-lithium alloys such as lithium fluoride and aluminum) are preferable. In order to improve the electron injection efficiency to improve the element characteristics, lithium, sodium, potassium, cesium, calcium, magnesium, or an alloy containing these low work function metals is effective. However, in general, these low work function metals are most often unstable in the atmosphere. In order to improve this, for example, a method of doping a small amount of lithium, cesium, or magnesium into an organic layer and using an electrode having high stability is known. As the other dopant, inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide, and cesium oxide can be used. However, the present invention is not limited to these examples.
Further, the following are preferable examples: metals such as platinum, gold, silver, copper, iron, tin, aluminum, and indium, alloys using these metals, inorganic substances such as silicon dioxide, titanium dioxide, and silicon nitride, polyvinyl alcohol, vinyl chloride, 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 for 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 can be used alone to form each layer, or can be dispersed in polyvinyl chloride, polycarbonate, polystyrene, poly (N-vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin as a polymer binder, a solvent-soluble resin such as a phenoxy resin, polyamide, ethylcellulose, vinyl acetate resin, Acrylonitrile Butadiene Styrene (ABS) resin, or polyurethane resin, or a curable resin such as a 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 EL element can be formed by forming a material to be each layer into a thin film by a method such as vapor deposition, resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination, printing, spin coating, casting, or coating. In the manner describedThe thickness of each layer to be formed is not particularly limited, and may be suitably set depending on the properties of the material, but is usually in the range of 2nm to 5000 nm. The film thickness can be measured by a quartz oscillation type film thickness measuring apparatus or the like. When a thin film is formed by a vapor deposition method, the vapor deposition conditions vary depending on the type of material, the target crystal structure and association structure of the film to be formed, and the like. The deposition conditions are preferably set to +50 ℃ to +400 ℃ in a boat heating temperature and 10 degrees of vacuum -6 Pa～10 -3 Pa, a deposition rate of 0.01nm/sec to 50nm/sec, a substrate temperature of-150 ℃ to +300 ℃, and a film thickness of 2nm to 5 μm.
When a dc voltage is applied to the organic EL element obtained as described above, the anode may be applied with a positive polarity and the cathode with a negative polarity, and when a voltage of about 2V to 40V is applied, light emission can be observed from the transparent or translucent electrode side (anode or cathode, or both). In addition, the organic EL element emits light even when a pulse current or an alternating current is applied thereto. Further, the waveform of the applied alternating current may be arbitrary.
Next, as an example of a method for manufacturing an organic EL element, a method for manufacturing an organic EL element including an anode, a hole injection layer, a hole transport layer, a light-emitting layer including a host material and a dopant material, an electron transport layer, an electron injection layer, and a cathode will be described.
< vapor deposition method >
An anode is formed by forming a thin film of an anode material on an appropriate substrate by vapor deposition or the like, and then a thin film of a hole injection layer and a hole transport layer is formed on the anode. A target organic EL element is obtained by co-evaporating a host material and a dopant material on the thin film to form a thin film as a light-emitting layer, forming an electron transport layer and an electron injection layer on the light-emitting layer, and further forming a thin film containing a substance for a cathode as a cathode by an evaporation method or the like. In the production of the organic EL element, the order of production may be reversed, and the organic EL element may be produced by using a cathode, an electron injection layer, an electron transport layer, a light-emitting layer, a hole transport layer, a hole injection layer, and an anode in this order. In the co-evaporation, there is a method of simultaneously performing evaporation of a plurality of materials from respective evaporation sources, and a method of performing evaporation at once by placing a mixture of the co-evaporated materials in one evaporation source (premix method).
< Wet film Forming method >
A low-molecular-weight compound capable of forming each organic layer of an organic EL element is prepared as a liquid composition for forming an organic layer, and a wet film-forming method is performed using the composition. In the case where an appropriate organic solvent for dissolving the low-molecular compound is not present, the composition for forming an organic layer may be prepared from a high-molecular compound which is polymerized together with another monomer or main chain polymer having a solubility function as a reactive compound obtained by substituting a reactive substituent in the low-molecular compound, or the like.
In general, a wet film-forming method forms a coating film by passing through a coating step of coating a composition for forming an organic layer on a substrate and a drying step of removing a solvent from the coated composition for forming an organic layer. In the case where the polymer compound has a crosslinkable substituent (also referred to as a crosslinkable polymer compound), the polymer compound is further crosslinked by the drying step to form a crosslinked polymer. Depending on the coating process, a method using a spin coater is called a spin coating method, a method using a slit coater is called a slit coating method, a method using a plate is called a gravure, offset, reverse offset, or flexo printing method, a method using an ink jet printer is called an ink jet method, and a method of spraying in a mist form is called a spray method. The drying step may be carried out by air drying, heating, drying under reduced pressure, or the like. The drying step may be performed only once, or may be performed a plurality of times by using different methods or conditions. Alternatively, for example, different methods may be used in combination as in the case of calcination under reduced pressure.
The wet film formation method is a film formation method using a solution, and examples thereof include a partial printing method (ink jet method), a spin coating method, a casting method, and a coating method. Unlike the vacuum deposition method, the wet film formation method can form a film under atmospheric pressure without using an expensive vacuum deposition apparatus. In addition, the wet film formation method can be performed in a large area or in a continuous manner, which leads to a reduction in manufacturing cost.
On the other hand, in the case of a wet film formation method, lamination may be difficult as compared with a vacuum deposition method. In the case of producing a laminated film by a wet film formation method, it is necessary to prevent dissolution of the lower layer by the composition of the upper layer and to use a composition having controlled solubility, a crosslinking and an Orthogonal solvent (mutually insoluble solvent) of the lower layer, and the like. However, even when these techniques are used, it is sometimes difficult to use the wet film formation method for coating all films.
Therefore, the following method is generally employed: only a plurality of layers were formed by a wet film formation method, and the remaining layers were formed by a vacuum evaporation method, thereby producing an organic EL element.
For example, a part of the following description describes a process for producing an organic EL element by applying a wet film formation method.
(procedure 1) film formation of Anode by vacuum vapor deposition method
(procedure 2) film formation by Wet film formation method of composition for Forming hole injection layer containing Material for hole injection layer
(procedure 3) film formation of composition for hole transport layer formation containing material for hole transport layer by Wet film formation method
(procedure 4) film formation of light-emitting layer Forming composition comprising host Material and dopant Material by Wet film formation method
(program 5) film formation of Electron transport layer by vacuum deposition
(procedure 6) film formation of the Electron injection layer by vacuum deposition
(program 7) film formation of cathode by vacuum vapor deposition
By going through the procedure, an organic EL element including an anode/a hole injection layer/a hole transport layer/a light emitting layer containing a host material and a dopant material/an electron transport layer/an electron injection layer/a cathode can be obtained.
There is a measure of preventing the dissolution of the light-emitting layer of the lower layer, and a means for forming a film from the cathode side in the reverse of the above procedure is used to prepare a composition for forming a layer containing a material for an electron-transporting layer or a material for an electron-injecting layer, and the above can be formed by a wet film-forming method.
< other film formation method >
For forming a film of the composition for forming an organic layer, a Laser Induced Thermal Imaging (LITI) method may be used. LITI is a method of performing thermal vapor deposition of a compound attached to a substrate by using a laser, and the composition for forming an organic layer can be used for a material to be coated on a substrate.
< optional Process >
Before and after each step of film formation, an appropriate treatment step, cleaning step and drying step may be added as appropriate. Examples of the treatment step include: exposure treatment, plasma surface treatment, ultrasonic treatment, ozone treatment, cleaning treatment using an appropriate solvent, heat treatment, and the like. Further, a series of steps for producing the bank (bank) can be included.
Photolithography may be used in the fabrication of the banks. As the bank material that can be used for photolithography, a positive resist material and a negative resist material can be used. Further, a printing method capable of forming a pattern, such as an ink jet method, gravure offset printing, reverse offset printing, or screen printing, may be used. At this time, a permanent resist material may also be used.
Examples of the material for the banks include polysaccharides and derivatives thereof, homopolymers and copolymers of vinyl monomers having a hydroxyl group, biopolymer compounds, polyacryl compounds, polyesters, polystyrenes, polyimides, polyamideimides, polyetherimides, polythioethers, polysulfones, polyphenylenes, polyphenylethers, polyurethanes, epoxy (meth) acrylates, melamine (meth) acrylates, examples of the fluorinated polymer include, but are not limited to, polyolefins, cyclic polyolefins, acrylonitrile-butadiene-styrene copolymer (ABS), silicone resins, polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, polyacetate, polynorbornene, synthetic rubbers, fluorinated polymers such as polyvinylidene fluoride, polytetrafluoroethylene, and polyhexafluoropropylene, and copolymers of fluoroolefin and hydrocarbon olefin, and fluorocarbon polymers.
< composition for forming organic layer used in Wet film Forming method >
The composition for forming an organic layer is obtained by dissolving a low-molecular compound capable of forming each organic layer of an organic EL element or a high-molecular compound obtained by polymerizing the low-molecular compound in an organic solvent. For example, the composition for forming a light-emitting layer contains a polycyclic aromatic compound (or a polymer compound thereof) as a first component, which is at least one dopant material, at least one host material as a second component, and at least one organic solvent as a third component. The first component functions as a dopant component of the light-emitting layer obtained from the composition, and the second component functions as a host component of the light-emitting layer. The third component functions as a solvent for dissolving the first component and the second component in the composition, and a smooth and uniform surface shape is obtained by utilizing a controlled evaporation rate of the third component itself at the time of coating.
< organic solvent >
The composition for forming an organic layer contains at least one organic solvent. The film forming property and the presence or absence of defects, surface roughness and smoothness of the coating film can be controlled and improved by controlling the evaporation rate of the organic solvent during film formation. In addition, when the film is formed by the ink jet method, the meniscus (meniscus) stability at the pin hole of the ink jet head can be controlled, and the ejection property can be controlled/improved. In addition, by controlling the drying rate of the film and the orientation of the derivative molecules, the electrical characteristics, light emission characteristics, efficiency, and lifetime of an organic EL element having an organic layer obtained from the composition for forming an organic layer can be improved.
(1) Physical Properties of organic solvent
The boiling point of the at least one organic solvent is 130 to 300 ℃, more preferably 140 to 270 ℃, and still more preferably 150 to 250 ℃. From the viewpoint of the ejection property of the inkjet, the boiling point is preferably higher than 130 ℃. In addition, from the viewpoint of defects, surface roughness, residual solvent and smoothness of the coating film, the boiling point is preferably less than 300 ℃. The organic solvent is more preferably a composition containing two or more organic solvents from the viewpoint of good ink jet ejection properties, film formation properties, smoothness, and low residual solvent. On the other hand, the organic layer-forming composition may be a composition which is made into a solid state by removing the solvent from the composition in consideration of the transportability and the like.
The organic solvent further contains a Good Solvent (GS) and a Poor Solvent (PS) for at least one of the solutes, and the Boiling Point (BP) of the Good Solvent (GS) is particularly preferable GS ) Lower than the Boiling Point (BP) of the Poor Solvent (PS) PS ) The composition of (1).
By adding poor solvent with high boiling point, the good solvent with low boiling point volatilizes first during film forming, the concentration of the content in the composition and the concentration of the poor solvent are increased, and the rapid film forming is promoted. As a result, a coating film having few defects, small surface roughness, and high smoothness can be obtained.
Difference in solubility (S) GS -S PS ) Preferably 1% or more, more preferably 3% or more, and still more preferably 5% or more. Difference in Boiling Point (BP) PS -BP GS ) Preferably 10 ℃ or higher, more preferably 30 ℃ or higher, and still more preferably 50 ℃ or higher.
The organic solvent is removed from the coating film by a drying step such as vacuum, reduced pressure, or heating after film formation. In the case of heating, from the viewpoint of improving coating film formability, it is preferable to perform the heating at a glass transition temperature (Tg) of at least one of the solutes) +30 ℃. From the viewpoint of reducing the residual solvent, it is preferable to heat at least one solute at a glass transition temperature (Tg) of-30 ℃. Even if the heating temperature is lower than the boiling point of the organic solvent, the organic solvent is sufficiently removed because the film is thin. Further, the drying may be performed a plurality of times at different temperatures, or a plurality of drying methods may be used in combination.
(2) Specific examples of organic solvents
Examples of the organic solvent used in the composition for forming an organic layer include: an alkylbenzene solvent, a phenyl ether solvent, an alkyl ether solvent, a cyclic ketone solvent, an aliphatic ketone solvent, a monocyclic ketone solvent, a solvent having a diester skeleton, a fluorine-containing solvent, and the like, and specific examples thereof include: pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tetradecanol, hexan-2-ol, heptan-2-ol, octan-2-ol, decan-2-ol, dodecane-2-ol, cyclohexanol, alpha-terpineol, beta-terpineol, gamma-terpineol, delta-terpineol, terpineol (mixture), ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, Triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, polyethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, p-xylene, m-xylene, o-xylene, 2, 6-lutidine, 2-fluoro-m-xylene, 3-fluoro-o-xylene, 2-chlorobenzotrifluoride, cumene, toluene, 2-chloro-6-fluorotoluene, 2-fluorophenylmethyl ether, anisole, 2, 3-dimethylpyrazine, bromobenzene, 4-fluorophenylmethyl ether, 3-trifluoromethylanisole, mesitylene, 1,2, 4-trimethylbenzene, tert-butylbenzene, 2-methylanisole, phenetole, benzodioxane (benzodioxyle), 4-methylanisole, sec-butylbenzene, 3-methylanisole, tert-butylbenzene, 2-methylanisole, phenetole, benzodioxyle (benzodioxyle), 4-fluoro-3-methylanisole, isopropyltoluene (cymene), 1,2, 3-trimethylbenzene, 1, 2-dichlorobenzene, 2-fluorobenzonitrile, 4-fluoro-o-dimethoxybenzene (4-fluorodimethoxyantrole), 2, 6-dimethylanisole, n-butylbenzene, 3-fluorobenzonitrile, decalin (decahydronaphthalene), neopentylbenzene, 2, 5-dimethylanisole, 2, 4-dimethylanisole, benzonitrile, 3, 5-dimethylanisole, diphenylether, 1-fluoro-3, 5-dimethoxybenzene, methyl benzoate, isoamylbenzene, 3, 4-dimethylanisole, o-tolunitrile (o-tolunitrile), n-pentylbenzene, o-dimethoxybenzene (veratrole), 1,2,3, 4-tetrahydronaphthalene, ethyl benzoate, N-hexylbenzene, propyl benzoate, cyclohexylbenzene, 1-methylnaphthalene, butyl benzoate, 2-methylbiphenyl, 3-phenoxytoluene, 2 '-dimethylbiphenyl (2,2' -bitolyl), dodecylbenzene, dipentylbenzene, tetramethylbenzene, trimethoxybenzene, trimethoxytoluene, 2, 3-dihydrobenzofuran, 1-methyl-4- (propoxymethyl) benzene, 1-methyl-4- (butyloxymethyl) benzene, 1-methyl-4- (pentyloxymethyl) benzene, 1-methyl-4- (hexyloxymethyl) benzene, 1-methyl-4- (heptyloxymethyl) benzene, benzylbutyl ether, benzylpentyl ether, benzylhexyl ether, benzylheptyl ether, benzyloctyl ether, etc., but not limited thereto. The solvents may be used alone or in combination.
< optional component >
The composition for forming an organic layer may contain any component within a range not impairing the properties thereof. Examples of the optional component include a binder and a surfactant.
(1) Adhesive agent
The organic layer-forming composition may contain a binder. The binder forms a film at the time of film formation, while joining the obtained film to a substrate. In addition, the organic layer forming composition plays a role in dissolving, dispersing, and binding other components.
Examples of the binder used in the composition for forming an organic layer include: acrylic resin, polyethylene terephthalate, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, acrylonitrile-ethylene-styrene copolymer (AES) resin, ionomer (ionomer), chlorinated polyether, diallyl phthalate resin, unsaturated polyester resin, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, Teflon (Teflon), acrylonitrile-butadiene-styrene copolymer (ABS) resin, acrylonitrile-styrene copolymer (AS) resin, phenol resin, epoxy resin, melamine resin, urea resin, alkyd resin, polyurethane, and copolymers of the resins and polymers, but is not limited thereto.
The binder used in the composition for forming an organic layer may be one kind or a mixture of two or more kinds.
(2) Surface active agent
The organic layer forming composition may contain a surfactant, for example, in order to control the film surface uniformity of the organic layer forming composition, and the solvent affinity and liquid repellency of the film surface. Surfactants are classified into ionic and nonionic surfactants according to the structure of hydrophilic groups, and further classified into alkyl surfactants, silicone surfactants, and fluorine surfactants according to the structure of hydrophobic groups. Further, depending on the molecular structure, the molecular weight is classified into a simple molecular system having a relatively small molecular weight and a high molecular system having a side chain or branch having a large molecular weight. Further, the compositions are classified into a single system and a mixed system in which two or more surfactants and a base material are mixed. As the surfactant that can be used in the composition for forming an organic layer, all kinds of surfactants can be used.
Examples of the surfactant include: perlipulforo (Polyflow) No.45, Perlipulforo (Polyflow) KL-245, Perlipulforo (Polyflow) No.75, Perlipulforo (Polyflow) No.90, Perlipulforo (Polyflow) No.95 (trade name, manufactured by Co., Ltd.) chemical industry, Dispalk (Disperbyk)161, Disperbyk (Disperbyk)162, Disperbyk (Disperbyk)163, Disperbyk (Disperbyk)164, Disperbyk (Disperbyk)166, Disperbyk (Disperbyk)170, Disperbyk (Disperbyk)180, Disperbyk (Disperbyk)181, Disperbyk (Disperbyk)182, BYk 300, BYk 306, Disperbyk) 320, DisperbyK 310, DisperbyK-ByK 310, KP-310, KPbyk (KP) 358, KP (KP) 342, KP ByK, KP (KPyK) 320, KP (KP) 310, Disperbyk)161, KPyk, KP (Byk) 161, KP (Byk)320, KP (Byk, KP) 320, KP (Byk)320, KP Byk)180, KP (KP) 180, KP Byk, KP (KP Byk, III, KP III, KP III, KP Byk, KP III, KP III, III B III, III B III, III B III, III B III, III B III, KF-96-50CS, KF-50-100CS (trade name, manufactured by shin-Etsu Chemical industries, Ltd.), Shafu Long (Surflon) SC-101, Shafu Long (Surflon) KH-40 (trade name, manufactured by Qingmei Chemical industries, Ltd.), Fugu (Ftergent)222F, Fugu (Ftergent)251, FTX-218 (trade name, manufactured by Nieuss (NEOS) (stock)), Aifu Tugu (EFTOP) EF-351, Aifu (EFTOP) EF-352, Aifu Tugu (EFTOP) EF-601, Aifu Tugu (EFTOP) EF-801, Aifu Tugu (EFTOP) 802 (trade name, manufactured by Mitsubishi Material (Mitsubishi) (stock)), Meijia Fac (Megafac) F-470, Meijiac (Megac) F-477, Meijia Fac (Megac) F-475, Megac Fafa-475, Megac (Megac) F-475, Megac-475, Meijia method (Megafac) F-479, Meijia method (Megafac) F-553, Meijia method (Megafac) F-554 (trade name, manufactured by Diesen (DIC) (Doku Co., Ltd.), fluoroalkyl benzenesulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetra (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethylammonium salt, fluoroalkyl sulfamate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, and the like, Polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate and alkyldiphenyl ether disulfonate.
One kind of surfactant may be used, or two or more kinds may be used in combination.
< composition and Property of composition for Forming organic layer >
The content of each component in the composition for forming an organic layer is determined in consideration of good solubility, storage stability, and film forming property of each component in the composition for forming an organic layer, good film quality of a coating film obtained from the composition for forming an organic layer, good ejection property when an inkjet method is used, and good electrical characteristics, light emission characteristics, efficiency, and lifetime of an organic EL element having an organic layer manufactured using the composition. For example, in the case of the composition for forming a light-emitting layer, it is preferable that: the first component is 0.0001 to 2.0 wt% based on the total weight of the composition for forming a light-emitting layer, the second component is 0.0999 to 8.0 wt% based on the total weight of the composition for forming a light-emitting layer, and the third component is 90.0 to 99.9 wt% based on the total weight of the composition for forming a light-emitting layer.
More preferably: the first component is 0.005 to 1.0 wt% based on the total weight of the composition for forming a light-emitting layer, the second component is 0.095 to 4.0 wt% based on the total weight of the composition for forming a light-emitting layer, and the third component is 95.0 to 99.9 wt% based on the total weight of the composition for forming a light-emitting layer. More preferably: the first component is 0.05 to 0.5 wt% based on the total weight of the composition for forming a light-emitting layer, the second component is 0.25 to 2.5 wt% based on the total weight of the composition for forming a light-emitting layer, and the third component is 97.0 to 99.7 wt% based on the total weight of the composition for forming a light-emitting layer.
The composition for forming an organic layer can be produced by appropriately selecting the above components by a known method, and stirring, mixing, heating, cooling, dissolving, dispersing, or the like. After the preparation, filtration, degassing (also referred to as degassing), ion exchange treatment, inert gas substitution/encapsulation treatment, and the like may be optionally performed.
As the viscosity of the organic layer forming composition, a good film forming property and a good ejection property when an inkjet method is used can be obtained in the case of a high viscosity. On the other hand, when the viscosity is low, a film can be easily formed. Accordingly, the viscosity of the organic layer forming composition is preferably 0.3 to 3mPa · s, more preferably 1 to 3mPa · s, at 25 ℃. In the present invention, the viscosity is a value measured using a cone-plate type rotational viscometer (cone-plate type).
When the surface tension of the composition for forming an organic layer is low, a coating film having good film-forming properties and no defects can be obtained. On the other hand, when the surface tension is high, good ink ejection properties can be obtained. Therefore, the surface tension of the organic layer forming composition is preferably 20 to 40mN/m, more preferably 20 to 30mN/m, at 25 ℃. In the present invention, the surface tension is a value measured using a pendant drop method.
< crosslinkable Polymer Compound: a compound represented by the general formula (XLP-1) >
Next, a case where the polymer compound has a crosslinkable substituent will be described. Such a crosslinkable polymer compound is, for example, a compound represented by the following general formula (XLP-1).
[ solution 111]
Figure BDA0003527825380001081
In the formula (XLP-1),
MUx, ECx and k are defined as the same as MU, EC and k in the formula (H3), wherein the compound represented by the formula (XLP-1) has at least one crosslinkable substituent (XLS), and preferably the content of the monovalent or divalent aromatic group having the crosslinkable substituent is 0.1 to 80% by weight in the molecule.
The content of the monovalent or divalent aromatic group having a crosslinkable substituent is preferably 0.5 to 50% by weight, more preferably 1 to 20% by weight.
The crosslinkable substituent (XLS) is not particularly limited as long as it is a group capable of further crosslinking the polymer compound, and is preferably a substituent having the following structure. Each structural formula represents a bonding site.
[ solution 112]
Figure BDA0003527825380001091
L is independently a single bond, -O-, -S-, > C ═ O, -O-C (═ O) -, C1-12 alkylene, C1-12 oxyalkylene, or C1-12 polyoxyalkylene. Among the substituents, preferred is a group represented by formula (XLS-1), formula (XLS-2), formula (XLS-3), formula (XLS-9), formula (XLS-10) or formula (XLS-17), and more preferred is a group represented by formula (XLS-1), formula (XLS-3) or formula (XLS-17).
Examples of the divalent aromatic compound having a crosslinkable substituent include compounds having the following partial structures. In the following structural formula, a symbol indicates a bonding position.
[ solution 113]
Figure BDA0003527825380001092
[ chemical formula 114]
Figure BDA0003527825380001101
[ solution 115]
Figure BDA0003527825380001102
[ solution 116]
Figure BDA0003527825380001103
< method for producing Polymer Compound and crosslinkable Polymer Compound
The production methods of the polymer compound and the crosslinkable polymer compound are described by taking the compound represented by the above formula (H3) and the compound represented by the above formula (XLP-1) as examples. These compounds can be synthesized by appropriately combining known production methods.
Examples of the solvent used in the reaction include: examples of the aromatic solvent, saturated/unsaturated hydrocarbon solvent, alcohol solvent, and ether solvent include: dimethoxyethane, 2- (2-methoxyethoxy) ethane, 2- (2-ethoxyethoxy) ethane, and the like.
Alternatively, the reaction may be carried out in a two-phase system. In the case of carrying out the reaction in a two-phase system, a phase transfer catalyst such as quaternary ammonium salt may be added as required.
When the compound of formula (H3) or the compound of formula (XLP-1) is produced, it can be produced in one stage or through multiple stages. The polymerization may be carried out by an all-round polymerization method in which the reaction is started after all the raw materials are charged into the reaction vessel, by a dropping polymerization method in which the raw materials are added by dropping into the reaction vessel, by a precipitation polymerization method in which the product precipitates as the reaction proceeds, and by combining these methods as appropriate. For example, when a compound represented by formula (H3) is synthesized in one stage, the target compound is obtained by carrying out the reaction in a state where Monomer Unit (MU) and end-cap unit (EC) are added to the reaction vessel. In addition, when the compound represented by the general formula (H3) is synthesized in multiple stages, the target compound is obtained by adding and reacting an end-capping unit (EC) after polymerizing the Monomer Unit (MU) to a target molecular weight. When different kinds of Monomer Units (MU) are added in multiple stages to carry out the reaction, a polymer having a concentration gradient with respect to the structure of the monomer units can be produced. In addition, after the precursor polymer is prepared, a polymer as a target can be obtained by a subsequent reaction.
Further, when the polymerizable group of the Monomer Unit (MU) is selected, the primary structure of the polymer can be controlled. For example, as shown in 1 to 3 of the synthesis flow, a polymer having a random primary structure (1 of the synthesis flow), a polymer having a regular primary structure (2 and 3 of the synthesis flow), and the like can be synthesized, and can be used in combination as appropriate depending on the target. Further, when a monomer unit having three or more polymerizable groups is used, a hyperbranched polymer or a dendrimer (dendrimer) can be synthesized.
[ solution 117]
Figure BDA0003527825380001111
The monomer unit usable in the present invention can be synthesized by the methods described in Japanese patent laid-open No. 2010-189630, International publication No. 2012/086671, International publication No. 2013/191088, International publication No. 2002/045184, International publication No. 2011/049241, International publication No. 2013/146806, International publication No. 2005/049546, International publication No. 2015/145871, Japanese patent laid-open No. 2008-106241, Japanese patent laid-open No. 2010-215886, International publication No. 2016/031639, and Japanese patent laid-open No. 2011-174062.
Further, as for a specific polymer synthesis procedure, it can be synthesized according to the methods described in Japanese patent laid-open Nos. 2012-036388, 2015/008851, 2012-36381, 2015/194448, 2013/146806, 2015/145871, 2016/031639, 2016/125560, 2011/049241 and 2012-144722.
< example of application of organic electroluminescent element >
In addition, the present invention is also applicable to a display device including an organic EL element, an illumination device including an organic EL element, or the like.
A display device or a lighting device including the organic EL element can be manufactured by a known method such as connecting the organic EL element of this embodiment to a known driving device, and can be driven by a known 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 mode and a 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 screen, a pixel having a side of mm level is used. In the case of monochrome display, pixels of the same color may be arranged, and in the case of color display, pixels of red, green, and blue are arranged in parallel to perform display. In this case, a triangular shape and a striped shape are typical. Also, as a driving method of the matrix, any one of a line-sequential (line-sequential) driving method or an active matrix may be used. The line sequential driving has an advantage of a simple structure, but when the operation characteristics are taken into consideration, the active matrix may be more excellent, and therefore the driving method needs to be used separately depending on the application.
In the segment method (type), a pattern is formed so as to display predetermined information, and the determined region is caused to emit light. Examples thereof include: time and temperature display in a digital clock or a thermometer, operation state display of an audio device or an induction cooker, panel display of an automobile, and the like.
Examples of the illumination device include an illumination device such as an indoor illumination, and a backlight of a liquid crystal display device (see, for example, japanese patent laid-open nos. 2003-257621, 2003-277741, and 2004-119211). Backlights are used mainly for improving visibility of display devices that do not emit light, and are used for liquid crystal display devices, clocks, audio devices, automobile panels, display panels, signs, and the like. In particular, as a backlight for personal computers, which is a subject of thinning in liquid crystal display devices, the backlight using the light emitting element of the present embodiment has characteristics of thinness and light weight, considering that it is difficult to thin the backlight in the conventional manner because it includes a fluorescent lamp or a light guide plate.
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 for controlling 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 can be arbitrarily blocked to control the current. A field effect transistor is easy to be miniaturized compared with a single transistor (bipolar transistor), and is often used as an element constituting an integrated circuit or the like.
In general, the organic field effect transistor may be configured such that a source electrode and a drain electrode are provided in contact with an organic semiconductor active layer formed using the polycyclic aromatic compound of the present invention, and a gate electrode is provided through an insulating layer (dielectric layer) in contact with the organic semiconductor active layer. Examples of the element structure include the following structures.
(1) Substrate/gate electrode/insulator layer/source 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 configured as described above can be used as a pixel driving switching element of an active matrix driving type liquid crystal display or 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. In an organic thin film solar cell, the polycyclic aromatic compound of the present invention can function as a hole transport material or an electron transport material. The organic thin-film solar cell may suitably include a hole blocking layer, an electron injection layer, a hole injection layer, a smoothing layer, and the like, in addition to the above. In the organic thin film solar cell, known materials used in the organic thin film solar cell can be appropriately selected to be used in combination.
< wavelength conversion material >
The polycyclic aromatic compound of the present invention is useful as a wavelength converting material.
The application of multicolor technology based on a color conversion method to a liquid crystal display or an organic EL display, illumination, and the like is being actively studied. Color conversion is to convert the emission wavelength from the phosphor into light having a longer wavelength, and means, for example, converting ultraviolet light or blue light into green light or red light. The wavelength conversion material having the color conversion function is formed into a film, and for example, is combined with a blue light source, whereby three primary colors of blue, green, and red, that is, white light can be extracted from the blue light source. A full-color display can be manufactured by using a white light source, which is a combination of a blue light source and a wavelength conversion film having a color conversion function, as a light source unit, and combining the white light source with a liquid crystal driving section and a color filter. In addition, without a liquid crystal driving portion, the liquid crystal display device can be used as a white light source as it is, and can be applied to a white light source such as a light-emitting diode (LED) lighting. Further, a full-color organic EL display can be manufactured without using a metal mask by using a blue organic EL element as a light source and using it in combination with a wavelength conversion film that converts blue light into green light and red light. Further, a low-cost full-color micro LED display can be manufactured by using a blue micro LED as a light source and combining it with a wavelength conversion film that converts blue light into green light and red light.
[ examples ]
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples. First, a synthesis example of the polycyclic aromatic compound will be described below.
Synthesis example (1): synthesis of Compound (2A-szs-0004)
Boron tribromide (1.13ml, 12mmol, 4eq.) was added to a flask containing compound (Int-2A-szs-0004) (2.95g, 3.0mmol, 1eq.) and o-dichlorobenzene (400ml) at room temperature under nitrogen. After the completion of the dropwise addition, the temperature was raised to 180 ℃ and the mixture was stirred for 20 hours. Then, it was cooled again to room temperature, and N, N-diisopropylethylamine (7.70ml, 45mmol, 15eq.) was added thereto and stirred until the generation of heat was completed. Then, the reaction solution was distilled off at 60 ℃ and reduced pressure to obtain a crude product. The obtained crude product was washed with acetonitrile, methanol and toluene in this order, purified by a silica gel column (eluent: toluene), and then recrystallized twice from o-dichlorobenzene to obtain compound (2A-szs-0004) (0.22 g).
The compound (2A-szs-0004) was confirmed as a target at M/z (M + H) 998.388 by Mass Spectrometry (MS).
[ chemical formula 118]
Figure BDA0003527825380001141
Synthesis example (2): synthesis of Compound (2A-zsz-0004)
Compound (2A-zsz-0004) (0.25g) was obtained by the same procedure as in synthesis example 1 except that compound (Int-2A-szs-0004) (2.95g, 3.0mmol, 1eq.) was changed to compound (Int-2A-zsz-0004) (2.80g, 3.0mmol, 1 eq.).
The compound (2A-zsz-0004) was confirmed as the target compound at M/z (M + H) 950.388949.380 by MS.
[ solution 119]
Figure BDA0003527825380001142
Synthesis example (3): synthesis of Compound (2A-zzz-0002)
Compound (2A-zzz-0002) (0.19g) was obtained by the same procedure as in synthesis example 1 except that compound (Int-2A-szs-0004) (2.95g, 3.0mmol, 1eq.) was changed to compound (Int-2A-zzz-0002) (2.66g, 3.0mmol, 1 eq.).
The compound (2A-zzz-0002) was confirmed as the target compound at M/z (M + H) ═ 902.388 by MS.
[ chemical formula 120]
Figure BDA0003527825380001143
Synthesis example (4): synthesis of Compound (2B-szs-0001)
Boron tribromide (1.70ml, 18mmol, 6eq.) was added to a flask containing compound (Int-2A-szs-0004) (2.95g, 3.0mmol, 1eq.) and o-dichlorobenzene (400ml) at room temperature under nitrogen. After the completion of the dropwise addition, the temperature was raised to 180 ℃ and the mixture was stirred for 20 hours. Then, it was cooled again to room temperature, and N, N-diisopropylethylamine (11.6ml, 68mmol, 23eq.) was added thereto and stirred until the generation of heat was completed. Then, the reaction solution was distilled off at 60 ℃ and reduced pressure to obtain a crude product. The obtained crude product was washed with acetonitrile, methanol and toluene in this order, purified by a silica gel column (eluent: toluene), and then recrystallized twice from o-dichlorobenzene to obtain compound (2B-szs-0001) (0.24 g).
The compound (2B-szs-0001) as the target compound was confirmed at M/z (M + H) ═ 1006.374 by MS.
[ solution 121]
Figure BDA0003527825380001151
Synthesis example (5): synthesis of Compound (2B-zsz-0001)
Compound (2B-zsz-0001) (0.21g) was obtained by the same procedure as in synthesis example 4 except that compound (Int-2A-szs-0004) (2.95g, 3.0mmol, 1eq.) was changed to compound (Int-2A-zsz-0004) (2.80g, 3.0mmol, 1 eq.).
The compound (2B-zsz-0001) as the target compound was confirmed by MS at M/z (M + H) 958.374.
[ chemical formula 122]
Figure BDA0003527825380001152
Synthesis example (6): synthesis of Compound (2B-zzz-0001)
Compound (2B-zzz-0001) (0.20g) was obtained by the same procedure as in synthesis example 4 except that compound (Int-2A-szs-0004) (2.95g, 3.0mmol, 1eq.) was changed to compound (Int-2A-zzz-0002) (2.66g, 3.0mmol, 1 eq.).
The compound (2B-zzz-0001) as the target was confirmed by MS at M/z (M + H) ═ 910.374.
[ solution 123]
Figure BDA0003527825380001161
By appropriately changing the compound as a raw material, another polycyclic aromatic compound of the present invention can be synthesized by the method according to the above synthesis example.
Next, evaluation of basic properties of the compound of the present invention, and production and evaluation of an organic EL element using the compound of the present invention will be described. The application of the compound of the present invention is not limited to the examples shown below, and the film thickness and the constituent material of each layer may be appropriately changed depending on the basic physical properties of the compound of the present invention.
< evaluation of vapor deposition type organic EL element >
Organic EL elements of examples 1-1 to 1-6 and comparative examples 1-1 to 1-4 were fabricated, and luminance was measured at 500cd/m 2 Emission wavelength, half-value width, drive voltage, external quantum efficiency, and LT50 (using initial luminance of 500 cd/m) 2 The current density at the time of continuous driving is maintained at 250cd/m 2 The above time of brightness).
[ Table 1]
Figure BDA0003527825380001162
In Table 1, "NPD", "TcTa", "mCP", "Ir (ppy) 3 "," 2CZBN "," BPy-TP2 ", and" GH-1 ".
[ solution 124]
Figure BDA0003527825380001171
The chemical structures of RGD-1, RGD-2, and RGD-3 in Table 1 are shown below.
[ solution 125]
Figure BDA0003527825380001172
< example 1-1 >)
A glass substrate (manufactured by Opto Science) having a thickness of 26mm by 28mm by 0.7mm obtained by polishing ITO deposited to a thickness of 200nm 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 Showa vacuum deposition (Strand)), and a vapor deposition boat made of molybdenum and a vapor deposition boat made of tungsten were respectively loaded with NPD, TcTa, mCP, GH-1, a compound (2A-szs-0004), 2CZBN, and BPy-TP 2.
The following layers are sequentially formed on the ITO film of the transparent support substrate. The vacuum vessel was depressurized to 5X 10 -4 Pa, NPD was first heated and vapor-deposited to a film thickness of 40nm to form a hole injection layer. Next, TcTa was heated and vapor-deposited to have a film thickness of 15nm, and mCP was heated and vapor-deposited to have a film thickness of 15nm, thereby forming a hole transport layer including two layers. Then, GH-1 and the compound (2A-szs-0004) were simultaneously heated and vapor-deposited to a film thickness of 20nm to form a light-emitting layer. The deposition rate was adjusted so that the weight ratio of GH-1 to the compound (2A-szs-0004) became approximately 99 to 1. Next, 2CzBN was heated and vapor-deposited so that the film thickness became 10nm, and BPy-TP2 was heated and vapor-deposited so that the film thickness became 20nm, thereby forming an electron transport layer including two layers. The deposition rate of each layer is 0.01nm/sec to 1 nm/sec. Then, LiF was heated and vapor-deposited at a vapor deposition rate of 0.01nm/sec to 0.1nm/sec so that the film thickness became 1nm, and aluminum was heated and vapor-deposited so that the film thickness became 100nm to form a cathode, thereby obtaining an organic EL element. In this case, the deposition rate of aluminum is adjusted to 1nm/sec to 10 nm/sec.
< example 1-2 to example 1-6 >
The compound (2A-szs-0004) as a dopant in example 1 was changed to the dopants shown in table 1 and the mixing ratios thereof to prepare elements.
< comparative example 1-1 to comparative example 1-4 >
Each element was produced by changing the compound (2A-szs-0004) as a dopant in example 1 to each dopant shown in table 1.
The evaluation results of the respective elements are shown in table 2.
[ Table 2]
Figure BDA0003527825380001181
In examples 1-1 to 1-6, the results of high external quantum efficiency and long device lifetime were obtained as compared with comparative examples 1-1 to 1-4.
< evaluation of vapor deposition type organic EL element >
Organic EL elements of example G2-1 to example G2-6, comparative example G2-1, example G3-1 to example G3-6 and comparative example G3-1 were prepared, and luminance was measured at 500cd/m 2 Emission wavelength, half-value width, drive voltage, external quantum efficiency, and LT50 (using initial luminance of 500 cd/m) 2 The current density at the time of continuous driving is maintained at 250cd/m 2 The above time of brightness).
[ Table 3]
Figure BDA0003527825380001191
In Table 3, the chemical structures of "HATCN", "TBB", "CBP", "TPBi" and "GH-2" are shown below.
[ solution 126]
Figure BDA0003527825380001201
< example G2-1 >)
A glass substrate (manufactured by Opto Science) having a thickness of 26mm by 28mm by 0.7mm obtained by polishing ITO deposited to a thickness of 200nm 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 showa vacuum (jet)), and a molybdenum vapor deposition boat and a tungsten vapor deposition boat were respectively placed therein, the molybdenum vapor deposition boat containing HATCN, TBB, TcTa, CBP, the compound (2A-szs-0004), and TPBi, and the tungsten vapor deposition boat containing LiF and aluminum.
The following layers are sequentially formed on the ITO film of the transparent support substrate. The vacuum vessel was depressurized to 5X 10 -4 Pa, HATCN was heated and vapor-deposited to a film thickness of 5nm to form a hole injection layer. Next, TBB was heated and vapor-deposited to a film thickness of 65nm, and TcTa was heated and vapor-deposited to a film thickness of 10nm, thereby forming a hole transport layer including two layers. Next, CBP and the compound (2A-szs-0004) were simultaneously heated and vapor-deposited to a film thickness of 30nm to form a light-emitting layer. The deposition rate was adjusted so that the weight ratio of CBP to compound (2A-szs-0004) became approximately 99 to 1. Next, TPBi was heated and vapor-deposited to a film thickness of 50nm to form an electron transport layer. The deposition rate of each layer is 0.01nm/sec to 1 nm/sec. Then, LiF was heated and vapor-deposited at a vapor deposition rate of 0.01nm/sec to 0.1nm/sec so that the film thickness became 1nm, and aluminum was heated and vapor-deposited so that the film thickness became 100nm to form a cathode, thereby obtaining an organic EL element. In this case, the deposition rate of aluminum is adjusted to 1nm/sec to 10 nm/sec.
< example G2-2 to example G2-6, comparative example G2-1, example G3-1 to example G3-6 and comparative example G3-1 >)
Each element was produced by changing the host CBP, the dopant compound (2A-szs-0004) and the mixing ratio of example G2-1 to the host, the dopant and the mixing ratio described in Table 3.
The evaluation results of the respective elements are shown in table 4.
[ Table 4]
Figure BDA0003527825380001211
In examples G2-1 to G2-6 and G3-1 to G3-6, higher efficiency and longer element life were obtained as compared with comparative examples G2-1 and G3-1.
< evaluation of vapor deposition type organic EL element >
Organic EL elements of example G4-1 to example G4-4 and comparative example G4-1 were prepared, and luminance was measured at 500cd/m 2 Emission wavelength, half-value width, drive voltage, external quantum efficiency, and LT50 (using initial luminance of 500 cd/m) 2 Lower current density of 250cd/m 2 The time of the above luminance).
[ Table 5]
Figure BDA0003527825380001212
In Table 5, the chemical structures of "T2T", "4 CzIPN", "BCC-TPTA" and "Liq" are shown below.
[ solution 127]
Figure BDA0003527825380001221
< embodiment G4-1 >
A glass substrate (manufactured by Opto Science) having a thickness of 200nm formed by sputtering and having a thickness of 26mm × 28mm × 0.7mm polished 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 (manufactured by showa vacuum (stock)), and a molybdenum vapor deposition boat and a tungsten vapor deposition boat each containing HATCN, TBB, TcTa, 4CzIPN, a compound (2A-szs-0004), T2T, Liq, and TPBi were set.
The following layers are sequentially formed on the ITO film of the transparent support substrate. The vacuum vessel was depressurized to 5X 10 -4 Pa isFirst, HATCN was heated and vapor-deposited to a film thickness of 5nm to form a hole injection layer. Next, TBB was heated and vapor-deposited to a film thickness of 65nm, and TcTa was heated and vapor-deposited to a film thickness of 10nm, thereby forming a hole transport layer including two layers. Then, TcTa, 4CzIPN and the compound (2A-szs-0004) were simultaneously heated and vapor-deposited to a film thickness of 30nm to form a light-emitting layer. The deposition rate was adjusted so that the weight ratio of CBP to 4CzIPN and compound (2A-szs-0004) was approximately 85 to 14 to 1. Next, T2T was heated and vapor-deposited so that the film thickness became 10nm, and then TPBi and Liq were heated and vapor-deposited so that the film thickness became 40nm, thereby forming an electron transport layer including two layers. The deposition rate was adjusted so that the weight ratio of TPBi to Liq became approximately 70 to 30. The deposition rate of each layer is 0.01nm/sec to 1 nm/sec. Then, LiF was heated and vapor-deposited at a vapor deposition rate of 0.01nm/sec to 0.1nm/sec so that the film thickness became 1nm, and aluminum was heated and vapor-deposited so that the film thickness became 100nm to form a cathode, thereby obtaining an organic EL element. In this case, the deposition rate of aluminum is adjusted to 1nm/sec to 10 nm/sec.
< example G4-2 to example G4-4 and comparative example G4-1 >)
Each element was produced by changing the 4CzIPN as an auxiliary dopant and the compound (2A-szs-0004) as a dopant and the mixing ratio of example G4-1 to the auxiliary dopants and the mixing ratios described in Table 5.
The evaluation results of the respective elements are shown in table 6.
[ Table 6]
Figure BDA0003527825380001231
Examples G4-1 to G4-4 gave higher efficiencies and longer element lifetimes than comparative example G4-1. As in the case of examples G4-3 and G4-4, devices using exciplex (exiplex) and auxiliary dopant were realized.
< evaluation of coated organic EL element >
Next, an organic EL device obtained by forming an organic layer by coating will be described.
< macromolecular host compound: synthesis of SPH-101
SPH-101 was synthesized according to the method described in International publication No. 2015/008851. A copolymer having M2 or M3 bonded to the ortho-position of M1 was obtained, and each unit was estimated to be 50: 26: 24 (molar ratio). In the following structural formula, Me is methyl, Bpin is pinacolato boron group, and is the connection part of each unit.
[ solution 128]
Figure BDA0003527825380001232
< high molecular hole transport compound: synthesis of XLP-101
XLP-101 was synthesized according to the method described in Japanese patent laid-open publication No. 2018-61028. A copolymer having M5 or M6 bonded to the ortho-position of M4 was obtained, and each unit was estimated to be 40: 10: 50 (molar ratio). In the following structural formula, Me is methyl, Bpin is pinacolato boron group, and is the connection part of each unit.
[ solution 129]
Figure BDA0003527825380001241
< example 2-1 to example 2-9 >
A coating solution of the material forming each layer was prepared to prepare a coating type organic EL element.
< production of organic EL elements in examples 2-1 to 2-3 >
The material composition of each layer in the organic EL element is shown in table 7.
[ Table 7]
Figure BDA0003527825380001242
The structure of "ET 1" in table 7 is shown below.
[ chemical formula 130]
Figure BDA0003527825380001251
< preparation of composition (1) for Forming light-emitting layer >
The composition (1) for forming a light-emitting layer was prepared by stirring the following components until a uniform solution was formed. The prepared composition for forming a light-emitting layer was spin-coated on a glass substrate, and heat-dried under reduced pressure, thereby obtaining a coating film free of film defects and excellent in smoothness.
Figure BDA0003527825380001252
The compound (a) is a polycyclic aromatic compound represented by the general formula (1A) or the general formula (1B) (for example, the compound (1A-32)), a polymer compound obtained by polymerizing the polycyclic aromatic compound as a monomer (that is, the monomer has a reactive substituent), or a crosslinked polymer obtained by further crosslinking the polymer compound. The polymer compound used for obtaining the polymer crosslinked body has a crosslinkable substituent.
< PEDOT: PSS solution >
Commercially available PEDOT was used: PSS solution (Clevios (TM) P VP AI4083, PEDOT: aqueous dispersion of PSS, manufactured by Heraeus Holdings).
[ solution 131]
Figure BDA0003527825380001253
< preparation of OTPD solution >
OTPD (LT-N159, manufactured by luminology Technology Corp) and IK-2 (photo cation polymerization initiator, manufactured by Sanapro) were dissolved in toluene to prepare an OTPD solution having an OTPD concentration of 0.7 wt% and an IK-2 concentration of 0.007 wt%.
[ solution 132]
Figure BDA0003527825380001261
< preparation of XLP-101 solution >
XLP-101 was dissolved in xylene at a concentration of 0.6 wt% to prepare a 0.6 wt% XLP-101 solution.
< preparation of PCz solution
PCz (polyvinylcarbazole) was dissolved in dichlorobenzene to prepare a 0.7 wt% PCz solution.
[ solution 133]
Figure BDA0003527825380001262
< example 2-1 >)
On a glass substrate on which ITO with a thickness of 150nm was evaporated, PEDOT: PSS solution, calcined on a hot plate at 200 ℃ for 1 hour, thus producing PEDOT: PSS film (hole injection layer). Subsequently, the OTPD solution was spin-coated, dried on a hot plate at 80 ℃ for 10 minutes, and then exposed to light at 100mJ/cm 2 The film was exposed to light and calcined on a hot plate at 100 ℃ for 1 hour, thereby forming an OTPD film (hole transport layer) having a film thickness of 30nm, which was insoluble in the solution. Subsequently, the composition (1) for forming a light-emitting layer was spin-coated and calcined on a hot plate at 120 ℃ for 1 hour, thereby forming a light-emitting layer having a thickness of 20 nm.
The multilayer film thus produced was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by showa vacuum (jet)), and a molybdenum vapor deposition boat containing ET1, a molybdenum vapor deposition boat containing LiF, and a tungsten vapor deposition boat containing aluminum were installed therein. The vacuum vessel was depressurized to 5X 10 -4 Pa, ET1 was heated and vapor-deposited to a film thickness of 30nm, thereby forming an electron transport layer. The deposition rate in forming the electron transport layer was set to 1 nm/sec. However, the device is not suitable for use in a kitchenThen, LiF is heated and vapor deposition is performed at a vapor deposition rate of 0.01nm/sec to 0.1nm/sec so that the film thickness becomes 1 nm. Then, aluminum was heated and vapor-deposited to a film thickness of 100nm to form a cathode. An organic EL element was obtained in the manner described.
< example 2-2 >
An organic EL element was obtained in the same manner as in example 2-1. Further, the hole transport layer was formed into a film having a thickness of 30nm by spin-coating an XLP-101 solution and calcining the solution on a hot plate at 200 ℃ for 1 hour.
< example 2-3 >
An organic EL element was obtained in the same manner as in example 2-1. The hole-transporting layer was formed into a film having a thickness of 30nm by spin-coating PCz solution and calcining the solution on a hot plate at 120 ℃ for 1 hour.
< evaluation of organic EL elements of examples 2-1 to 2-3 >
It is envisioned that: the coating-type organic EL element obtained as described above also has excellent driving voltage and external quantum efficiency as in the vapor deposition-type organic EL element.
< production of organic EL element in embodiments 2-4 to 2-6 >
The material composition of each layer in the organic EL device is shown in table 8.
[ Table 8]
Figure BDA0003527825380001271
< preparation of composition (2) for Forming light-emitting layer to composition (4) for Forming light-emitting layer >
The composition (2) for forming a light-emitting layer was prepared by stirring the following components until a uniform solution was formed.
0.02% by weight of Compound (A)
mCBP 1.98 wt.%
98.00% by weight of toluene
The composition (3) for forming a light-emitting layer was prepared by stirring the following components until a uniform solution was formed.
0.02% by weight of Compound (A)
SPH-1011.98 wt.%
98.00% by weight of xylene
The composition (4) for forming a light-emitting layer was prepared by stirring the following components until a uniform solution was formed.
0.02% by weight of Compound (A)
DOBNA 1.98% by weight
98.00% by weight of toluene
In Table 8, "mCBP" is 3,3 '-bis (N-carbazolyl) -1,1' -biphenyl, "DOBNA" is 3, 11-di-o-tolyl-5, 9-dioxa-13 b-bora-naphtho [3,2,1-de ] anthracene, and "TSPO 1" is diphenyl [4- (triphenylsilyl) phenyl ] phosphine oxide. The chemical structure is shown below.
[ solution 134]
Figure BDA0003527825380001272
< example 2-4 >
An ND-3202 (manufactured by Nissan chemical industries) solution was spin-coated on a glass substrate on which ITO was formed to a thickness of 45nm, and then the substrate was heated at 50 ℃ for 3 minutes and 230 ℃ for 15 minutes in an atmospheric environment, thereby forming an ND-3202 film (hole injection layer) having a thickness of 50 nm. Subsequently, an XLP-101 solution was spin-coated, and heated on a hot plate at 200 ℃ for 30 minutes under a nitrogen atmosphere, thereby forming an XLP-101 film (hole transport layer) having a film thickness of 20 nm. Subsequently, the composition (2) for forming a light-emitting layer was spin-coated and heated at 130 ℃ for 10 minutes in a nitrogen atmosphere, thereby forming a light-emitting layer of 20 nm.
The multilayer film thus produced was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by showa vacuum (jet)), and a molybdenum vapor deposition boat containing TSPO1, a molybdenum vapor deposition boat containing LiF, and a tungsten vapor deposition boat containing aluminum were installed therein. The vacuum vessel was depressurized to 5X 10 -4 After Pa, TSPO1 was heated to a film thickness of 30nmThe electron transport layer is formed by evaporation. The deposition rate in forming the electron transport layer was set to 1 nm/sec. Then, LiF is heated and vapor deposition is performed at a vapor deposition rate of 0.01nm/sec to 0.1nm/sec so that the film thickness becomes 1 nm. Then, aluminum was heated and vapor-deposited to a film thickness of 100nm to form a cathode. An organic EL element was obtained in the manner described.
< examples 2 to 5 and 2 to 6 >
An organic EL device was obtained in the same manner as in example 2-4 using the composition (3) for forming a light-emitting layer or the composition (4) for forming a light-emitting layer.
< evaluation of organic EL elements of examples 2-4 to 2-6 >
It is envisioned that: the coating-type organic EL element obtained as described above also has excellent driving voltage and external quantum efficiency as in the vapor deposition-type organic EL element.
< production of organic EL elements in examples 2-7 to 2-9 >
The material composition of each layer in the organic EL device is shown in table 9.
[ Table 9]
Figure BDA0003527825380001281
< preparation of composition (5) for Forming light-emitting layer to composition (7) for Forming light-emitting layer >
The composition (5) for forming a light-emitting layer was prepared by stirring the following components until a uniform solution was formed.
Figure BDA0003527825380001282
The composition (6) for forming a light-emitting layer was prepared by stirring the following components until a uniform solution was formed.
Figure BDA0003527825380001283
The composition (7) for forming a light-emitting layer was prepared by stirring the following components until a uniform solution was formed.
Figure BDA0003527825380001284
In Table 9, "2 PXZ-TAZ" is 10,10' - ((4-phenyl-4H-1, 2, 4-triazole-3, 5-diyl) bis (4, 1-phenyl)) bis (10H-phenoxazine). The chemical structure is shown below.
[ solution 135]
Figure BDA0003527825380001291
< example 2-7 >
An ND-3202 (manufactured by Nissan chemical industries) solution was spin-coated on a glass substrate on which ITO was formed to a thickness of 45nm, and then the substrate was heated at 50 ℃ for 3 minutes and 230 ℃ for 15 minutes in an atmospheric environment, thereby forming an ND-3202 film (hole injection layer) having a thickness of 50 nm. Subsequently, an XLP-101 solution was spin-coated, and heated on a hot plate at 200 ℃ for 30 minutes under a nitrogen atmosphere, thereby forming an XLP-101 film (hole transport layer) having a film thickness of 20 nm. Subsequently, the composition (5) for forming a light-emitting layer was spin-coated and heated at 130 ℃ for 10 minutes in a nitrogen atmosphere, thereby forming a light-emitting layer of 20 nm.
The multilayer film thus produced was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by showa vacuum (jet)), and a molybdenum vapor deposition boat containing TSPO1, a molybdenum vapor deposition boat containing LiF, and a tungsten vapor deposition boat containing aluminum were installed therein. The vacuum vessel was depressurized to 5X 10 -4 After Pa, TSPO1 was heated and vapor-deposited to a film thickness of 30nm, thereby forming an electron transport layer. The deposition rate in forming the electron transport layer was set to 1 nm/sec. Then, LiF is heated and vapor deposition is performed at a vapor deposition rate of 0.01nm/sec to 0.1nm/sec so that the film thickness becomes 1 nm. Then, aluminum was heated and vapor-deposited to a film thickness of 100nm to form a cathode. An organic EL element was obtained in the manner described.
< examples 2 to 8 and 2 to 9 >
An organic EL device was obtained in the same manner as in examples 2 to 7, using the composition (6) for forming a light-emitting layer or the composition (7) for forming a light-emitting layer.
< evaluation of organic EL elements of examples 2-7 to 2-9 >
It is envisioned that: the coating-type organic EL element obtained as described above also has excellent driving voltage and external quantum efficiency as in the vapor deposition-type organic EL element.
As described above, although some of the compounds of the present invention were evaluated as materials for organic EL devices, they were shown to be excellent materials, other compounds not evaluated also had the same basic skeleton and were also compounds having similar structures as a whole, and those skilled in the art would understand that the same excellent materials for organic EL devices were also excellent.
[ Industrial Applicability ]
According to a preferred embodiment of the present invention, an organic EL device having a narrow half-value width of an emission spectrum and excellent color purity, and further an organic EL device having excellent quantum efficiency and device lifetime can be provided by manufacturing an organic EL device using a novel polycyclic aromatic compound, for example, as a dopant material. In addition, in terms of having a rigid structure, the novel polycyclic aromatic compound of the present invention is often a compound that gives light emission with a sharper emission spectrum, a narrow half-value width of the emission spectrum, and high color purity.

Claims (24)

1. A polycyclic aromatic compound represented by the following general formula (1A) or general formula (1B),
Figure FDA0003527825370000011
in the formula (1A) or the formula (1B),
R a is hydrogen or a substituent, -C (-R) in the a ring a ) Either unsubstituted or substituted with "-N ═ N",
ring B, ring C, ring D, ring E, ring F, and ring G are each independently an aryl or heteroaryl ring, at least one hydrogen in these rings being unsubstituted or substituted,
Y 1 、Y 2 and Y 3 Each independently is > B-, > P (═ O) -, > P (═ S) -, > Al-, > Ga-, > As-, > C (-R) -, > Si (-R) -or > Ge (-R) -, R of > C (-R) -, > R of Si (-R) -and R of > Ge (-R) -are each independently substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl,
In the formula (1A), the compound (A),
X 1 and X 2 Are each independently > N-R, > O, > S, > C (-R) 2 、＞Si(-R) 2 Or > Se, R, > C (-R) of > N-R 2 R and > Si (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > C (-R) 2 And > Si (-R) 2 At least one of two R is not bonded by a single bond or a linking group, or is bonded by a single bond or a linking group,
as X 1 R of > N-R, > C (-R) 2 R or > Si (-R) 2 R of (A) is bonded to at least one of the a ring and the B ring as X through a single bond or a linking group 2 R of > N-R, > C (-R) 2 R or > Si (-R) 2 Wherein R of (A) is bonded to at least one of the a-ring and the E-ring via a single bond or a linking group, wherein the linking groups are the same or different,
in the formula (1A) or the formula (1B),
l are each independently a single bond or a linking group, wherein at least one of L is substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene, substituted or unsubstituted alkenylene, substituted or unsubstituted alkynylene, substituted or unsubstituted arylene, or substituted or unsubstituted heteroalkylene Aryl, at least one of the ring B, ring C, ring D, ring E, ring F, ring G, aryl and heteroaryl in the compound of formula (1A) or formula (1B) being not condensed or condensed with at least one cycloalkane in which at least one hydrogen is unsubstituted or substituted, at least one-CH in the cycloalkane being unsubstituted or substituted 2 -unsubstituted or substituted by-O-,
at least one hydrogen in the compound represented by the formula (1A) or the formula (1B) is not substituted by deuterium, cyano or halogen, or is substituted.
2. The polycyclic aromatic compound according to claim 1, wherein in the formula (1A) or the formula (1B),
R a is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboryl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted arylthio, or substituted silyl, the two aryl groups of the diarylamino being not bonded to each other or to a linking group, the two heteroaryl groups of the diheteroarylamino being not bonded to each other or to a linking group, the aryl and heteroaryl groups of the arylheteroarylamino not being bonded to each other, or bonded via a linking group, the two aryl groups of the diarylboron group being not bonded to each other, or bonded via a single bond or a linking group,
-C (-R) in the a-ring a ) Either unsubstituted or substituted with "-N ═ N",
ring B, ring C, ring D, ring E, ring F, and ring G are each independently an aryl or heteroaryl ring, at least one of which rings may be substituted with a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted diarylamino, a substituted or unsubstituted diheteroarylamino, a substituted or unsubstituted arylheteroarylamino, a substituted or unsubstituted diarylboryl, a substituted or unsubstituted alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryloxy, a substituted or unsubstituted arylthio, or a substituted silyl, the two aryl groups of the diarylamino groups not being bonded to each other, or being bonded via a linking group, the two heteroaryl groups of the diheteroarylamino groups not being bonded to each other, or bonded via a linking group, the aryl and heteroaryl groups of the arylheteroarylamino group being not bonded to one another or bonded via a linking group, the two aryl groups of the diarylboron group being not bonded to one another or bonded via a single bond or a linking group,
Y 1 、Y 2 And Y 3 Each independently is > B-, > P (═ O) -, > P (═ S) -, > Al-, > Ga-, > As-, > C (-R) -, > Si (-R) -or > Ge (-R) -, R of > C (-R) -, > R of Si (-R) -and R of > Ge (-R) -are each independently aryl, heteroaryl, alkyl or cycloalkyl, at least one of these hydrogens being substituted with alkyl or cycloalkyl,
in the formula (1A), the compound (A),
X 1 and X 2 Are each independently > N-R, > O, > S, > C (-R) 2 、＞Si(-R) 2 Or > Se, R of said > N-R, said > C (-R) 2 R of (a) and said > Si (-R) 2 Each R of (A) is independently hydrogen, aryl, heteroaryl, alkyl or cycloalkyl, at least one of these hydrogens being unsubstituted or substituted by alkyl or cycloalkyl, said > C (-R) 2 And > Si (-R) 2 Wherein the two R's are not bonded to each other by a single bond or a linking group, or are bonded by a single bond or a linking group, wherein the linking groups are the same or different,
as X 1 R of > N-R, > C (-R) 2 R or > Si (-R) 2 R of (A) is bonded to at least one of the a ring and the B ring as X through a single bond or a linking group 2 R of > N-R, > C (-R) 2 R is＞Si(-R) 2 Wherein R of (A) is bonded to at least one of the a-ring and the E-ring via a single bond or a linking group, wherein the linking groups are the same or different,
In the formula (1A) or the formula (1B),
l are each independently a single bond or a linking group, wherein at least one L is substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene, substituted or unsubstituted alkenylene, substituted or unsubstituted alkynylene, substituted or unsubstituted arylene, and substituted or unsubstituted heteroarylene,
the linking group is-N (-R) -, -O-, -S-, -C (-R) 2 -、-Si(-R) 2 -, -Se-, a substituted or unsubstituted cycloalkylene, a substituted or unsubstituted alkylene, a substituted or unsubstituted alkenylene, a substituted or unsubstituted alkynylene, a substituted or unsubstituted arylene, or a substituted or unsubstituted heteroarylene, R of the-N (-R) -, the-C (-R) 2 R of (A) and said-Si (-R) 2 Each R of-is independently hydrogen, aryl, heteroaryl, alkyl or cycloalkyl, at least one of these hydrogens being unsubstituted or substituted by alkyl or cycloalkyl,
at least one of the B ring, C ring, D ring, E ring, F ring, G ring, aryl group and heteroaryl group in the compound represented by the formula (1A) or (1B) is not condensed or condensed with at least one cycloalkane, at least one hydrogen in the cycloalkane is unsubstituted or substituted, and at least one-CH in the cycloalkane is substituted 2 -unsubstituted or substituted by-O-,
at least one hydrogen in the compound represented by the formula (1A) or the formula (1B) is not substituted by deuterium, cyano or halogen, or is substituted.
3. The polycyclic aromatic compound according to claim 1, represented by the following general formula (2A) or the following general formula (2B),
Figure FDA0003527825370000031
in the formula (2A) or the formula (2B),
R a is hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboranyl, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl or alkylbicycloalkylsilyl, at least one of the hydrogens of which is unsubstituted or substituted by aryl, heteroaryl, alkyl or cycloalkyl, the two aryl groups of the diarylamino group are not bonded to one another or are bonded via a linking group, the two heteroaryl groups of the diheteroarylamino group are not bonded to one another or are bonded via a linking group, the aryl and heteroaryl groups of the arylheteroarylamino group are not bonded to one another or are bonded via a linking group, the two aryl groups of the diarylboranyl group are not bonded to one another or are bonded via a single bond or a linking group,
-C (-R) in the a-ring a ) May be substituted with "-N ═ N",
R b 、R c 、R d 、R e 、R f and R g Independently of one another, hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl or alkylbicycloalkylsilyl, at least one hydrogen of which is unsubstituted or substituted by aryl, heteroaryl, alkyl or cycloalkyl, the two aryl radicals of the diarylamino group not being bonded to one another or being bonded via a linking group, the two heteroaryl radicals of the diheteroarylamino group not being bonded to one another or being bonded via a linking group, the aryl and heteroaryl radicals of the arylheteroarylamino group not being bonded to one another or being bonded via a linking group, the two aryl radicals of the diarylboryl group not being bonded to one another or being bonded via a single bond or a linking group,
in addition, R b 、R c 、R d 、R e 、R f And R g Wherein adjacent radicals can be bonded to one another and form, together with the b-, c-, d-, e-, f-and g-rings, respectively, an aryl or heteroaryl ring, at least one hydrogen in the ring formed being unsubstituted or substituted by aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl or alkylbicycloalkylsilyl, at least one hydrogen in these being unsubstituted or substituted by aryl, heteroaryl, alkyl or cycloalkyl, the two aryl radicals of the diarylamino radical not being bonded to one another or being bonded via a linking group, the two heteroaryl radicals of the diheteroarylamino radical not being bonded to one another or being bonded via a linking group, the aryl and heteroaryl groups of the arylheteroarylamino group are not bonded to each other or are bonded via a linking group, the two aryl groups of the diarylboron group are not bonded to each other or are bonded via a single bond or a linking group,
Any of the rings "C (-R) ═ unsubstituted or substituted with" -N ═ in the ring b, ring C, ring d, ring e, ring f and ring g, and any of the rings "C (-R) ═ C (-R) -" unsubstituted or substituted with "-N (-R) -", "-O-", "-S-", "-C (-R) 2 -”、“-Si(-R) 2 - "or" -Se- ", R of" -C (-R) ═ and R of "-C (-R) ═ C (-R) -" being R b 、R c 、R d 、R e 、R f Or R g R of the "-N (-R) -", "-C (-R) 2 R of- "and" -Si (-R) 2 R of- "is hydrogen, aryl, heteroaryl, alkyl or cycloalkyl, at least one hydrogen of these being unsubstituted or substituted by alkyl or cycloalkyl, said" -C (-R) 2 Two R of- "are each other and" -Si (-R) 2 Two R's of- "may be bonded to each other by a single bond or a linking group,
l are each independently a single bond or a linking group, wherein at least one L is alkylene, cycloalkylene, alkenylene, alkynylene, arylene, heteroarylene, at least one hydrogen of the cycloalkylene, alkenylene, alkynylene, arylene, and heteroarylene is unsubstituted or substituted with respect to at least one hydrogen of aryl, heteroaryl, diarylamino, diheteroarylamino, diarylboron, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, or alkylbicycloalkylsilyl, at least one hydrogen of which is unsubstituted or substituted with respect to aryl, heteroaryl, alkyl, or cycloalkyl, and two aryl groups of the diarylamino are not bonded to each other or are bonded via a linking group, the two heteroaryl groups of the diheteroarylamino are not bonded to one another or via a linking group, the aryl and heteroaryl groups of the arylheteroarylamino are not bonded to one another or via a linking group, the two aryl groups of the diarylboron group are not bonded to one another or are bonded via a single bond or a linking group,
The linking group is-N (-R) -, -O-, -S-, -C (-R) 2 -、-Si(-R) 2 -, -Se-, cycloalkylene, alkylene, alkenylene, alkynylene, arylene, heteroarylene, R of said-N (-R) -, said-C (-R) 2 R of (A) and said-Si (-R) 2 R of (a) are each independently hydrogen, aryl, heteroaryl, alkyl or cycloalkyl, at least one of these hydrogen being unsubstituted or substituted by alkyl or cycloalkyl, at least one of the cycloalkylene, the alkylene, the alkenylene, the alkynylene, the arylene and the heteroarylene being unsubstituted or substituted by aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl or alkylbicycloalkylsilyl, at least one of these hydrogen being unsubstituted or substituted by aryl, heteroaryl, alkyl or cycloalkyl, two aryl groups of the diarylamino groups not being bonded to one another, or via a linking group, the two heteroaryl groups of the diheteroarylamino being not bonded to one another, or via a linking group, the aryl and heteroaryl groups of the arylheteroarylamino being not bonded to one another Bonded to each other or via a linking group, the two aryl groups of the diarylboron group are not bonded to each other or are bonded via a single bond or a linking group,
Y 1 、Y 2 and Y 3 Each independently is > B-, > P (═ O) -, > P (═ S) -, > Al-, > Ga-, > As-, > C (-R) -, > Si (-R) -or > Ge (-R) -, R of > C (-R) -, > R of Si (-R) -and R of > Ge (-R) -are each independently aryl, heteroaryl, alkyl or cycloalkyl, at least one of these hydrogens being substituted with alkyl or cycloalkyl,
in the formula (2A), the compound (A),
X 1 and X 2 Independently from each other > N-R, > O, > S, > C (-R) 2 、＞Si(-R) 2 Or > Se, R, > C (-R) of > N-R 2 R and > Si (-R) 2 Each R of (A) is independently hydrogen, aryl, heteroaryl, alkyl or cycloalkyl, at least one of these hydrogens being unsubstituted or substituted by alkyl or cycloalkyl, said > C (-R) 2 And > Si (-R) 2 Are not bonded to each other by a single bond, a linking group, or are bonded by a single bond, a linking group, wherein a plurality of the linking groups are different or the same,
as X 1 R of > N-R, > C (-R) 2 R or > Si (-R) 2 R of (A) is bonded to at least one of the ring a and the ring b as X through a single bond or a linking group 2 R of > N-R, > C (-R) 2 R or > Si (-R) 2 R of (A) is bonded to at least one of the a-ring and the e-ring via a single bond or a linking group, and a plurality of the linking groups are different from or the same as each other,
at least one of the B-ring, the c-ring, the d-ring, the e-ring, the f-ring, the g-ring, the formed ring, the aryl and the heteroaryl in the compound represented by the formula (2A) or (2B) is not condensed or condensed with at least one cycloalkane having 3 to 24 carbon atoms, wherein at least one hydrogen in the cycloalkane is not substituted with or substituted with an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms, an alkyl having 1 to 24 carbon atoms or a cycloalkyl having 3 to 24 carbon atoms, and at least one of the cycloalkanes isIs one of 2 -unsubstituted or substituted by-O-,
at least one hydrogen in the compound represented by the formula (2A) or the formula (2B) is not substituted by deuterium, cyano or halogen, or is substituted.
4. The polycyclic aromatic compound according to any one of claims 1 to 3, represented by any one of the following structural formulae,
Figure FDA0003527825370000051
in the following formulas, the first and second groups,
r is independently hydrogen, an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a diarylamino group, a diarylboron group, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 16 carbon atoms, at least one hydrogen of these groups may be substituted by an alkyl group having 1 to 5 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms, two aryl groups of the diarylamino group may be bonded to each other or via a linking group, two aryl groups of the diarylboron group may be bonded to each other or via a single bond or a linking group, an aryl group of the diarylamino group may be an aryl group having 6 to 10 carbon atoms, and an aryl group of the diarylboron group may be an aryl group having 6 to 10 carbon atoms,
o is an integer of 1 to 3,
p is independently an integer of 1 to 4,
q is an integer of 1 to 5,
at least one hydrogen in the compounds of each formula may be substituted with deuterium, cyano or halogen.
5. The polycyclic aromatic compound according to claim 1, represented by any one of the following structural formulae,
Figure FDA0003527825370000061
6. a reactive compound obtained by substituting a reactive substituent in the polycyclic aromatic compound of any one of claims 1 to 5.
7. A polymer compound obtained by polymerizing the reactive compound according to claim 6 as a monomer, or a crosslinked polymer obtained by further crosslinking the polymer compound.
8. A pendant polymer compound obtained by substituting the reactive compound according to claim 6 in a main chain polymer or a pendant crosslinked polymer obtained by further crosslinking the pendant polymer compound.
9. A material for organic devices, comprising the polycyclic aromatic compound according to any one of claims 1 to 5.
10. A material for organic devices, comprising the reactive compound according to claim 6.
11. A material for organic devices, which comprises the polymer compound or the crosslinked polymer according to claim 7.
12. A material for organic devices, which comprises the pendant type polymeric compound or the pendant type crosslinked polymeric compound according to claim 8.
13. The material for organic devices according to any one of claims 9 to 12, 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.
14. The material for organic devices according to claim 13, wherein the material for organic electroluminescent elements is a material for light-emitting layers.
15. An ink composition comprising the polycyclic aromatic compound according to any one of claims 1 to 5, and an organic solvent.
16. An ink composition comprising the reactive compound of claim 6, and an organic vehicle.
17. An ink composition comprising a main chain polymer, the reactive compound according to claim 6, and an organic solvent.
18. An ink composition comprising the polymer compound or polymer crosslinked material according to claim 7 and an organic solvent.
19. An ink composition comprising the pendant polymer compound or the crosslinked pendant polymer according to claim 8 and an organic solvent.
20. An organic electroluminescent element comprising: a pair of electrodes including an anode and a cathode; and an organic layer disposed between the pair of electrodes and containing the polycyclic aromatic compound according to any one of claims 1 to 5, the reactive compound according to claim 6, the polymer compound or the crosslinked polymer according to claim 7, or the pendant polymer compound or the crosslinked polymer according to claim 8.
21. The organic electroluminescent element according to claim 20, wherein the organic layer is a light-emitting layer.
22. The organic electroluminescent element according to claim 21, wherein the light-emitting layer comprises a host, and the polycyclic aromatic compound, the reactive compound, the polymer compound, the crosslinked polymer, the pendant polymer compound, or the crosslinked pendant polymer as a dopant.
23. The organic electroluminescent element according to claim 22, wherein the light-emitting layer further comprises at least one selected from the group consisting of a compound represented by the following general formula (H1), a compound represented by the following general formula (H2), a compound represented by the following general formula (H3), a compound having a structure represented by the following general formula (H4), a compound represented by the following general formula (H5), a compound represented by the following general formula (H6), and a thermally activated delayed fluorescence material,
Figure FDA0003527825370000071
In the general formula (H1), L 1 Is an arylene group having 6 to 30 carbon atoms or a heteroarylene group having 2 to 30 carbon atoms,
in the general formula (H2), L 2 And L 3 Each independently an aryl group having 6 to 30 carbon atoms or a heteroaryl group having 2 to 30 carbon atoms,
in the general formula (H3), MU is a divalent group represented by removing any two hydrogen atoms from an aromatic compound, EC is a monovalent group represented by removing any one hydrogen atom from an aromatic compound, two hydrogens in MU are replaced by EC or MU, k is an integer of 2-50000,
in the general formula (H4), G is independently ═ C (-H) -or ═ N-, and H in the ═ C (-H) -may be substituted with a substituent or with a structure represented by another formula (H4),
in the general formula (H5), in the formula,
R 1 ～R 11 each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl or cycloalkyl, at least one of which may be further substituted by aryl, heteroaryl, diarylamino, alkyl or cycloalkyl, the two aryl groups of the diarylamino groups not being bonded to each other or bonded via a linking group, the two heteroaryl amino groups of the diarylamino groups being bonded via a linking groupThe heteroaryl groups are not bonded to each other or via a linking group, the aryl and heteroaryl groups of the arylheteroarylamino groups are not bonded to each other or are bonded via a linking group,
R 1 ～R 11 Wherein adjacent radicals may 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 be substituted by an aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl or cycloalkyl group, at least one of these may be further substituted by an aryl, heteroaryl, diarylamino, alkyl or cycloalkyl group, the two aryl groups of the diarylamino groups being not bonded to each other or being bonded via a linking group, the two heteroaryl groups of the diheteroarylamino groups being not bonded to each other or being bonded via a linking group, the aryl and heteroaryl groups of the arylheteroarylamino groups being not bonded to each other or being bonded via a linking group,
any of the rings a, b and C may be substituted with "N" —, and R of the "C (-R) ═ is R 1 ～R 11 ，
In the general formula (H6), in the formula,
R 1 ～R 16 independently of one another, hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl or cycloalkyl, at least one of which may be further substituted by aryl, heteroaryl, diarylamino, alkyl or cycloalkyl, the two aryl groups of the diarylamino group not being bonded to one another or being bonded via a linking group, the two heteroaryl groups of the diheteroarylamino group not being bonded to one another or being bonded via a linking group, the aryl and heteroaryl groups of the arylheteroarylamino group not being bonded to one another or being bonded via a linking group,
R 1 ～R 16 May be bonded to each other and together with the a-ring, b-ring, c-ring or d-ring form an aryl or heteroaryl ring, at least one hydrogen in the ring formed may be substituted by aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl or cycloalkyl, at least one of which may be further substituted by aryl, heteroaryl, diheteroaryl, or cycloalkylArylamino, alkyl or cycloalkyl, the two aryl groups of the diarylamino groups are not bonded to each other or are bonded via a linking group, the two heteroaryl groups of the diheteroarylamino groups are not bonded to each other or are bonded via a linking group, the aryl and heteroaryl groups of the arylheteroarylamino groups are not bonded to each other or are bonded via a linking group, and
at least one hydrogen in the compound or structure represented by each 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.
24. A display device or a lighting device comprising the organic electroluminescent element according to any one of claims 20 to 23.
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