Compound, organic electroluminescent element, display device, and lighting device

Abstract

The compound represented by the general formula is useful for organic electroluminescent elements. Ar represents an arylene group substituted with an acceptor group, or a heteroarylene group. D1 and D2 each represent a donor group, and Ter represents a terphenyldiyl group. Ar is bonded to D2 at an atom in the β-position or the γ-position when the atom to which D1 is bonded is in the α-position.

Description

Compounds, organic electroluminescent elements, display devices, and lighting devices

[0001] This invention relates to compounds having good properties. The invention also relates to organic electroluminescent elements, display devices, and lighting devices using these compounds.

[0002] Research into improving organic electroluminescent devices (organic EL devices) is actively underway. In particular, various efforts are being made to improve the performance of these devices by developing new light-emitting materials, electron transport materials, and hole transport materials that constitute the organic electroluminescent devices. Among these efforts, there is also research on organic electroluminescent devices utilizing delayed fluorescence materials.

[0003] Delayed fluorescence materials are materials that, in their excited state, emit fluorescence when they return from the excited singlet state to the ground state after undergoing a reverse intersystem crossover from the excited triplet state to the excited singlet state. This fluorescence is called delayed fluorescence because it is observed later than fluorescence directly generated from the excited singlet state (normal fluorescence) from the ground state. For example, when a luminescent compound is excited by carrier injection, the probability of generating the excited singlet state and the excited triplet state is statistically 25%:75%, so there is a limit to improving the luminescence efficiency if only fluorescence from the directly generated excited singlet state is used. On the other hand, with delayed fluorescence materials, not only the excited singlet state but also the excited triplet state can be used for fluorescence emission via the reverse intersystem crossover pathway described above, resulting in higher luminescence efficiency compared to normal fluorescence materials.

[0004] Since this principle was revealed, various delayed fluorescence materials have been discovered through various studies, and their application to organic electroluminescent devices has been proposed. Among these are many compounds in which a benzene ring is substituted with a donor group and an acceptor group. For example, compounds such as 5CzBN, which has a skeleton in which a benzene ring is substituted with a 9H-carbazole-9-yl group (a donor group) and a cyano group (an acceptor group), have been proposed (see Comparative Compound 1 and Patent Document 1 below).

[0005] Mater. Horiz.,2016, 3, 145-151

[0006] It is known that using 5CzBN in the light-emitting layer of an organic electroluminescent device can improve its luminescence efficiency. However, there is still room for improvement in the performance of the device, and it is necessary to provide materials for organic electroluminescent devices with even better performance. However, the improvement of compounds is still in the trial-and-error stage, and it is not easy to generalize the chemical structure of useful compounds.

[0007] Under these circumstances, the inventors conducted extensive research with the aim of providing a more useful compound for organic electroluminescent devices. Furthermore, they diligently pursued studies with the aim of deriving and generalizing a general formula for a more useful compound for organic electroluminescent devices.

[0008] As a result of diligent research to achieve the above objectives, the inventors have found that by using compounds having a structure that satisfies specific conditions, it is possible to provide organic electroluminescent elements with superior performance. The present invention is proposed based on this finding and specifically has the following configuration.

[0009] [1] A compound represented by the following general formula (1). General formula (1) [In general formula (1), Ar represents an arylene group which is substituted with at least one acceptor group and which may also be substituted with substituents other than acceptor groups or with a deuterium atom, or a heteroarylene group which may also be substituted with a deuterium atom or substituent. D １ and D ２ Each of these independently represents a donor group. Ar is D １ When the atom to which it is bonded is designated as the α position, then D is present at the β or γ position of the atom. ２[1] The compound according to [1], wherein the central phenylene group constituting the terphenyldiyl group is a 1,4-phenylene group which may be substituted with a deuterium atom or a substituent. [3] The compound according to [2], wherein the phenylene groups at both ends constituting the terphenyldiyl group are each independently substituted with a deuterium atom or a substituent. [4] The compound according to [1], wherein the central phenylene group constituting the terphenyldiyl group is a 1,2-phenylene group which may be substituted with a deuterium atom or a substituent. [5] The compound according to [4], wherein the phenylene groups at both ends constituting the terphenyldiyl group are each independently substituted with a deuterium atom or a substituent. [6] Ar is a phenylene group substituted with at least one acceptor group and which may also be substituted with substituents other than acceptor groups or deuterium atoms, a naphthalene diyl group substituted with at least one acceptor group and which may also be substituted with substituents other than acceptor groups or deuterium atoms, a pyridinediyl group which may be fused and which may be substituted with deuterium atoms or substituents, a pyrimidinediyl group which may be fused and which may be substituted with deuterium atoms or substituents, a pyridazinediyl group which may be fused and which may be substituted with deuterium atoms or substituents, and The compound according to any one of [1] to [5], wherein the compound is a pyrazinediyl group which may be present and substituted with a deuterium atom or a substituent, a triazinediyl group which may be substituted with a deuterium atom or a substituent, a carbazolediyl group which may be fused and substituted with a deuterium atom or a substituent, a dibenzofranziyl group which may be fused and substituted with a deuterium atom or a substituent, a dibenzothiophendiyl group which may be fused and substituted with a deuterium atom or a substituent, or a dibenzoselediyl group which may be fused and substituted with a deuterium atom or a substituent.[7] The compound according to any one of [1] to [5], wherein Ar is a condensed aromatic heterocyclic group which may be substituted with a deuterium atom or a substituent and an arylene group substituted with at least one acceptor group, or a heteroarylene group substituted with a condensed aromatic heterocyclic group which may be substituted with a deuterium atom or a substituent. [8] The compound according to any one of [1] to [5], wherein Ar is an arylene group substituted with an aryl group which is substituted with at least one acceptor group and may be substituted with a deuterium atom or a substituent, or a heteroarylene group substituted with an aryl group which may be substituted with a deuterium atom or a substituent. [9] Ar is D. １ When the atom to which is bonded is defined as the α-position, D is at the γ-position atom. ２ The compound according to any one of [1] to [8], which binds to.

[10] Ar is D. １ When the atom to which is bonded is defined as the α-position, D is at the β-position atom. ２ The compound according to any one of [1] to [8], which binds to.

[11] The compound according to any one of [1] to

[10] , wherein Ar is an arylene group substituted with one or more selected from the group consisting of a cyano group, a silyl group, a halogen atom, a deuterium atom, a pyridyl group which may be substituted with a substituent, a pyrimidyl group which may be substituted with a deuterium atom or a substituent, a pyridazinyl group which may be substituted with a deuterium atom or a substituent, a pyrazyl group which may be substituted with a deuterium atom or a substituent, a triazyl group which may be substituted with a deuterium atom or a substituent, and an aryl group substituted with these atoms or groups.

[12] D １ and D ２ are each independently a 9H-carbazolediyl group which may be condensed and may be substituted with a deuterium atom or a substituent, according to any one of [1] to

[11] . The compound described.

[13] D １ and D ２ are bonded to Ar at the 9-position of 9H-carbazole, according to the compound of

[12] .

[14] D １ and D ２ are bonded to Ter at the 3-position of 9H-carbazole, according to the compound of

[12] or

[13] .

[15] D１ and D ２ A compound according to

[12] or

[13] wherein Ter is bonded at the 2 position of 9H-carbazole.

[16] A compound according to any one of [1] to

[15] having at least one deuterium atom.

[17] An organic electroluminescent element having a pair of electrodes consisting of an anode and a cathode and an organic layer disposed between the pair of electrodes, wherein the organic layer contains a compound according to any one of [1] to

[16] .

[18] An organic electroluminescent element according to

[17] , wherein the organic layer is a light-emitting layer.

[19] A display device or lighting device comprising the organic electroluminescent element according to

[17] or

[18] .

[0010] By using the compound of the present invention, it is possible to provide an organic electroluminescent element with excellent performance.

[0011] The contents of the present invention will be described in detail below. The following descriptions of constituent elements may be based on representative embodiments and specific examples of the present invention, but the present invention is not limited to such embodiments and specific examples. In this specification, numerical ranges expressed using "~" mean a range that includes the numbers written before and after "~" as the lower and upper limits. Also, some or all of the hydrogen atoms present in the molecule of the compound used in the present invention are deuterium atoms ( ２ It can be substituted with H (deuterium D). In the chemical structural formulas herein, hydrogen atoms are either represented as H or omitted. For example, when the representation of an atom bonded to a carbon atom in the ring skeleton of a benzene ring is omitted, it is assumed that H is bonded to the carbon atom in the ring skeleton where the representation is omitted. In this specification, the term "substituent" means an atom or group of atoms other than hydrogen and deuterium atoms.

[0012] [Compounds represented by general formula (1)] The compound represented by the general formula (1) below will be explained. General formula (1)

[0013] In general formula (1), Ar represents an arylene group which is substituted with at least one acceptor group and which may also be substituted with substituents other than acceptor groups or deuterium atoms, or Ar represents a heteroarylene group which may also be substituted with deuterium atoms or substituents. Here, an "arylene group" is an aromatic ring whose ring skeleton consists only of carbon atoms, and which has two of its ring skeleton constituent atoms as D １ and D ２ These are divalent groups that bond to each other. The number of constituent atoms of the ring skeleton of the arylene group is preferably in the range of 6 to 30, more preferably in the range of 6 to 20, and may be selected from, for example, the range of 6 to 16, or from, for example, the range of 6 to 12. The aromatic ring may be a monoring, or two or more rings may be fused together. The monoring arylene group is a phenylene group. It may be any of 1,2-arylene, 1,3-arylene, or 1,4-arylene, but 1,2-arylene or 1,3-arylene is preferred. For example, a 1,2-arylene group. For example, a 1,3-arylene group. Examples of arylene groups in which two or more rings are fused together include naphthalenediyl, anthracenediyl, phenanthrenediyl, and pyrenediyl groups. In one aspect of the present invention, the arylene group, which is formed by the fusion of two or more rings, is a divalent group bonded to adjacent ring skeleton constituent atoms, and examples include naphthalene-1,2-diyl group, naphthalene-2,3-diyl group, anthracene-1,2-diyl group, anthracene-2,3-diyl group, phenanthrene-1,2-diyl group, phenanthrene-2,3-diyl group, phenanthrene-9,10-diyl group, and pyrene-1,2-diyl group. In one aspect of the present invention, the arylene group, which is formed by the fusion of two or more rings, is a divalent group bonded at the first and third atoms of three consecutively linked ring skeleton constituent atoms. Examples include naphthalene-1,3-diyl group, naphthalene-1,8-diyl group, anthracene-1,3-diyl group, anthracene-1,9-diyl group, phenanthrene-1,3-diyl group, phenanthrene-2,4-diyl group, phenanthrene-1,10-diyl group, pyrene-1,3-diyl group, and pyrene-1,10-diyl group.

[0014] The arylene groups that Ar can adopt are substituted with at least one acceptor group. The acceptor group can be selected from groups with a positive Hammett σp value. Hammett's σp value was proposed by L. P. Hammett and quantifies the effect of substituents on the reaction rate or equilibrium of para-substituted benzene derivatives. Specifically, it is a constant (σp) specific to the substituent in the following equation that holds between the substituent and the reaction rate constant or equilibrium constant in a para-substituted benzene derivative: log(k / k0) = ρσp or log(K / K0) = ρσp. In the above equation, k0 is the rate constant of the unsubstituted benzene derivative, k is the rate constant of the substituted benzene derivative, K0 is the equilibrium constant of the unsubstituted benzene derivative, K is the equilibrium constant of the substituted benzene derivative, and ρ is the reaction constant determined by the type and conditions of the reaction. For an explanation of "Hammett's σp value" in this invention and the numerical values ​​of each substituent, refer to the description of σp value in Hansch, C. et. al., Chem. Rev., 91, 165-195 (1991).

[0015] Examples of acceptor groups that can be used as substituents on the arylene group include cyano groups, silyl groups, halogen atoms, deuterium atoms, or optionally substituted pyridyl groups, pyrimidyl groups, pyridazyl groups, pyridazyl groups, pyridazyl groups, pyridazyl groups, pyridazyl groups, and triazyl groups. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Examples of silyl groups include trialkoxysilyl groups such as trimethoxysilyl and triarylsilyl groups such as triphenylsilyl. Examples of aryl groups substituted with cyano groups include p-cyanophenyl, m-cyanophenyl, and o-cyanophenyl groups. Examples of triazyl groups include 1,3,5-triazine-2-yl groups. The substituents or deuterium atoms that can be substituted for the aryl, pyridyl, pyrimidyl, pyridazyl, and triazyl groups substituted with a cyano group, as referred to herein, may be selected from, for example, group A, group B, group C, group D, or group E described below. Adjacent groups may also bond to each other to form a cyclic structure. In one aspect of the present invention, a cyano group is used as the acceptor group. In one aspect of the present invention, a 1,3,5-triazyl group which may be substituted with a deuterium atom or an aryl group is used as the acceptor group, for example, a 4,6-diaryl-1,3,5-triazine-2-yl group which may be substituted with a deuterium atom (in particular a 4,6-diphenyl-1,3,5-triazine-2-yl group which may be substituted with a deuterium atom) can be used.

[0016] Accepting groups that can be used as substituents for the arylene group include aryl groups (especially substituted or unsubstituted phenyl groups) substituted with one or more atoms selected from the group consisting of the above-mentioned cyano group, silyl group, halogen atom, deuterium atom, or optionally substituted pyridyl group, optionally substituted deuterium atom, or substituted pyrimidyl group, optionally substituted deuterium atom, or substituted pyridazyl group, optionally substituted deuterium atom, or substituted pyrazyl group. The aryl groups referred to here include phenyl groups, naphthyl groups, anthracenyl groups, and phenantrenyl groups. For example, a phenyl group substituted at the 4th position, a phenyl group substituted at the 3rd position, or a phenyl group substituted at the 2nd position may be used. The aryl group referred to herein may be substituted, and the substituent or deuterium atom that can be substituted for the aryl group may be selected from, for example, group A, group B, group C, group D, or group E described below. In one aspect of the present invention, the aryl group (especially the phenyl group) is unsubstituted. In one aspect of the present invention, a cyanophenyl group (e.g., 4-cyanophenyl group, e.g., 3-cyanophenyl group, e.g., 2-cyanophenyl group), which may be substituted with a deuterium atom or substituent, is used as an acceptor group that can be used as a substituent for the arylene group. In one aspect of the present invention, as an acceptor group that can be adopted as a substituent of the arylene group, a phenyl group substituted with a 1,3,5-triazine-2-yl group which may be substituted with a deuterium atom or an aryl group can be adopted, for example, a phenyl group substituted with a 4,6-diaryl-1,3,5-triazine-2-yl group which may be substituted with a deuterium atom (in particular a phenyl group substituted with a 4,6-diphenyl-1,3,5-triazine-2-yl group which may be substituted with a deuterium atom) can be adopted.

[0017] The acceptor groups that can be adopted as substituents for the arylene group are preferably selected from groups with a σp of 0.3 or more, but may also be selected from groups with a σp of 0.5 or more, or from groups with a σp of 0.7 or more, or from groups with a σp of 0.9 or more, or from groups with a σp of 1.1 or more. The number of acceptor groups that Ar can take is preferably one or two, for example one or two. If there are two, they may be the same or different. In particular, the number of acceptor groups with a σp of 0.3 or more is preferably one or two, for example one or two. In one preferred embodiment of the present invention, the acceptor groups that Ar can take are only one or two cyano groups, for example only one cyano group. In one aspect of the present invention, at least one of the acceptor groups substituted on the arylene group represented by Ar is a cyanoaryl group (e.g., a cyanophenyl group). For example, the acceptor groups that Ar can substitute on the arylene group are either one cyano group and one cyanoaryl group, or two cyanoaryl groups. In one aspect of the present invention, at least one of the acceptor groups substituted on the arylene group represented by Ar is a 4,6-diaryl-1,3,5-triazine-2-yl group, and the hydrogen atom may or may not be substituted. In one aspect of the present invention, at least one of the acceptor groups substituted on the arylene group represented by Ar is a phenyl group substituted with a 4,6-diaryl-1,3,5-triazine-2-yl group, and the hydrogen atom may or may not be substituted.In one aspect of the present invention, the acceptor group that Ar can substitute for the arylene group is one or two selected from the group consisting of a triazyl group which may be substituted with a deuterium atom or substituent, a pyrimidyl group which may be substituted with a deuterium atom or substituent, a pyridazyl group which may be substituted with a deuterium atom or substituent, a pyrazyl group which may be substituted with a deuterium atom or substituent, and a pyridyl group which may be substituted with a deuterium atom or substituent (preferably the group consisting of a triazyl group which may be substituted with a deuterium atom or substituent, and a pyrimidyl group which may be substituted with a deuterium atom or substituent), for example, just one or just two. In one aspect of the present invention, the acceptor group that Ar can substitute for the arylene group is one selected from the group consisting of a triazyl group which may be substituted with a deuterium atom or a substituent, a pyrimidyl group which may be substituted with a deuterium atom or a substituent, a pyridazyl group which may be substituted with a deuterium atom or a substituent, and a pyridyl group which may be substituted with a deuterium atom or a substituent (preferably the group consisting of a triazyl group which may be substituted with a deuterium atom or a substituent, and a pyrimidyl group which may be substituted with a deuterium atom or a substituent) and one cyano group. Examples of substituents for the triazyl group, pyrimidyl group, pyridazyl group, pyridazyl group and pyridyl group referred to here include an aryl group which may be substituted with a deuterium atom or a substituent, a heteroaryl group which may be substituted with a deuterium atom or a substituent, and an alkyl group which may be substituted with a deuterium atom or a substituent. For example, the aryl group may be substituted with a deuterium atom, an alkyl group, an aryl group, a heteroaryl group, or a group in which two or more of these are linked (e.g., a phenyl group); or it may be substituted with a heteroaryl group may be substituted with a deuterium atom, an alkyl group, an aryl group, a heteroaryl group, or a group in which two or more of these are linked (e.g., a 9H-carbazole-9-yl group); or it may be substituted with the aryl group (e.g., a phenyl group) and the heteroaryl group (e.g., a 9H-carbazole-9-yl group).In this specification, alkyl groups may be linear, branched, or cyclic, and two or more of these may be mixed. The number of carbon atoms in an alkyl group can be, for example, 1 or more, 2 or more, or 4 or more. The number of carbon atoms can also be 30 or less, 20 or less, 10 or less, 6 or less, or 4 or less. Specific examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and tert-butyl group.

[0018] Ar may be a heteroarylene group which may be substituted with a deuterium atom or substituent. Here, "heteroarylene group" is an aromatic ring which contains heteroatoms as constituent atoms of the ring skeleton, and two of the constituent atoms of the ring skeleton are D １ and D ２These are divalent groups that bond to each other. Preferably, the two bonding atoms are carbon atoms. Examples of heteroatoms constituting the ring skeleton of the heteroarylene group include nitrogen atoms, oxygen atoms, and sulfur atoms, and it is preferable that at least a nitrogen atom is included. For example, a heteroarylene group can be described as having only a nitrogen atom as a heteroatom and the other ring skeleton constituent atoms being carbon atoms. The number of ring skeleton constituent atoms of the heteroarylene group is preferably in the range of 5 to 30, more preferably in the range of 5 to 20, and may be selected from, for example, the range of 5 to 16 or the range of 6 to 12. The aromatic ring may be a monoring or may be a fused ring of two or more rings. Examples of monoring heteroarylene groups include pyridinediyl group, pyrimidinediyl group, pyridazinediyl group, pyrazinediyl group, and triazinediyl group. Examples of pyridinediyl groups include 2,3-pyridinediyl, 3,4-pyridinediyl, 2,4-pyridinediyl, and 2,6-pyridinediyl groups, with 2,6-pyridinediyl being a preferred example. Examples of pyrimidinediyl groups include 2,4-pyrimidinediyl, 4,6-pyrimidinediyl, and 4,5-pyrimidinediyl groups. Examples of pyridazinediyl groups include 3,4-pyridazinediyl, 4,5-pyridazinediyl, and 3,5-pyridazinediyl groups. Examples of pyrazinediyl groups include 2,3-pyrazinediyl and 2,6-pyrazinediyl groups. In a heteroarylene group formed by the condensation of two or more rings, all condensed rings may be heteroaromatic rings, or some of the condensed rings may be heteroaromatic rings and the other rings may be aromatic rings having a ring skeleton consisting only of carbon atoms. For example, structures can be described in which an aromatic ring is further condensed onto the above-mentioned pyridinediyl group, pyrimidinediyl group, pyridazinediyl group, pyrazinediyl group, or triazinediyl group. For example, structures can be described in which a benzene ring is condensed onto a pyrrole ring, furan ring, or thiophene ring.Specific examples include carbazolediyl groups such as 1,2-carbazolediyl group, 2,3-carbazolediyl group, 3,4-carbazolediyl group, 1,3-carbazolediyl group, and 2,4-carbazolediyl group; dibenzofranzyl groups such as 1,2-dibenzofranzyl group, 2,3-dibenzofranzyl group, 3,4-dibenzofranzyl group, 1,3-dibenzofranzyl group, and 2,4-dibenzofranzyl group; and 1,2-dibenzothio Examples of dibenzothiophenediyl groups include phendiyl group, 2,3-dibenzothiophenediyl group, 3,4-dibenzothiophenediyl group, 1,3-dibenzothiophenediyl group, and 2,4-dibenzothiophenediyl group; and dibenzoselediyl groups such as 1,2-dibenzoselediyl group, 2,3-dibenzoselediyl group, 3,4-dibenzoselediyl group, 1,3-dibenzoselediyl group, and 2,4-dibenzoselediyl group.

[0019] The heteroarylene group that Ar can adopt may be substituted with at least one acceptor group, or it may not be substituted with an acceptor group. For details of the acceptor group in the case of substitution, refer to the description of the acceptor group in the description of the arylene group that Ar can adopt. In one aspect of the present invention, the acceptor group that Ar can adopt is substituted with only one cyano group. In one aspect of the present invention, the acceptor group that Ar can adopt is substituted with only one triazyl group which may be substituted with a deuterium atom or a substituent, or a pyrimidyl group which may be substituted with a deuterium atom or a substituent.

[0020] The arylene groups and heteroarylene groups that Ar may adopt may be substituted with substituents other than acceptor groups or deuterium atoms. The substituents or deuterium atoms referred to here may be selected from, for example, group A, group B, group C, group D, or group E described below. Adjacent groups may also bond to each other to form a cyclic structure. Furthermore, the term "substituents other than acceptor groups" refers to substituents other than acceptor groups as defined in the claims for substituents of arylene groups that Ar may adopt.

[0021] As substituents other than acceptor groups, fused aromatic heterocyclic groups which may be substituted with deuterium atoms or substituents can be preferably used. A fused aromatic heterocyclic group is one in which at least one of the two or more fused aromatic rings contains a heteroatom as a constituent atom of the ring skeleton. Examples of heteroatoms here include nitrogen atoms, oxygen atoms, and sulfur atoms, and fused aromatic heterocyclic groups containing nitrogen atoms can be preferably selected, and among these, fused aromatic heterocyclic groups bonded by the nitrogen atom can be preferably selected. A typical fused aromatic heterocyclic group is the 9H-carbazole-9-yl group which may be substituted with deuterium atoms or substituents. The deuterium atoms or substituents that can be substituted on the 9H-carbazole-9-yl group can be selected from, for example, group A, group B, group C, group D, or group E described below. Furthermore, adjacent groups may bond to each other to form a cyclic structure. In one aspect of the present invention, the arylene group and heteroarylene group that Ar can adopt are substituted with only one 9H-carbazole-9-yl group, which may be substituted with a deuterium atom or a substituent. In one aspect of the present invention, the arylene group and heteroarylene group that Ar can adopt are substituted with only two 9H-carbazole-9-yl groups, which may be substituted with a deuterium atom or a substituent. These two 9H-carbazole-9-yl groups may be bonded to each other via a linking group, an example of such a linking group being -D１ -Ter-D ２ - can be given. In one aspect of the present invention, the arylene group and heteroarylene group that Ar can take is substituted with three 9H-carbazole-9-yl groups, which may be substituted with deuterium atoms or substituents. Two of these three 9H-carbazole-9-yl groups may be bonded to each other via a linking group, an example of such a linking group is -D １ -Ter-D ２ - can be listed. In one aspect of the present invention, in the arylene group that Ar can form, all hydrogen atoms except those substituted with acceptor groups are substituted with deuterium atoms. In one aspect of the present invention, in the heteroarylene group that Ar can form, all hydrogen atoms are substituted with deuterium atoms. In one aspect of the present invention, in the arylene group and heteroarylene group that Ar can form, only acceptor groups are substituted. In one aspect of the present invention, the heteroarylene group that Ar can form is unsubstituted.

[0022] Other substituents besides acceptor groups include aryl groups which may be substituted with deuterium atoms or substituents. In particular, other substituents besides acceptor groups include aryl groups which may be substituted with one or more atoms selected from group E described below (e.g., phenyl groups). For example, other substituents besides acceptor groups include phenyl groups and hyperdeuterated phenyl groups.

[0023] In one aspect of the present invention, the arylene group and heteroarylene group that Ar can adopt are substituted with an acceptor group (preferably 1 to 2, for example 1) and a 9H-carbazole-9-yl group (preferably 1 to 3, for example 1, for example 2, for example 3) which may be substituted with a deuterium atom or a substituent, and are not substituted with any other substituents, but may be substituted with a deuterium atom. When two or three 9H-carbazole-9-yl groups which may be substituted with a deuterium atom or a substituent are substituted, two of the carbazole rings may be bonded to each other via a linking group, an example of such a linking group being -D １ -Ter-D ２- can be cited. In one aspect of the present invention, the arylene group and heteroarylene group that Ar can take is substituted with an acceptor group (preferably 1 to 2, for example 1), a 9H-carbazole-9-yl group which may be substituted with a deuterium atom or a substituent (preferably 1 to 2, for example 1, for example 2), and an aryl group which may be substituted with one or more atoms selected from group E described below (preferably 1 to 2, for example 1, for example 2), and is not substituted with any other substituents, but may be substituted with a deuterium atom. When two or three 9H-carbazole-9-yl groups which may be substituted with a deuterium atom or a substituent are substituted, two of the carbazole rings may be bonded to each other via a linking group, an example of such a linking group is -D １ -Ter-D ２ - can be cited. In one aspect of the present invention, the arylene group and heteroarylene group that Ar can take is substituted with an acceptor group (preferably 1 to 2, for example 1) and an aryl group (preferably 1 to 3, for example 1, for example 2, for example 3) which may be substituted with one or more selected from group E described later, and is not substituted with any other substituents, but may be substituted with a deuterium atom. In one aspect of the present invention, the arylene group and heteroarylene group that Ar can take is substituted with an acceptor group (preferably 1 to 2, for example 1), and is not substituted with any other substituents, but may be substituted with a deuterium atom. In one aspect of the present invention, the heteroarylene group that Ar can take may be substituted with an aryl group (preferably 1 to 3, for example 1, for example 2, for example 3) which may be substituted with one or more selected from group E described later, or a deuterium atom, but is not substituted with any substituents other than the aryl group.

[0024] In general formula (1), D １ and D ２Each of these independently represents a donor group. The donor group here can be selected from the groups with negative Hammett σp values ​​mentioned above. It is preferable to select the donor group from groups with a σp of -0.3 or less, but it may also be selected from groups with a σp of -0.5 or less, or from groups with a σp of -0.7 or less, or from groups with a σp of -0.9 or less, or from groups with a σp of -1.1 or less. D １ and D ２ The σp of the group represented by is the σp of the monovalent group when Ter is substituted with a hydrogen atom. General formula (1) is a donor group (D) bonded to Ar. １ , D ２ It can be described as a structure in which ) further combines with Ter to form a cyclic structure.

[0025] In general formula (1), Ar is D １ When the atom to which it is bonded is designated as the α position, then D is present at the β or γ position of the atom. ２ It combines with D. １ When the atom to which it is bonded is designated as the α position, the atom at the β position is D ２ When bonded with, Ar is a divalent group bonded to adjacent ring-skeleton constituent atoms. １ When the atom to which it is bonded is designated as the α position, the atom at the γ position is D ２ When bonded with , Ar is a divalent group bonded at the first and third atoms of the three consecutively linked ring skeleton constituent atoms. D is the shortest link between Ar and Ter. １ or D ２ The number of linked atoms (hereinafter referred to as the "minimum number of linked atoms") is preferably 3 to 6 for each element independently. In one aspect of the present invention, D １ and D ２ The minimum number of linked atoms in at least one of the atoms is 4. In one aspect of the present invention, D １ and D ２ The shortest number of linked atoms in at least one of them is 5. In one aspect of the present invention, D １ and D ２ The minimum number of linked atoms is 4 for both. In one aspect of the present invention, D １ and D ２ The minimum number of linked atoms for both is 5.

[0026] D １ and D ２ As a donor group that can be adopted, a substituted amino group can be mentioned. Preferably, the substituted amino group has a structure in which two substituents are bonded to the nitrogen atom constituting the amino group. Examples of substituents include aryl groups which may be substituted with a deuterium atom or substituents, heteroaryl groups which may be substituted with a deuterium atom or substituents, and alkyl groups which may be substituted with a deuterium atom or substituents. For aryl groups and heteroaryl groups, refer to the description of the ring and ring skeleton constituent atoms of arylene groups and heteroarylene groups in the description of Ar. In one aspect of the present invention, the two substituents bonded to the nitrogen atom of the substituted amino group are selected from the group consisting of aryl groups which may be substituted with a deuterium atom or substituents, and heteroaryl groups which may be substituted with a deuterium atom or substituents. The two substituents bonded to the nitrogen atom constituting the amino group may be bonded to each other by a single bond or by a linking group. Examples of linking groups include -O-, -S-, -(C=O)-[carbonyl group], -(NR ａ )-,-(SiR ｂ R ｃ )- can be given as an example. Here, R ａ ~R ｃ Each of these independently represents a hydrogen atom, a deuterium atom, or a substituent. The deuterium atom or substituent may be selected, for example, from group A, group B, group C, group D, or group E described below. ｂ and R ｃ They may be connected to each other to form a ring structure.

[0027] D １ and D ２As a donor group that can be adopted, a 9H-carbazolediyl group may be fused and may be substituted with a deuterium atom or a substituent. The 9H-carbazolediyl group referred to here is preferably bonded to Ar at the 9th position of carbazole. For example, bonded to Ar at the 9th position of carbazole and bonded to Ter at the 3rd position. For example, bonded to Ar at the 9th position of carbazole and bonded to Ter at the 2nd position. The substituents and deuterium atoms that can be substituted for the 9H-carbazolediyl group may be selected from, for example, group A, group B, group C, group D, or group E described below. Furthermore, adjacent groups may be bonded to each other to form a cyclic structure. For example, a 9H-carbazolediyl group in which benzofloxacin is fused and a 9H-carbazolediyl group in which benzothieno is fused can be mentioned. In one aspect of the present invention, D １ and D ２ The donor group that can be adopted is a 9H-carbazolediyl group which may be substituted only with a deuterium atom (i.e., an unsubstituted 9H-carbazolediyl group). In one aspect of the present invention, D １ and D ２ The donor group that can be adopted is the hyperhydrogenated 9H-carbazolediyl group.

[0028] D １ and D ２ The donor groups that can be adopted may be the same or different. In one aspect of the present invention, D １ and D ２ D is a donor group with the same structure, and its bonding position to Ar and its bonding position to Ter are also the same. In one aspect of the present invention, D １ and D ２ D is a donor group of the same structure, but at least one of the bonding positions to Ar and Ter is different. In one aspect of the present invention, D １ and D ２ These are donor groups with different structures. For example, they may have the same skeletal structure but different substitution configurations. Another example is when their skeletal structures are completely different.

[0029] D １ and D ２ The number of atoms containing substituents in the donor group that can be formed is preferably in the range of 8 to 100. For example, it may be selected from the range of 8 to 70, from the range of 10 to 60, or from the range of 18 to 50.

[0030] In general formula (1), Ter represents a terphenyldiyl group which may be substituted with a deuterium atom or a substituent. The terphenyldiyl group has a structure in which three phenylene groups are linked in a chain, but each phenylene group may be a 1,2-phenylene group, a 1,3-phenylene group, or a 1,4-phenylene group. In one aspect of the present invention, the central phenylene group is a 1,2-phenylene group. In one aspect of the present invention, the central phenylene group is a 1,3-phenylene group. In one aspect of the present invention, the central phenylene group is a 1,4-phenylene group. In one aspect of the present invention, at least one of the phenylene groups at both ends is a 1,2-phenylene group. In one aspect of the present invention, at least one of the phenylene groups at both ends is a 1,3-phenylene group. In one aspect of the present invention, at least one of the phenylene groups at both ends is a 1,4-phenylene group. In one aspect of the present invention, both phenylene groups at both ends are 1,2-phenylene groups. In one aspect of the present invention, both phenylene groups at both ends are 1,3-phenylene groups. In one aspect of the present invention, both phenylene groups at both ends are 1,4-phenylene groups. In a preferred aspect of the present invention, the central phenylene group is a 1,4-phenylene group, and both phenylene groups at both ends are 1,2-phenylene groups. In a preferred aspect of the present invention, the central phenylene group is a 1,2-phenylene group, and both phenylene groups at both ends are 1,4-phenylene groups.

[0031] The deuterium atoms and substituents that can be substituted for the terphenyldiyl group that Ter can take may be selected from, for example, group A, group B, group C, group D, or group E described below. Adjacent groups may also bond to each other to form a cyclic structure. For explanations and specific examples of alkyl groups included in groups A to E, refer to the explanation and specific examples of "alkyl groups as defined herein" in the arylene group that Ar can take above. In one aspect of the present invention, the terphenyldiyl group is unsubstituted. In one aspect of the present invention, the terphenyldiyl group is substituted only with a deuterium atom, for example, a hyperdeuterated terphenyldiyl group. In one aspect of the present invention, the terphenyldiyl group is substituted with at least one alkyl group (e.g., methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group). In one aspect of the present invention, the terphenyldiyl group is substituted with at least one methyl group. In one aspect of the present invention, the terphenyldiyl group is substituted with at least one tert-butyl group. The number of substituent atoms that Ter can take is preferably in the range of 29 to 100. For example, it may be selected from the range of 29 to 70, 29 to 60, or 29 to 50.

[0032] In general formula (1), Ar and D form the ring. １ , Ter, D ２ The number of atoms that form the shortest possible linkage (hereinafter referred to as the "shortest linkage number for ring formation") is preferably in the range of 18 to 23, for example, in the range of 19 to 22. In one aspect of the present invention, the shortest linkage number for ring formation is 20. In one aspect of the present invention, the shortest linkage number for ring formation is 21.

[0033] Compounds represented by general formula (1) include compounds represented by the following general formula (1a): General formula (1a)

[0034] The compound represented by the general formula (1) includes the compound represented by the following general formula (1b). General formula (1b)

[0035] For the definitions and explanations of Ar, D １ , D ２ in the general formulas (1a) and (1b), reference can be made to the definitions and explanations of Ar, D １ , D ２ in the general formula (1). R １ to R ３ in the general formula (1a) and R ４ to R ６ in the general formula (1b each independently represent a deuterium atom or a substituent. n1 to n3 in the general formula (1a) and n4 to n6 in the general formula (1b) each independently represent an integer from 0 to 4. When n1 to n6 are 0, it indicates that the corresponding phenylene group is unsubstituted. When n1 is any integer from 2 to 4, the 2 to 4 R １ may be the same as or different from each other. Similarly, when n2 to n6 are each any integer from 2 to 4, the 2 to 4 R ２ to R ６ may be the same as or different from each other.

[0036] The compound represented by the general formula (1) includes the compound represented by the following general formula (1c). General formula (1c)

[0037] The compound represented by the general formula (1) includes the compound represented by the following general formula (1d). General formula (1d)

[0038] For the definitions and explanations of D １ , D ２ , Ter in the general formulas (1c) and (1d), reference can be made to the definitions and explanations of D １ , D ２ , Ter in the general formula (1). R ７ to R １０ in the general formula (1c) and R ７ to R １０Each of these independently represents a deuterium atom or a substituent. R in general formula (1c) ７ ~R １０ At least one of the following, and R in general formula (1d) １１ ~R １４ At least one of them is an acceptor group. For the definition and explanation of acceptor groups and substituents as used herein, refer to the corresponding definition and description in general formula (1). C-R in general formula (1c) ７ , C-R ８ , C-R ９ , C-R １０ Each of these may be independently substituted with N, and C-R in general formula (1d) １１ , C-R １２ , C-R １３ , C-R １４ Each of these can be independently substituted for N.

[0039] With respect to general formula (1c), in one aspect of the present invention, at least R ７ is an acceptor group. In one aspect of the present invention, at least R ８ is an acceptor group. In one aspect of the present invention, at least R １０ is an acceptor group. In one aspect of the present invention, R ７ Only is an acceptor group. In one aspect of the present invention, R ８ Only is an acceptor group. In one aspect of the present invention, R １０ Only is an acceptor group. In one aspect of the present invention, R ７ ~R １０ At least one (e.g., one, e.g., two) of these is a triazyl group which may be substituted with a deuterium atom or a substituent, or a pyrimidyl group which may be substituted with a deuterium atom or a substituent. For the types and ranges of substituents on the triazyl and pyrimidyl groups referred to here, refer to the corresponding description in general formula (1). ７ ~R １０ At least one (e.g., one, two, or three) of the group is a substituted amino group, which may be a fused ring, a deuterium atom, or a substituent, and is a 9H-carbazole-9-yl group. In one aspect of the present invention, C-R７ , C-R ８ , C-R ９ , C-R １０ None of these are substituted with N. In one aspect of the present invention, C-R ７ , C-R ８ , C-R ９ , C-R １０ At least one of them (for example, one, two, or three) is substituted with N. In one aspect of the present invention, C-R ８ is replaced with N. In one aspect of the present invention, C-R ９ It has been replaced with N.

[0040] With respect to general formula (1d), in one aspect of the present invention, at least R １１ is an acceptor group. In one aspect of the present invention, at least R １２ is an acceptor group. In one aspect of the present invention, R １１ Only is an acceptor group. In one aspect of the present invention, R １２ Only is an acceptor group. In one aspect of the present invention, R １０ Only is an acceptor group. In one aspect of the present invention, R １１ ~R １４ At least one (e.g., one, e.g., two) of these is a triazyl group which may be substituted with a deuterium atom or a substituent, or a pyrimidyl group which may be substituted with a deuterium atom or a substituent. For the types and ranges of substituents on the triazyl and pyrimidyl groups referred to here, refer to the corresponding description in general formula (1). １１ ~R １４ At least one (e.g., one, two, or three) of the group is a substituted amino group, which may be a fused ring, a deuterium atom, or a substituent, and is a 9H-carbazole-9-yl group. In one aspect of the present invention, C-R １１ , C-R １２ , C-R １３ , C-R １４ None of these are substituted with N. In one aspect of the present invention, C-R ７ , C-R ８ , C-R ９ , C-R １０At least one of them (for example, one, two, or three) is substituted with N. In one aspect of the present invention, C-R １３ is replaced with N. In one aspect of the present invention, C-R １４ It has been replaced with N.

[0041] Compounds represented by general formula (1) include compounds represented by the following general formula (1e): General formula (1e)

[0042] Compounds represented by general formula (1) include compounds represented by the following general formula (1f): General formula (1f)

[0043] D in general formula (1e) and general formula (1f) １ , D ２ For the definition and explanation of Ter, see D in general formula (1). １ , D ２ You can refer to the definition and explanation of Ter. D in general formula (1e) and general formula (1f) ３ , D ４ Regarding the definition and explanation of Ter', see D in general formula (1). １ , D ２ You can refer to the definition and explanation of Ter. In one aspect of the present invention, D １ and D ３ They are identical, D ２ and D ４ They are identical. In one aspect of the present invention, D １ and D ４ They are identical, D ２ and D ３ They are identical. In one aspect of the present invention, D １ ~D ４ They are identical. In one aspect of the present invention, Ter and Ter' are identical. In one aspect of the present invention, -D １ -Ter-D ２ - and -D ３ -Ter'-D ４ - is the same. In one aspect of the present invention, -D １ -Ter-D ２ - and -D ４ -Ter'-D ３- are identical. R in general formula (1e) １５ and R １６ and R in general formula (1f) １７ and R １８ Each of these independently represents a deuterium atom or a substituent. R in general formula (1e) １５ and R １６ At least one of the following, and R in general formula (1f) １７ and R １８ At least one of them is an acceptor group. For the definition and explanation of acceptor groups and substituents as used herein, refer to the corresponding definition and description in general formula (1). C-R in general formula (1e) １５ , C-R １６ Each of these may be independently substituted for N, and C-R in general formula (1f) １７ , C-R １８ Each of these can be independently substituted for N.

[0044] With respect to general formula (1e), in one aspect of the present invention, at least R １５ is an acceptor group. In one aspect of the present invention, R １５ Only is an acceptor group. In one aspect of the present invention, R １５ and R １６ Both are acceptor groups independently, for example R １５ and R １６ They are identical, for example R １５ and R １６ They are different from each other. In one aspect of the present invention, R １５ and R １６ At least one (e.g., one, e.g., two) of is a cyano group. In one aspect of the present invention, R １５ and R １６ At least one (e.g., one, e.g., two) of the aryl group (e.g., a phenyl group) is substituted with a cyano group and may be further substituted with a deuterium atom or a substituent other than a cyano group. In one aspect of the present invention, R １５ and R １６At least one (e.g., one, e.g., two) of these is a triazyl group which may be substituted with a deuterium atom or a substituent, or a pyrimidyl group which may be substituted with a deuterium atom or a substituent. For the types and ranges of substituents on the triazyl and pyrimidyl groups referred to here, refer to the corresponding description in general formula (1). １５ and R １６ At least one (e.g., one, e.g., two) of is a substituted amino group, which may be a fused ring, a deuterium atom, or a substituent, and is a 9H-carbazole-9-yl group. In one aspect of the present invention, C-R １５ , C-R １６ None of these are substituted with N. In one aspect of the present invention, C-R １５ , C-R １６ At least one of them (for example, one, two, or three) is substituted with N.

[0045] Regarding the general formula (1f), in one aspect of the present invention, at least R １７ is an acceptor group. In one aspect of the present invention, R １７ Only is an acceptor group. In one aspect of the present invention, R １７ and R １８ Both are acceptor groups independently, for example R １７ and R １８ They are identical, for example R １７ and R １８ They are different from each other. In one aspect of the present invention, R １７ and R １８ At least one (e.g., one, e.g., two) of is a cyano group. In one aspect of the present invention, R １７ and R １８ At least one (e.g., one, e.g., two) of the aryl group (e.g., a phenyl group) is substituted with a cyano group and may be further substituted with a deuterium atom or a substituent other than a cyano group. In one aspect of the present invention, R １７ and R １８At least one (e.g., one, e.g., two) of these is a triazyl group which may be substituted with a deuterium atom or a substituent, or a pyrimidyl group which may be substituted with a deuterium atom or a substituent. For the types and ranges of substituents on the triazyl and pyrimidyl groups referred to here, refer to the corresponding description in general formula (1). １７ and R １８ At least one (e.g., one, e.g., two) of is a substituted amino group, which may be a fused ring, a deuterium atom, or a substituent, and is a 9H-carbazole-9-yl group. In one aspect of the present invention, C-R １７ , C-R １８ None of these are substituted with N. In one aspect of the present invention, C-R １７ , C-R １８ At least one of them (for example, one, two, or three) is substituted with N.

[0046] Each of the general formulas (1a) to (1f) can be limited by applying the embodiments and ranges described in general formula (1). The compounds represented by general formulas (1) to (1f) may be compounds having a symmetrical structure or compounds having an asymmetrical structure.

[0047] In this specification, "Group A" means deuterium atoms, hydroxyl groups, halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), alkyl groups (e.g., C1-C40), alkoxy groups (e.g., C1-C40), alkylthio groups (e.g., C1-C40), aryl groups (e.g., C6-C30), aryloxy groups (e.g., C6-C30), arylthio groups (e.g., C6-C30), heteroaryl groups (e.g., ring skeleton constituent atoms numbering 5-30), heteroaryloxy groups (e.g., This group consists of alkyl groups (e.g., ring skeleton with 5 to 30 constituent atoms), heteroarylthio groups (e.g., ring skeleton with 5 to 30 constituent atoms), acyl groups (e.g., 1 to 40 carbon atoms), alkenyl groups (e.g., 1 to 40 carbon atoms), alkynyl groups (e.g., 1 to 40 carbon atoms), alkoxycarbonyl groups (e.g., 1 to 40 carbon atoms), heteroaryloxycarbonyl groups (e.g., 1 to 40 carbon atoms), silyl groups (e.g., trialkylsilyl groups with 1 to 40 carbon atoms), and nitro groups. The alkyl groups, alkoxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, heteroaryl groups, heteroaryloxy groups, heteroarylthio groups, acyl groups, alkenyl groups, alkynyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, heteroaryloxycarbonyl groups, silyl groups, and nitro groups referred to here may be substituted with substituents having a structure in which one or more of the deuterium atoms constituting group A and any of the substituents listed above are bonded. In this specification, "Group B" refers to the group consisting of a deuterium atom, an alkyl group (e.g., having 1 to 40 carbon atoms), an alkoxy group (e.g., having 1 to 40 carbon atoms), an aryl group (e.g., having 6 to 30 carbon atoms), an aryloxy group (e.g., having 5 to 30 atoms in the ring skeleton), an heteroaryl group (e.g., having 5 to 30 atoms in the ring skeleton), and a diarylaminoamino group (e.g., having 0 to 20 carbon atoms). The alkyl group, alkoxy group, aryl group, aryloxy group, heteroaryl group, heteroaryloxy group, and diarylaminoamino group referred to herein may be substituted with substituents having a structure in which one or more of the deuterium atoms constituting Group B and any of the substituents listed above are bonded.In this specification, "Group C" refers to the group consisting of a deuterium atom, alkyl groups (e.g., 1 to 20 carbon atoms), aryl groups (e.g., 6 to 22 carbon atoms), heteroaryl groups (e.g., 5 to 20 atoms in the ring skeleton), and diarylamino groups (e.g., 12 to 20 carbon atoms). The alkyl groups, aryl groups, heteroaryl groups, and diarylamino groups referred to here may be substituted with substituents having a structure in which one or more of the substituents listed above are bonded to the deuterium atom constituting Group C. In this specification, "Group D" refers to the group consisting of a deuterium atom, alkyl groups (e.g., 1 to 20 carbon atoms), aryl groups (e.g., 6 to 22 carbon atoms), and heteroaryl groups (e.g., 5 to 20 atoms in the ring skeleton). The alkyl groups, aryl groups, and heteroaryl groups referred to here may be substituted with substituents having a structure in which one or more of the substituents listed above are bonded to the deuterium atom constituting Group D. In this specification, "Group E" refers to the group consisting of a deuterium atom, alkyl groups (e.g., 1 to 20 carbon atoms), and aryl groups (e.g., 6 to 22 carbon atoms). The alkyl and aryl groups referred to herein may be substituted with substituents having a structure in which one or more of the deuterium atoms constituting group E and any of the substituents described above are bonded.

[0048] Specific examples of compounds represented by general formula (1) are given below. However, the compounds represented by general formula (1) that can be used in the present invention should not be interpreted as being limited by these specific examples. In the following examples, "Ph" represents a phenyl group.

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059] The following linking groups are present in the specific examples of the above compounds Compounds in which each of the following linking groups is replaced can also be given as specific examples. These substituted compounds are also disclosed individually in this specification as specific examples. The wavy lines indicate the bond position.

[0060] Furthermore, the following linking groups are present in the specific examples of the above compounds Compounds in which each of the following linking groups is replaced can also be given as specific examples. These substituted compounds are also disclosed individually in this specification as specific examples.

[0061] The molecular weight of the compound represented by general formula (1) is preferably 1500 or less, more preferably 1200 or less, even more preferably 1000 or less, and even more preferably 900 or less, when intended to be used as a film formed by vapor deposition on an organic layer containing the compound represented by general formula (1). The lower limit of the molecular weight is the molecular weight of the smallest compound in the group of compounds represented by general formula (1). The compound represented by general formula (1) may be formed as a film by coating regardless of its molecular weight. Using the coating method makes it possible to form films even of compounds with relatively large molecular weights. The compound represented by general formula (1) has the advantage of being easily soluble in organic solvents. For this reason, the compound represented by general formula (1) is easy to apply the coating method to and is easy to purify to increase its purity.

[0062] Applying the present invention, it is conceivable to use compounds containing multiple structures represented by general formula (1) within the molecule as luminescent materials. For example, polymerizable groups may be pre-existing in the structure represented by general formula (1), and polymers obtained by polymerizing these polymerizable groups may be used as luminescent materials. Specifically, monomers containing polymerizable functional groups in any of the structures represented by general formula (1) may be prepared, and polymers having repeating units may be obtained by polymerizing them alone or copolymerizing them with other monomers, and these polymers may be used as luminescent materials. Alternatively, dimers or trimers may be obtained by coupling compounds represented by general formula (1), and these may be used as luminescent materials.

[0063] Examples of polymers having repeating units that include a structure represented by general formula (1) include polymers that include a structure represented by either of the following two general formulas.

[0064] In the general formula above, Q represents a group containing the structure represented by general formula (1), and L １ and L ２ The symbol represents a linking group. The number of carbon atoms in the linking group is preferably 0 to 20, more preferably 1 to 15, and even more preferably 2 to 10. The linking group is -X １１ -L １１ It is preferable that the structure is represented by -. Here, X １１ L represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom. １１ R represents a linking group, which is preferably a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, and more preferably a substituted or unsubstituted alkylene group or a substituted or unsubstituted phenylene group having 1 to 10 carbon atoms. ２０１ , R ２０２ , R ２０３ and R ２０４Each of these independently represents a hydrogen atom, a deuterium atom, or a substituent. Preferred substituents are substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 6 carbon atoms, and halogen atoms; more preferably, unsubstituted alkyl groups having 1 to 3 carbon atoms, unsubstituted alkoxy groups having 1 to 3 carbon atoms, fluorine atoms, and chlorine atoms; and even more preferably, unsubstituted alkyl groups having 1 to 3 carbon atoms and unsubstituted alkoxy groups having 1 to 3 carbon atoms. １ and L ２ The linking group represented by is at any position in the structure represented by the general formula (1) that constitutes Q (for example, Ar １ D, A, R １ ~R ４ It can bond to either of the following. Two or more linking groups may be linked to one Q to form a cross-linked structure or a network structure.

[0065] As a concrete example of a repeating unit structure, we can cite the structure represented by the following formula.

[0066] Polymers having repeating units including these formulas can be synthesized by introducing a hydroxyl group into one of the structures represented by general formula (1), reacting it with the following compounds as a linker to introduce polymerizable groups, and then polymerizing those polymerizable groups.

[0067] A polymer containing a structure represented by general formula (1) within its molecule may consist only of repeating units having the structure represented by general formula (1), or it may contain repeating units having other structures. Furthermore, the repeating units having the structure represented by general formula (1) contained in the polymer may be of a single type or two or more types. Examples of repeating units that do not have the structure represented by general formula (1) include those derived from monomers commonly used in copolymerization. For example, repeating units derived from monomers having ethylenically unsaturated bonds, such as ethylene and styrene, can be cited.

[0068] It is preferable that the compound represented by general formula (1) does not contain metal atoms. For example, as the compound represented by general formula (1), a compound consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms, oxygen atoms, and sulfur atoms can be selected. For example, as the compound represented by general formula (1), a compound consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms, and oxygen atoms can be selected. For example, as the compound represented by general formula (1), a compound consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms, and sulfur atoms can be selected. For example, as the compound represented by general formula (1), a compound consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, and nitrogen atoms can be selected. For example, as the compound represented by general formula (1), a compound consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, and nitrogen atoms can be selected.

[0069] Compounds represented by general formula (1) are useful as light-emitting materials. Compounds represented by general formula (1) include compounds that can emit delayed fluorescence. In some embodiments of this disclosure, when excited by thermal or electronic means, a compound represented by general formula (1) can emit light in the UV region, the blue, green, yellow, orange, and red regions of the visible spectrum (e.g., about 420 nm to about 500 nm, about 500 nm to about 600 nm, or about 600 nm to about 700 nm), or the near-infrared region. In some embodiments of this disclosure, when excited by thermal or electronic means, a compound represented by general formula (1) can emit light in the red or orange region of the visible spectrum (e.g., about 620 nm to about 780 nm, or about 650 nm). In some embodiments of this disclosure, when excited by thermal or electronic means, a compound represented by general formula (1) can emit light in the orange or yellow region of the visible spectrum (e.g., about 570 nm to about 620 nm, about 590 nm, or about 570 nm). In some embodiments of this disclosure, the compound represented by general formula (1) can emit light in the green region of the visible spectrum (e.g., about 490 nm to about 575 nm, about 510 nm) when excited by thermal or electronic means. In some embodiments of this disclosure, the compound represented by general formula (1) can emit light in the blue region of the visible spectrum (e.g., about 400 nm to about 490 nm, about 475 nm) when excited by thermal or electronic means. In some embodiments of this disclosure, the compound represented by general formula (1) can emit light in the ultraviolet spectral region (e.g., 280 to 400 nm) when excited by thermal or electronic means. In some embodiments of this disclosure, the compound represented by general formula (1) can emit light in the infrared spectral region (e.g., 780 nm to 2 μm) when excited by thermal or electronic means. In some embodiments of this disclosure, organic semiconductor devices can be fabricated using the compound represented by general formula (1). For example, CMOS (complementary metal-oxide-semiconductor) devices can be fabricated using the compound represented by general formula (1).In some embodiments of this disclosure, organic optical elements such as organic electroluminescent elements and solid-state image sensors (e.g., CMOS image sensors) can be fabricated using a compound represented by general formula (1).

[0070] The electronic properties of a small molecule chemical library can be calculated using known ab initio quantum chemical calculations. For example, the Hartree-Fock equation (TD-DFT / B3LYP / 6-31G*) can be analyzed using time-dependent density functional theory with 6-31G*, Becke's three parameters, and a set of functions known as the Lee-Yang-Parr hybrid functional as a basis, to screen molecular fragments (parts) having HOMO above a certain threshold and LUMO below a certain threshold. This allows for the selection of donor parts ("D") when the HOMO energy (e.g., ionization potential) is above -6.5 eV, for example. Alternatively, when the LUMO energy (e.g., electron affinity) is below -0.5 eV, for example, acceptor parts ("A") can be selected. The bridge portion ("B") is a strongly conjugated system that can strictly restrict the receptor and donor portions to specific stereochemistrys, for example, thereby preventing duplication between the π-conjugated systems of the donor and receptor portions. In one embodiment, the compound library is selected using one or more of the following characteristics: 1. Emission near a specific wavelength; 2. A calculated triplet state above a specific energy level; 3. ΔE below a specific value. ＳＴ Value 4. Quantum yield above a specific value 5. HOMO level 6. LUMO level In one embodiment, the difference (ΔE) between the lowest singlet excited state and the lowest triplet excited state at 77K ＳＴ ) is less than about 0.5 eV, less than about 0.4 eV, less than about 0.3 eV, less than about 0.2 eV, or less than about 0.1 eV. In one embodiment, ΔE ＳＴThe values ​​are less than about 0.09 eV, less than about 0.08 eV, less than about 0.07 eV, less than about 0.06 eV, less than about 0.05 eV, less than about 0.04 eV, less than about 0.03 eV, less than about 0.02 eV, or less than about 0.01 eV. In some embodiments, the compound represented by general formula (1) exhibits a quantum yield of more than 25%, for example, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, or higher.

[0071] [Synthesis Method of Compounds Represented by General Formula (1)] Compounds represented by general formula (1) are novel compounds. Compounds represented by general formula (1) can be synthesized by combining known reactions. For example, D １ and D ２ However, when synthesizing a compound which is a 9H-carbazole-9-yl group that may be fused or substituted with a deuterium atom or substituent, D １ and D ２ Ar and D have a fluorine atom at the bonding site. １ -Ter-D ２ It can be synthesized by reacting with [the other two components]. For specific synthesis conditions, please refer to the synthesis examples described later.

[0072] [Constructions using compounds represented by general formula (1)] In some embodiments, a solid film or layer is formed by combining the compound represented by general formula (1) with one or more materials (e.g., small molecules, polymers, metals, metal complexes, etc.) that disperse the compound, covalently bond with the compound, coat the compound, support the compound, or associate with the compound. For example, a film can be formed by combining the compound represented by general formula (1) with an electroactive material. In some cases, the compound represented by general formula (1) may be combined with a hole transport polymer. In some cases, the compound represented by general formula (1) may be combined with an electron transport polymer. In some cases, the compound represented by general formula (1) may be combined with both a hole transport polymer and an electron transport polymer. In some cases, the compound represented by general formula (1) may be combined with a copolymer having both a hole transport portion and an electron transport portion. Through these embodiments, electrons and / or holes formed in a solid film or layer can be made to interact with the compound represented by general formula (1).

[0073] [Film Formation] In one embodiment, a film containing the compound represented by general formula (1) can be formed by a wet process. In the wet process, a solution containing the composition with the compound represented by general formula (1) is applied to a surface, and the film is formed after the solvent is removed. Examples of wet processes include, but are not limited to, spin coating, slit coating, inkjet (spray) printing, gravure printing, offset printing, and flexographic printing. In the wet process, an appropriate organic solvent capable of dissolving the composition with the compound represented by general formula (1) is selected and used. In one embodiment, substituents (e.g., alkyl groups) that increase the solubility in organic solvents can be introduced into the compound contained in the composition. In one embodiment, a film containing the compound represented by general formula (1) can be formed by a dry process. In one embodiment, but is not limited to, vacuum deposition can be used as the dry process. When vacuum deposition is used, the compounds constituting the film may be co-deposited from individual deposition sources, or they may be co-deposited from a single deposition source containing a mixture of compounds. When using a single deposition source, a mixed powder of compound powders may be used, a compressed molded body made by compressing the mixed powder may be used, or a mixture obtained by heating, melting, and cooling each compound may be used. In one embodiment, by performing co-deposition under conditions where the deposition rates (weight loss rates) of multiple compounds contained in a single deposition source are the same or nearly the same, a film with a composition ratio corresponding to the composition ratio of multiple compounds contained in the deposition source can be formed. By mixing multiple compounds in the same composition ratio as the composition ratio of the formed film to create a deposition source, a film with a desired composition ratio can be easily formed. In one embodiment, the temperature at which each co-deposited compound has the same weight loss rate can be identified, and that temperature can be adopted as the temperature during co-deposition.

[0074] [Organic Electroluminescent Elements] This section describes organic electroluminescent elements containing a compound represented by general formula (1). Organic electroluminescent elements using a compound represented by general formula (1) have excellent performance. For example, some organic electroluminescent elements containing a compound represented by general formula (1) have a longer element lifespan by using the compound represented by general formula (1). For example, some organic electroluminescent elements containing a compound represented by general formula (1) have a higher luminescence efficiency by using the compound represented by general formula (1). For example, some organic electroluminescent elements containing a compound represented by general formula (1) have a lower driving voltage by using the compound represented by general formula (1). For example, some organic electroluminescent elements containing a compound represented by general formula (1) have a higher proportion of delayed fluorescence component during emission by using the compound represented by general formula (1). In one aspect of the present invention, a compound represented by general formula (1) is used as the light-emitting material of an organic electroluminescent element. For example, a compound represented by general formula (1) is used as the light-emitting material in the light-emitting layer. Among the compounds represented by general formula (1), there are compounds with a large amount of delayed fluorescence component. In one aspect of the present invention, a compound represented by general formula (1) is used as a host material. In one aspect of the present invention, a compound represented by general formula (1) is used together with one or more light-emitting materials. The light-emitting materials here may be fluorescent materials, phosphorescent materials, or delayed fluorescence materials. For example, a fluorescent material with a lower minimum excitation singlet energy than the compound represented by general formula (1) is used together with the compound represented by general formula (1). In one aspect of the present invention, a compound represented by general formula (1) is used as a hole transport material. In one aspect of the present invention, a compound represented by general formula (1) is used as an electron transport material. In one embodiment, the light-emitting layer of the organic electroluminescent element contains a compound represented by general formula (1), and the compound represented by general formula (1) is oriented parallel to the substrate. In one embodiment, the substrate is a film-forming surface.In some embodiments, the orientation of the compound represented by general formula (1) with respect to the film-forming surface influences or determines the direction of light propagation emitted by the aligned compound. In some embodiments, aligning the direction of light propagation emitted by the compound represented by general formula (1) improves the light extraction efficiency from the light-emitting layer. In some embodiments, the compound represented by general formula (1) assists the light emission of other light-emitting materials contained in the light-emitting layer (as a so-called assist dopant). In some embodiments, the lowest excited singlet energy level of the compound represented by general formula (1) contained in the light-emitting layer lies between the lowest excited singlet energy level of the host material contained in the light-emitting layer and the lowest excited singlet energy level of the other light-emitting materials contained in the light-emitting layer. In some embodiments, the organic electroluminescent element includes at least one light-emitting layer. In some embodiments, the organic electroluminescent element includes at least an anode, a cathode, and an organic layer between the anode and the cathode. In some embodiments, the organic layer includes at least a light-emitting layer. In some embodiments, the organic layer includes only a light-emitting layer. In some embodiments, the organic layer includes one or more organic layers in addition to the light-emitting layer. Examples of organic layers include hole transport layers, hole injection layers, electron barrier layers, hole barrier layers, electron injection layers, electron transport layers, and exciton barrier layers. In some embodiments, the hole transport layer may be a hole injection transport layer having a hole injection function, and the electron transport layer may be an electron injection transport layer having an electron injection function.

[0075] Emitting layer: In some embodiments, the emissive layer is a layer in which holes and electrons injected from the anode and cathode, respectively, recombine to form excitons. In some embodiments, the layer emits light. In some embodiments, only an emissive material is used as the emissive layer. In some embodiments, the emissive layer includes an emissive material and a host material. In some embodiments, the emissive material is one or more compounds represented by general formula (1). In some embodiments, singlet and triplet excitons generated in the emissive material are confined within the emissive material to improve the light emission efficiency of organic electroluminescent elements and organic photoluminescent elements. In some embodiments, a host material is used in addition to the emissive material in the emissive layer. In some embodiments, the host material is an organic compound. In some embodiments, the organic compound has excitation singlet energy and excitation triplet energy, at least one of which is higher than those of the emissive material of the present invention. In some embodiments, singlet and triplet excitons generated in the emissive material of the present invention are confined within the molecules of the emissive material of the present invention. In some embodiments, the singlet and triplet excitons are sufficiently confined to improve the light emission efficiency. In some embodiments, singlet and triplet excitons are not sufficiently confined, even though high photoluminescence efficiency can still be obtained; that is, any host material capable of achieving high photoluminescence efficiency can be used in the present invention without particular limitation. In some embodiments, photoluminescence occurs in the light-emitting material in the light-emitting layer of the device of the present invention. In some embodiments, the synchrotron radiation includes both fluorescence and delayed fluorescence. In some embodiments, the synchrotron radiation includes synchrotron radiation from the host material. In some embodiments, the synchrotron radiation consists of synchrotron radiation from the host material. In some embodiments, the synchrotron radiation includes synchrotron radiation from a compound represented by general formula (1) and synchrotron radiation from the host material. In some embodiments, a thermally activated delayed fluorescence material (TADF) and a host material are used. In some embodiments, the TADF is an assist dopant with a lower excitation singlet energy than the host material in the light-emitting layer and a higher excitation singlet energy than the light-emitting material in the light-emitting layer. In some embodiments, the organic electroluminescent device has a layer containing a compound represented by general formula (1). In some embodiments, the layer also contains the host material.In one embodiment, the layer containing the compound represented by general formula (1) and a host material also includes a delayed fluorescence material having a structure outside the range of general formula (1), wherein the lowest excitation singlet energy of the delayed fluorescence material is lower than that of the host material and higher than that of the compound represented by general formula (1). In this embodiment, when the organic electroluminescent element is energized, the amount of light emitted from the compound represented by general formula (1) is maximized. In another embodiment, the organic electroluminescent element has a layer containing the compound represented by general formula (1) and a light-emitting material having a structure outside the range of general formula (1) (this layer may further contain a host material). In one embodiment, the lowest excitation singlet energy of the light-emitting material having a structure outside the range of general formula (1) is lower than that of the compound represented by general formula (1). In one embodiment, when the organic electroluminescent element is energized, the amount of light emitted from the light-emitting material having a structure outside the range of general formula (1) is maximized.

[0076] When a compound represented by general formula (1) is used as an assist dopant, various compounds can be used as the luminescent material (preferably a fluorescent material). Such luminescent materials include anthracene derivatives, tetracene derivatives, naphthacene derivatives, pyrene derivatives, perylene derivatives, chrysene derivatives, rubrene derivatives, coumarin derivatives, pyran derivatives, stilbene derivatives, fluorene derivatives, anthryl derivatives, pyromethene derivatives, terphenyl derivatives, terphenylene derivatives, fluorantene derivatives, amine derivatives, quinacridone derivatives, oxadiazole derivatives, malononitrile derivatives, carbazole derivatives, juloridine derivatives, thiazole derivatives, and derivatives having metals (Al, Zn). These exemplary skeletons may or may not have substituents. Furthermore, these exemplary skeletons may be combined with each other. Below, examples of luminescent materials that can be used in combination with an assist dopant having the structure represented by general formula (1) are given.

[0077]

[0078] Furthermore, the compounds described in paragraphs 0220 to 0239 of Publication WO2015 / 022974 can also be particularly preferred as luminescent materials used together with an assist dopant having a structure represented by general formula (1).

[0079] In one embodiment, when a host material is used, the amount of the compound used in the present invention as a light-emitting material contained in the light-emitting layer is 0.1% by weight or more. In one embodiment, when a host material is used, the amount of the compound of general formula (1) as a light-emitting material contained in the light-emitting layer is 1% by weight or more. In one embodiment, when a host material is used, the amount of the compound of general formula (1) as a light-emitting material contained in the light-emitting layer is 50% by weight or less. In one embodiment, when a host material is used, the amount of the compound of general formula (1) as a light-emitting material contained in the light-emitting layer is 20% by weight or less. In one embodiment, when a host material is used, the amount of the compound of general formula (1) as a light-emitting material contained in the light-emitting layer is 10% by weight or less. In one embodiment, the host material of the light-emitting layer is an organic compound having hole transport function and electron transport function. In one embodiment, the host material of the light-emitting layer is an organic compound that prevents an increase in the wavelength of synchrotron radiation. In one embodiment, the host material of the light-emitting layer is an organic compound having a high glass transition temperature.

[0080] In some embodiments, the host material is selected from the group consisting of:

[0081] In one embodiment, the light-emitting layer contains two or more structurally different TADF molecules. For example, the light-emitting layer can contain three materials in which the excited singlet energy levels are highest in the host material, followed by the first TADF molecule and then the second TADF molecule. In this case, both the first TADF molecule and the second TADF molecule have a difference ΔE between their lowest excited singlet energy level and their lowest excited triplet energy level of 77K. ＳＴThe luminescence voltage is preferably 0.3 eV or less, more preferably 0.25 eV or less, more preferably 0.2 eV or less, more preferably 0.15 eV or less, even more preferably 0.1 eV or less, even more preferably 0.07 eV or less, even more preferably 0.05 eV or less, even more preferably 0.03 eV or less, and particularly preferably 0.01 eV or less. The concentration of the first TADF molecules in the luminescent layer is preferably greater than the concentration of the second TADF molecules. Also, the concentration of the host material in the luminescent layer is preferably greater than the concentration of the second TADF molecules. The concentration of the first TADF molecules in the luminescent layer may be greater than, less than, or the same as the concentration of the host material. In one embodiment, the composition of the luminescent layer may be 10 to 70% by weight of the host material, 10 to 80% by weight of the first TADF molecules, and 0.1 to 30% by weight of the second TADF molecules. In one embodiment, the composition of the light-emitting layer may be 20-45% by weight of the host material, 50-75% by weight of the first TADF molecule, and 5-20% by weight of the second TADF molecule. In one embodiment, the photo-excited emission quantum yield φPL1(A) of a co-evaporated film of the first TADF molecule and the host material (concentration of the first TADF molecule in this co-evaporated film = A by weight) and the photo-excited emission quantum yield φPL2(A) of a co-evaporated film of the second TADF molecule and the host material (concentration of the second TADF molecule in this co-evaporated film = A by weight) satisfy the relationship φPL1(A) > φPL2(A). In one embodiment, the photo-excited emission quantum yield φPL2(B) of a co-evaporated film of the second TADF molecule and the host material (concentration of the second TADF molecule in this co-evaporated film = B by weight) and the photo-excited emission quantum yield φPL2(100) of a film of the second TADF molecule alone satisfy the relationship φPL2(B) > φPL2(100). In one embodiment, the light-emitting layer can contain three different structural TADF molecules. The compound of general formula (1) may be any of the multiple TADF compounds contained in the light-emitting layer. In one embodiment, the light-emitting layer can be composed of a material selected from the group consisting of a host material, an assist dopant, and a light-emitting material. In one embodiment, the light-emitting layer does not contain any metal elements.In one embodiment, the light-emitting layer may be made of a material composed only of atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms, oxygen atoms, and sulfur atoms. Alternatively, the light-emitting layer may be made of a material composed only of atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms, and oxygen atoms. Alternatively, the light-emitting layer may be made of a material composed only of atoms selected from the group consisting of carbon atoms, hydrogen atoms, nitrogen atoms, and oxygen atoms. When the light-emitting layer contains a TADF material other than the compound of general formula (1), the TADF material may be a known delayed fluorescence material. Preferred delayed fluorescence materials include paragraphs 0008-0048 and 0095-0133 of WO2013 / 154064, paragraphs 0007-0047 and 0073-0085 of WO2013 / 011954, paragraphs 0007-0033 and 0059-0066 of WO2013 / 011955, and paragraph 0008 of WO2013 / 081088. ~0071 and 0118~0133, paragraphs 0009~0046 and 0093~0134 of Japanese Patent Publication No. 2013-256490, paragraphs 0008~0020 and 0038~0040 of Japanese Patent Publication No. 2013-116975, paragraphs 0007~0032 and 0079~0084 of WO2013 / 133359, paragraph 0 of WO2013 / 161437 Paragraphs 008-0054 and 0101-0121 of Japanese Patent Publication No. 2014-9352, paragraphs 0007-0041 and 0060-0069 of Japanese Patent Publication No. 2014-9224, paragraphs 0008-0048 and 0067-0076 of Japanese Patent Publication No. 2017-119663, paragraphs 0013-0025 of Japanese Patent Publication No. 2017-119664, Japanese Patent Publication No. 2 This includes compounds included in the general formulas described in paragraphs 0012 to 0025 of Japanese Patent Publication No. 017-222623, paragraphs 0010 to 0050 of Japanese Patent Application Publication No. 2017-226838, paragraphs 0012 to 0043 of Japanese Patent Application Publication No. 2018-100411, and paragraphs 0016 to 0044 of Japanese Patent Application Publication No. WO2018 / 047853, particularly exemplary compounds that can emit delayed fluorescence.Furthermore, here we have Japanese Patent Publication No. 2013-253121, WO2013 / 133359, WO2014 / 034535, WO2014 / 115743, WO2014 / 122895, WO2014 / 126200, WO2014 / 136758, WO2014 / 133121, WO20 14 / 136860, WO2014 / 196585, WO2014 / 189122, WO2014 / 168101, WO2015 / 008 580 publication, WO2014 / 203840 publication, WO2015 / 002213 publication, WO2015 / 016200 publication, WO2015 / 019725 publication, WO2015 / 072470, WO2015 / 108049, WO2015 / 080182, WO2015 / 072537, WO2015 / 080183, JP 2015-129240, WO2015 / 129714, WO2015 / 129715, WO2015 / 13350 A light-emitting material that can emit delayed fluorescence, as described in Publication No. 1, WO2015 / 136880, WO2015 / 137244, WO2015 / 137202, WO2015 / 137136, WO2015 / 146541, and WO2015 / 159541, can preferably be used. The above publications described in this paragraph are incorporated herein by reference as part of this specification.

[0082] The following describes each component of the organic electroluminescent element and each layer other than the light-emitting layer.

[0083] Substrate: In some embodiments, the organic electroluminescent element of the present invention is held by a substrate, which is not particularly limited and may be any material commonly used in organic electroluminescent elements, such as glass, transparent plastic, quartz, and silicon.

[0084] Anode: In some embodiments, the anode of an organic electroluminescent apparatus is made from a metal, alloy, conductive compound, or a combination thereof. In some embodiments, the metal, alloy, or conductive compound has a high work function (4 eV or more). In some embodiments, the metal is Au. In some embodiments, the conductive transparent material is CuI, indium tin oxide (ITO), SnO ２ and selected from ZnO. In some embodiments, IDIXO (In ２ O ３ An amorphous material capable of forming a transparent conductive film, such as -ZnO, is used. In some embodiments, the anode is a thin film. In some embodiments, the thin film is produced by vapor deposition or sputtering. In some embodiments, the film is patterned by a photolithography method. In some embodiments, if the pattern does not need to be highly accurate (e.g., about 100 μm or more), the pattern may be formed using a mask with a shape suitable for vapor deposition or sputtering onto the electrode material. In some embodiments, when a coating material such as an organic conductive compound can be applied, a wet film formation method such as a printing method or a coating method is used. In some embodiments, when synchrotron radiation passes through the anode, the anode has a transmittance of more than 10%, and the anode has a sheet resistance of several hundred ohms or less per unit area. In some embodiments, the thickness of the anode is 10 to 1,000 nm. In some embodiments, the thickness of the anode is 10 to 200 nm. In some embodiments, the thickness of the anode varies depending on the material used.

[0085] Cathode: In some embodiments, the cathode is made of an electrode material such as a metal with a low work function (4 eV or less) (referred to as an electron-injection metal), an alloy, a conductive compound or a combination thereof. In some embodiments, the electrode material is sodium, sodium-potassium alloy, magnesium, lithium, magnesium-copper mixture, magnesium-silver mixture, magnesium-aluminum mixture, magnesium-indium mixture, aluminum-aluminum oxide (Al ２ O３ ) mixtures, indium, lithium-aluminum mixtures and rare earth elements are selected. In some embodiments, a mixture of an electron-injection metal and a second metal which is a stable metal having a higher work function than the electron-injection metal is used. In some embodiments, the mixture is a magnesium-silver mixture, a magnesium-aluminum mixture, a magnesium-indium mixture, an aluminum-aluminum oxide (Al ２ O ３ ) are selected from a mixture, a lithium-aluminum mixture, and aluminum. In some embodiments, the mixture improves electron injection properties and resistance to oxidation. In some embodiments, the cathode is manufactured by forming the electrode material as a thin film by vapor deposition or sputtering. In some embodiments, the cathode has a sheet resistance of several hundred ohms or less per unit area. In some embodiments, the thickness of the cathode is 10 nm to 5 μm. In some embodiments, the thickness of the cathode is 50 to 200 nm. In some embodiments, either the anode or cathode of the organic electroluminescent element is transparent or translucent in order to transmit synchrotron radiation. In some embodiments, a transparent or translucent electroluminescent element improves light radiance. In some embodiments, a transparent or translucent cathode is formed by forming the cathode with respect to the anode from the conductive transparent material described above. In some embodiments, the element includes an anode and a cathode, both of which are transparent or translucent.

[0086] Injection layer: The injection layer is a layer between the electrode and the organic layer. In some embodiments, the injection layer reduces the driving voltage and enhances the light radiance. In some embodiments, the injection layer includes a hole injection layer and an electron injection layer. The injection layer can be located between the anode and the light-emitting layer or hole transport layer, and between the cathode and the light-emitting layer or electron transport layer. In some embodiments, an injection layer is present. In some embodiments, an injection layer is absent. The following are examples of preferred compounds that can be used as hole injection materials.

[0087]

[0088] Next, we will list some examples of preferred compounds that can be used as electron injection materials.

[0089] Barrier Layer: A barrier layer is a layer that can prevent charges (electrons or holes) and / or excitons present in the light-emitting layer from diffusing to the outside of the light-emitting layer. In some embodiments, an electron barrier layer exists between the light-emitting layer and the hole transport layer, preventing electrons from passing through the light-emitting layer to the hole transport layer. In some embodiments, a hole barrier layer exists between the light-emitting layer and the electron transport layer, preventing holes from passing through the light-emitting layer to the electron transport layer. In some embodiments, a barrier layer prevents excitons from diffusing to the outside of the light-emitting layer. In some embodiments, the electron barrier layer and the hole barrier layer constitute an exciton barrier layer. As used herein, the terms “electron barrier layer” or “exciton barrier layer” include layers that have both the functions of an electron barrier layer and an exciton barrier layer.

[0090] Hole barrier layer: The hole barrier layer functions as an electron transport layer. In some embodiments, the hole barrier layer prevents holes from reaching the electron transport layer during electron transport. In some embodiments, the hole barrier layer increases the probability of electron-hole recombination in the light-emitting layer. The material used for the hole barrier layer may be the same material described above for the electron transport layer. The following are examples of preferred compounds that can be used for the hole barrier layer.

[0091]

[0092] Electron barrier layer: The electron barrier layer transports holes. In some embodiments, during hole transport, the electron barrier layer prevents electrons from reaching the hole transport layer. In some embodiments, the electron barrier layer increases the probability of electron-hole recombination in the light-emitting layer. The material used for the electron barrier layer may be the same material described above for the hole transport layer. Specific examples of preferred compounds that can be used as electron barrier materials are listed below.

[0093]

[0094] Exciton barrier layer: The exciton barrier layer prevents excitons generated through the recombination of holes and electrons in the light-emitting layer from diffusing to the charge transport layer. In some embodiments, the exciton barrier layer enables effective confinement of excitons in the light-emitting layer. In some embodiments, the optical emission efficiency of the device is improved. In some embodiments, the exciton barrier layer is located on either the anode side or the cathode side and adjacent to the light-emitting layers on both sides. In some embodiments, when the exciton barrier layer is located on the anode side, it may be located between the hole transport layer and the light-emitting layer and adjacent to the light-emitting layer. In some embodiments, when the exciton barrier layer is located on the cathode side, it may be located between the light-emitting layer and the cathode and adjacent to the light-emitting layer. In some embodiments, a hole injection layer, electron barrier layer, or similar layer is located between the anode and the exciton barrier layer adjacent to the light-emitting layer on the anode side. In some embodiments, a hole injection layer, electron barrier layer, hole barrier layer, or similar layer is located between the cathode and the exciton barrier layer adjacent to the light-emitting layer on the cathode side. In some embodiments, the exciton barrier layer includes an excitation singlet energy and an excitation triplet energy, at least one of which is higher than the excitation singlet energy and excitation triplet energy of the light-emitting material, respectively.

[0095] Hole transport layer: The hole transport layer comprises a hole transport material. In some embodiments, the hole transport layer is a single layer. In some embodiments, the hole transport layer has multiple layers. In some embodiments, the hole transport material has one of the properties of hole injection or transport properties and electron barrier properties. In some embodiments, the hole transport material is an organic material. In some embodiments, the hole transport material is an inorganic material. Examples of known hole transport materials that can be used in the present invention include, but are not limited to, triazole derivatives, oxadiazole derivatives, imidazole derivatives, carbazole derivatives, indrocarbazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, allylamine derivatives, aminosubstituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers and conductive polymer oligomers (especially thiophene oligomers), or combinations thereof. In some embodiments, the hole transport material is selected from porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds. In some embodiments, the hole transport material is an aromatic tertiary amine compound. Specific examples of preferred compounds that can be used as hole transport materials are listed below.

[0096]

[0097] Electron transport layer: The electron transport layer comprises an electron transport material. In some embodiments, the electron transport layer is a single layer. In some embodiments, the electron transport layer has multiple layers. In some embodiments, the electron transport material only needs to have the function of transporting electrons injected from the cathode to the light-emitting layer. In some embodiments, the electron transport material also functions as a hole barrier material. Examples of electron transport layers that can be used in the present invention include, but are not limited to, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimides, fluorenylidene methane derivatives, anthraquinodimethane, anthrone derivatives, oxadiazole derivatives, azole derivatives, azine derivatives or combinations thereof, or polymers thereof. In some embodiments, the electron transport material is a thiadiazole derivative or a quinoxaline derivative. In some embodiments, the electron transport material is a polymer material. Specific examples of preferred compounds that can be used as electron transport materials are listed below.

[0098]

[0099] Furthermore, examples of preferred compounds that can be added to each organic layer are given. For example, they can be added as stabilizing materials.

[0100]

[0101] While specific examples of preferred materials that can be used in organic electroluminescent elements have been provided, the materials that can be used in the present invention are not limited to the following exemplary compounds. Furthermore, even compounds exemplified as materials with specific functions can be repurposed as materials with other functions.

[0102] Devices: In some embodiments, the light-emitting layer is incorporated into a device. For example, devices include, but are not limited to, OLED bulbs, OLED lamps, television displays, computer monitors, mobile phones, and tablets. In some embodiments, the electronic device includes an OLED having at least one organic layer comprising an anode, a cathode, and a light-emitting layer between the anode and the cathode. In some embodiments, the components described herein may be incorporated into a variety of photosensitive or photoactivated devices, such as OLEDs or optoelectronic devices. In some embodiments, the components may be useful for facilitating charge transfer or energy transfer within the device and / or as hole transport materials. Examples of such devices include organic light-emitting diodes (OLEDs), organic integrated circuits (OICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field-quench devices (O-FQDs), light-emitting fuel cells (LECs), or organic laser diodes (O-lasers).

[0103] Bulb or Lamp: In some embodiments, the electronic device includes an OLED comprising an anode, a cathode, and at least one organic layer comprising a light-emitting layer between the anode and the cathode. In some embodiments, the device includes OLEDs of different colors. In some embodiments, the device includes an array comprising a combination of OLEDs. In some embodiments, the combination of OLEDs is a combination of three colors (e.g., RGB). In some embodiments, the combination of OLEDs is a combination of colors other than red, green, or blue (e.g., orange and yellow-green). In some embodiments, the combination of OLEDs is a combination of two, four, or more colors. In some embodiments, the device is an OLED light comprising: a circuit board having a first surface with a mounting surface and a second surface opposite thereto, defining at least one opening; at least one OLED on the mounting surface having a light-emitting configuration comprising an anode, a cathode, and at least one organic layer including a light-emitting layer between the anode and the cathode; a housing for the circuit board; and at least one connector located at the end of the housing, wherein the housing and the connector define a package suitable for mounting to a lighting fixture. In some embodiments, the OLED light has a plurality of OLEDs mounted on the circuit board such that light is emitted in a plurality of directions. In some embodiments, some of the light emitted in the first direction is polarized and emitted in a second direction. In some embodiments, a reflector is used to polarize the light emitted in the first direction.

[0104] Displays or Screens: In some embodiments, the light-emitting layer of the present invention can be used in screens or displays. In some embodiments, the compounds according to the present invention are deposited onto a substrate using processes such as vacuum evaporation, deposition, vapor deposition, or chemical vapor deposition (CVD), but are not limited. In some embodiments, the substrate is a photoplate structure useful in two-sided etching, providing pixels with unique aspect ratios. The screen (also called a mask) is used in the manufacturing process of an OLED display. The design of the corresponding artwork pattern allows for the arrangement of very steep, narrow tie bars between pixels in the vertical direction, and large, wide oblique apertures in the horizontal direction. This enables the fine pattern configuration of pixels required for high-resolution displays while optimizing chemical vapor deposition onto the TFT backplane. Internal patterning of the pixels allows for the configuration of three-dimensional pixel apertures with various aspect ratios in the horizontal and vertical directions. Furthermore, the use of imaged "stripes" or halftone circles within a pixel area protects etching in a particular area until these specific patterns are undercut and removed from the substrate. At that time, all pixel areas are processed at a similar etching rate, but the depth varies depending on the halftone pattern. By changing the size and spacing of the halftone pattern, etching with varying degrees of protection within the pixels becomes possible, enabling localized, deep etching necessary to form steep vertical bevels. A preferred material for the deposition mask is Invar. Invar is a metal alloy that is cold-rolled into long, thin sheets at a steel mill. Invar cannot be electrodeposited onto a spin mandrel as a nickel mask. A suitable and low-cost method for forming aperture regions within the deposition mask is by wet chemical etching. In some embodiments, the screen or display pattern is a pixel matrix on a substrate. In some embodiments, the screen or display pattern is fabricated using lithography (e.g., photolithography and e-beam lithography).In some embodiments, the screen or display pattern is processed using wet chemical etching. In further embodiments, the screen or display pattern is processed using plasma etching.

[0105] Device manufacturing method: OLED displays are generally manufactured by forming a large mother panel and then cutting the mother panel into cell panels. Typically, each cell panel on the mother panel is formed by forming a thin-film transistor (TFT) having an active layer and source / drain electrodes on a base substrate, coating the TFT with a planarization film, sequentially forming pixel electrodes, an emissive layer, a counter electrode, and an encapsulation layer over time, and then cutting it from the mother panel.

[0106] In another aspect of the present invention, a method for manufacturing an organic light-emitting diode (OLED) display is provided, the method comprising the steps of: forming a barrier layer on a base substrate of a mother panel; forming a plurality of display units in cell panel units on the barrier layer; forming an encapsulation layer on each of the display units of the cell panel; and coating an organic film on the interface portions between the cell panels. In some embodiments, the barrier layer is an inorganic film formed of, for example, SiNx, and the edges of the barrier layer are covered with an organic film formed of polyimide or acrylic. In some embodiments, the organic film assists in the soft cutting of the mother panel in cell panel units. In some embodiments, the thin-film transistor (TFT) layer has a light-emitting layer, a gate electrode, and source / drain electrodes. Each of the plurality of display units may have a thin-film transistor (TFT) layer, a planarization film formed on the TFT layer, and a light-emitting unit formed on the planarization film, wherein the organic film coated on the interface portions is formed of the same material as the planarization film and is formed simultaneously with the formation of the planarization film. In some embodiments, the light-emitting unit is connected to the TFT layer by a passivation layer, a planarization film between them, and an encapsulation layer that covers and protects the light-emitting unit. In some embodiments of the manufacturing method, the organic film is not connected to the display unit or the encapsulation layer.

[0107] Each of the organic film and the planarization film may contain either polyimide or acrylic. In some embodiments, the barrier layer may be an inorganic film. In some embodiments, the base substrate may be formed of polyimide. The method may further include the steps of attaching a carrier substrate made of glass material to another surface of the base substrate before forming a barrier layer on one surface of the base substrate made of polyimide, and separating the carrier substrate from the base substrate before cutting along the interface. In some embodiments, the OLED display is a flexible display. In some embodiments, the passivation layer is an organic film placed on the TFT layer for coating the TFT layer. In some embodiments, the planarization film is an organic film formed on the passivation layer. In some embodiments, the planarization film, as well as the organic film formed at the edges of the barrier layer, is made of polyimide or acrylic. In some embodiments, the planarization film and the organic film are formed simultaneously during the manufacture of the OLED display. In some embodiments, the organic film may be formed at the edge of the barrier layer, so that a portion of the organic film is in direct contact with the base substrate, and the remaining portion of the organic film is in contact with the barrier layer while surrounding the edge of the barrier layer.

[0108] In some embodiments, the light-emitting layer includes a pixel electrode, a counter electrode, and an organic light-emitting layer disposed between the pixel electrode and the counter electrode. In some embodiments, the pixel electrode is connected to the source / drain electrodes of the TFT layer. In some embodiments, when a voltage is applied to the pixel electrode through the TFT layer, an appropriate voltage is formed between the pixel electrode and the counter electrode, causing the organic light-emitting layer to emit light, thereby forming an image. Hereinafter, an image forming unit having a TFT layer and a light-emitting unit will be referred to as a display unit. In some embodiments, the encapsulation layer covering the display unit and preventing the penetration of external moisture may be formed as a thin-film encapsulation structure in which organic films and inorganic films are alternately laminated. In some embodiments, the encapsulation layer has a thin-film encapsulation structure in which a plurality of thin films are laminated. In some embodiments, the organic film applied to the interface portion is spaced apart from each of the plurality of display units. In some embodiments, the organic film is formed such that a portion of the organic film is in direct contact with the base substrate, while the remaining portion of the organic film surrounds the edge of the barrier layer while in contact with the barrier layer.

[0109] In one embodiment, the OLED display is flexible and uses a flexible base substrate made of polyimide. In some embodiments, the base substrate is formed on a carrier substrate made of glass material, which is then separated. In some embodiments, a barrier layer is formed on the surface of the base substrate opposite the carrier substrate. In one embodiment, the barrier layer is patterned according to the size of each cell panel. For example, the base substrate is formed on all surfaces of the mother panel, while the barrier layer is formed according to the size of each cell panel, thereby creating grooves in the interface portions between the barrier layers of the cell panels. Each cell panel can be cut along the grooves.

[0110] In some embodiments, the manufacturing method further includes a step of cutting along the interface portion, where a groove is formed in the barrier layer, and at least a portion of the organic film is formed in the groove, and the groove does not penetrate the base substrate. In some embodiments, a TFT layer is formed for each cell panel, and a passivation layer, which is an inorganic film, and a planarization film, which is an organic film, are placed on the TFT layer and cover the TFT layer. For example, while a planarization film made of polyimide or acrylic is formed, the groove in the interface portion is covered with an organic film made of polyimide or acrylic, for example. This prevents cracking by allowing the organic film to absorb the impact generated when each cell panel is cut along the groove at the interface portion. That is, if all barrier layers are completely exposed without an organic film, when each cell panel is cut along the groove at the interface portion, the impact generated is transmitted to the barrier layer, thereby increasing the risk of cracking. However, in one embodiment, the groove in the interface portion between barrier layers may be covered with an organic film to absorb the impact that would otherwise be transmitted to the barrier layer, so that each cell panel is cut softly and cracking in the barrier layer is prevented. In one embodiment, the organic film and the planarizing film covering the grooves of the interface portion are arranged with a gap between them. For example, if the organic film and the planarizing film are connected to each other as a single layer, there is a risk that external moisture may penetrate the display unit through the remaining parts of the planarizing film and organic film. Therefore, the organic film and the planarizing film are arranged with a gap between them so that the organic film is spaced away from the display unit.

[0111] In some embodiments, the display unit is formed by forming a light-emitting unit, and an encapsulation layer is placed on the display unit to cover it. This separates the carrier substrate supporting the base substrate from the base substrate after the mother panel is completely manufactured. In some embodiments, when a laser beam is radiated onto the carrier substrate, the carrier substrate is separated from the base substrate due to the difference in thermal expansion coefficients between the carrier substrate and the base substrate. In some embodiments, the mother panel is cut in cell panel units. In some embodiments, the mother panel is cut along the interface portions between the cell panels using a cutter. In some embodiments, the grooves of the interface portions along which the mother panel is cut are covered with an organic film so that the organic film absorbs shock during cutting. In some embodiments, cracking of the barrier layer can be prevented during cutting. In some embodiments, the method reduces the defect rate of the product and stabilizes its quality. Another embodiment is an OLED display having a barrier layer formed on a base substrate, a display unit formed on the barrier layer, an encapsulation layer formed on the display unit, and an organic film coated on the edges of the barrier layer.

[0112] The features of the present invention will be further described in detail below with reference to synthesis examples and embodiments. The materials, processing content, processing procedures, etc. shown below can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the specific examples shown below. The luminescence characteristics were evaluated using a source meter (Keithley Corporation: 2400 series), a semiconductor parameter analyzer (Agilent Technologies: E5273A), an optical power meter measuring device (Newport Corporation: 1930C), an optical spectrometer (Ocean Optics Corporation: USB2000), a spectroradiometer (Topcon Corporation: SR-3), and a streak camera (Hamamatsu Photonics K.K.: C4334).

[0113] (Synthesis Example 1) Synthesis Intermediate I-1 of Compound 1

[0114] In a 100 mL two-necked round-bottom flask containing a magnetic stirring rod, add 2-bromophenylboronic acid (1.46 g, 7.27 mmol, 2.40 equivalents), 1,4-diiodobenzene (1.00 g, 3.03 mmol, 1.00 equivalent), and Pd (PPh ３ ) ２ Cl ２ (106 mg, 0.15 mmol, 0.05 equivalent), K ２ CO ３ (2.09 g, 15.16 mmol, 5.0 equivalents), 1,2-dimethoxyethane (30 mL), and water (10 mL) were added sequentially. The mixture was stirred in an oil bath at 75°C for 12 hours, and then the reaction was stopped with a saturated aqueous solution. NH ４ The product was purified with Cl and extracted with chloroform / water. The organic layer of chloroform was then dehydrated with sodium sulfate. The crude product was purified by flash chromatography (hexane:dichloromethane = 10:1) to obtain intermediate I-1 (1.18 g, white solid) in 88% yield. 1 H NMR (CDCl3, 495 MHz, rt) δ 7.70-7.68 (d, 2H), 7.48 (s, 4H), 7.41-7.36 (m, 4H), 7.25-7.20 (m, 2H). 13 C{ 1 H} NMR (CDCl3, 125 MHz, rt)δ 142.28, 140.35, 133.33, 131.50, 129.11, 128.89, 127.51, 122.68.

[0115] Intermediate I-2

[0116] In a 100 mL two-necked round-bottom flask containing a magnetic stirring bar, add the following: Intermediate I-1 (2.0 g, 5.15 mmol, 1.00 equivalent), 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (3.78 g, 12.88 mmol, 2.50 equivalent), Pd (PPh ３ ) ４ (595 mg, 0.51 mmol, 0.01 equivalent), K ２ CO ３(4.27 g, 30.92 mmol, 6.0 equivalents), tetrahydrofuran (60 mL), and water (15 mL) were added sequentially. The mixture was stirred in an oil bath at 65°C for 48 hours, followed by stirring at 70°C for 16 hours, after which the reaction was stopped with saturated sodium chloride aqueous solution. NH ４ The product was purified with Cl and extracted with dichloromethane / water. Next, the dichloromethane organic layer was dehydrated with sodium sulfate. The crude product was purified by column chromatography (hexane:dichloromethane = 10:2) to obtain intermediate I-2 (2.30 g, white solid) in 79% yield. 1 H NMR (CDCl3, 495 MHz, rt) δ 8.01-7.99 (d, 2H, J = 7.92 Hz), 7.87 (s, 2H), 7.49-7.37 (m, 16H), 6.94-6.90 (m, 6H), 6.77-6.76 (d, 2H, J = 8.4 Hz). 13 C{ 1 ¹H} NMR (CDCl3, 125 MHz, 50 o C) δ 141.50, 140.68, 139.91, 138.31, 133.42, 130.92, 130.44, 129.40, 128.65, 127.23, 126.95, 125.71, 123.84, 123.08, 120.99, 120.59, 119.48, 110.55, 109.73. HRMS (MALDI): m / z calcd. for C 42 H 29 N2: 560.2247 ([M] +), obsd. 560.2261.

[0117] Compound 1

[0118] In a 50 mL two-necked round-bottom flask containing a magnetic stirring bar, add intermediate I-2 (194 mg, 0.34 mmol, 1.10 equivalents) and CS. ２ CO ３(129 mg, 0.94 mmol, 3.00 equivalents) and dry N,N-dimethylformamide (DMF, 10 mL) were added sequentially. After stirring at room temperature under an argon atmosphere for 30 minutes, intermediate I-3 (300 mg, 0.31 mmol, 1.00 equivalent) in dry DMF (5 mL) was added dropwise. Next, the mixture was stirred in an oil bath at 130°C for 4 hours under the same inert atmosphere, the reaction was quenched with water, the precipitate was filtered and washed with water, and extracted with chloroform. The crude product obtained was purified by column chromatography (hexane:chloroform = 8:3), and precipitated from hot toluene / hexane / methanol to obtain compound 1 (215 mg) as a green powder in 59% yield. 1 H NMR (CDCl3, 495 MHz, rt) δ 7.99-7.98 (d, 2H, J = 7.92 Hz), 7.94-7.84 (m, 6H), 7.81-7.79 (m, 2H), 7.67-7.64 (m, 4H), 7.51-7.49 (d, 1H, J = 7.92 Hz), 7.41-7.29 (m, 14H), 7.24-7.11 (m, 6H), 7.07-7.02 (m, 3H), 6.85-6.77 (m, 6H), 6.60-6.57 (t, 2H), 6.42-6.39 (t, 3H), 6.19-6.15 (t, 1H). HRMS (MALDI): m / z calcd. for C 85 H 51 N6: 1155.4169 ([M] +), obsd. 1155.4196.

[0119] (Synthesis Example 2) Synthesis Intermediate I-4 of Compound 2

[0120] In a 50 mL two-necked round-bottom flask containing a magnetic stirring bar, add intermediate I-2 (824 mg, 1.47 mmol, 1.00 equivalent), CS ２ CO ３(600 mg, 4.41 mmol, 3.00 equivalents) and 20 mL of dry DMF were added sequentially. After stirring at room temperature under an argon atmosphere for 30 minutes, 500 mg, 1.47 mmol, 1.00 equivalent of 4-(9H-carbazole-9-yl)-2,3,5,6-tetrafluorobenzonitrile (10 mL of dry DMF) was added dropwise. Next, the mixture was stirred in an oil bath at 100°C for 16 hours under the same inert atmosphere, and the reaction was quenched with water. The precipitate was filtered, washed with water, and extracted with chloroform. The crude product was purified by column chromatography (hexane:chloroform = 8:3), and precipitated / recrystallized from hot toluene / hexane / methanol to obtain a yellow powdery intermediate I-4 (645 mg) in 51% yield. 1 H NMR (CDCl3, 495 MHz, rt) δ 8.32-8.31 (d, 2H, J = 1.48 Hz), 8.25-8.23 (d, 1H, J = 7.92 Hz), 8.20-8.18 (d, 1H, J = 7.42 Hz), 8.14-8.12 (d, 2H, J = 7.42 Hz), 7.74-7.70 (m, 6H), 7.55-7.45 (m, 10H), 7.41-7.28 (m, 6H), 7.11-7.09 (d, 2H, J = 8.41 Hz), 6.60 (m, 2H), 5.29 (s, 2H). 19 F NMR (495 MHz, CDCl3) δ -116.60 (2F). 13 C{ 1 ¹H} NMR (CDCl3, 125 MHz, 50 oC) δ 141.29, 141.18, 140.68, 140.24, 140.01, 139.69, 139.29, 134.95, 132.53, 130.83, 130.76, 129.73, 129.35, 129.03, 127.91, 127.50, 127.00, 126.85, 126.34, 125.56, 124.86, 124.72, 122.18, 121.97, 121.76, 121.02, 120.83, 110.45, 110.16, 109.68, 109.13. HRMS (MALDI): m / z calcd. for C 61 H 34 F2N4: 860.2746 ([M] +), obsd. 860.2760.

[0121] Compound 2

[0122] In a 50 mL two-necked round-bottom flask equipped with a magnetic stirring bar, carbazole (85 mg, 0.51 mmol, 2.20 equivalents), sodium hydride (60% in mineral oil, 20.5 mg, 0.51 mmol, 2.20 equivalents), and dry DMF (10 mL) were sequentially added at 0°C. After stirring at 0°C for 30 minutes under an argon atmosphere, a solution of intermediate I-4 (200 mg, 0.23 mmol, 1.00 equivalent) in dry DMF (5 mL) was added dropwise. Next, the mixture was stirred at room temperature under the same inert atmosphere for 4 hours, then the reaction was stopped with water, the precipitate was filtered and washed with water, and subsequently extracted with chloroform. The resulting crude product was purified by flash column chromatography (hexane:chloroform = 8:2), and precipitated / recrystallized from hot toluene / hexane / methanol to obtain compound 2 (210 mg) as a greenish-yellow powder in 78% yield. 1H NMR (CDCl3, 495 MHz, rt) δ 8.13-8.12 (d, 2H, J = 1.48 Hz), 7.92-7.90 (d, 2H, J = 7.92 Hz), 7.84-7.82 (d, 1H, J = 8.41 Hz), 7.77-7.76 (d, 2H, J = 7.92 Hz), 7.70 (s, 2H), 7.57-7.52 (m, 6H), 7.42-7.38 (m, 9H), 7.32-7.27 (m, 2H), 7.21-7.07 (m, 14H), 6.97-6.84 (m, 6H), 6.72-6.69 (t, 1H), 6.61-6.58 (t, 1H), 6.42 (s, 2H). HRMS (MALDI): m / z calcd. for C 85 H 51 N6: 1155.4169 ([M] +), obsd. 1155.4145.

[0123] (Synthesis Example 3) Synthesis of Compound 3

[0124] In a 50 mL two-necked round-bottom flask containing a magnetic stirring bar, add intermediate I-2 (133 mg, 0.24 mmol, 1.10 equivalents) and CS. ２ CO ３ (88 mg, 0.65 mmol, 3.0 equivalents) and dry DMF (10 mL) were added sequentially. After stirring at room temperature for 30 minutes under an inert atmosphere, 3,4-difluorobenzonitrile (30 mg, 0.21 mmol, 1.00 equivalent) in DMF was added dropwise. The mixture was stirred in an oil bath at 135°C for 24 hours, then cooled and subsequently quenched with an excess of water. The solid was then filtered, washed with water, and subsequently extracted with an excess of dichloromethane. The solution was then dried over sodium sulfate and subsequently evaporated to dryness. The crude product was then purified by column chromatography (hexane:dichloromethane = 10:1) and subsequently recrystallized with methanol to obtain compound 3 (80 mg) as a white solid in 56% yield. 11H NMR (CDCl3, 495 MHz, rt) δ 8.03 - 8.00 (4H, m), 7.91 - 7.89 (2H, d, J = 7.42 Hz), 7.82 - 7.80 (1H, d, J = 8.41 Hz), 7.52 - 7.50 (4H, m), 7.46 - 7.39 (6H, m), 7.27 - 7.12 (5H, m), 7.15 - 7.12 (2H, t, J = 7.42, 7.42 Hz), 6.96 - 6.94 (2H, m), 6.73 - 6.71 (2H, m), 6.28 (2H, s). 13 C{ 1 H} NMR (CDCl3, 125 MHz, 50 o C) δ 142.01, 141.32, 141.25, 141.03, 140.98, 139.84, 139.77, 139.40, 138.56, 137.09, 135.58, 134.56, 133.69, 132.82, 130.37, 130.25, 130.21, 130.14, 130.10, 128.83, 128.66, 127.33, 127.29, 125.86, 123.77, 123.38, 120.78, 120.55, 120.34, 116.97, 114.54, 109.65, 109.58, 109.26, 109.18. HRMS (MALDI).m / z calcd. for C 49 H 29 N3: 659.2356 ([M] +), obsd. 659.2373.

[0125] (Synthesis Example 4) Synthesis of Compound 4

[0126] A 50 mL two-neck round-bottom flask equipped with a magnetic stir bar was charged with Intermediate I-2 (403 mg, 0.72 mmol, 1.00 equivalent), CS ２ CO ３(293 mg, 2.16 mmol, 3.0 equivalents) and 10 mL of dry DMF were added sequentially. After stirring at room temperature for 30 minutes under an inert atmosphere, a solution of 3,5-difluorobenzonitrile (100 mg, 0.72 mmol, 1.00 equivalent) in 4 mL of DMF was added dropwise. The mixture was stirred in an oil bath at 140°C for 8 hours, then cooled and quenched with an excess of water. Next, the solid was filtered, washed with water, and extracted with an excess of dichloromethane solvent. Next, the solution was dried over sodium sulfate and evaporated to dryness. The crude product was then purified by column chromatography (hexane:dichloromethane = 10:1) and subsequently recrystallized with methanol to obtain compound 4 (305 mg) as a white solid in 64% yield. 1 H NMR (CDCl3, 495 MHz, rt) δ 8.30 (2H, s), 8.09-8.05 (4H, dd, J = 7.42, 2.0 Hz), 7.75-7.74 (2H, d, J = 7.42 Hz), 7.63 (1H, s), 7.52-7.49 (4H, m), 7.46-7.40 (6H, m), 7.32-7.27 (7H, m), 7.22-7.20 (3H, m). HRMS (MALDI): m / z calcd. for C 49 H 29 N3: 659.2356 ([M] +), obsd. 659.2313.

[0127] (Synthesis Example 5) Synthesis of Compound 5

[0128] In a 50 mL two-necked round-bottom flask containing a magnetic stirring bar, add intermediate I-2 (403 mg, 0.72 mmol, 1.00 equivalent), CS ２ CO ３(293 mg, 2.16 mmol, 3.0 equivalents) and 10 mL of dry DMF were added sequentially. After stirring at room temperature for 30 minutes under an inert atmosphere, 100 mg (80.26 mL), 0.72 mmol, 1.00 equivalent of 2,6-difluorobenzonitrile (4 mL of DMF) was added dropwise. The mixture was stirred in an oil bath at 140°C for 8 hours, then cooled and subsequently quenched with an excess of water. The solid was then filtered, washed with water, and subsequently extracted with an excess of dichloromethane. The solution was then dried over sodium sulfate and evaporated to dryness. The crude product was then purified by column chromatography (hexane:dichloromethane = 10:1) and subsequently recrystallized with methanol to obtain compound 5 (310 mg) as a white solid in 65% yield. 1 H NMR (CDCl3, 495 MHz, rt) δ 8.29 (2H, s), 8.16-8.11 (3H, m), 8.01-7.99 (2H, d, J = 7.92 Hz), 7.75-7.73 (2H, d, J = 7.92 Hz), 7.67 (2H, s), 7.50-7.46 (2H, m), 7.43-7.38 (5H, m), 7.35-7.29 (3H, m), 7.25-7.22 (5H, m), 6.95-6.93 ((2H, d, J = 8.41 Hz), 6.58 (2H, m). 13 C{ 1 ¹H} NMR (CDCl3, 125 MHz, 50 o C) δ 144.08, 141.78, 141.62, 140.69, 140.25, 139.56, 134.65, 134.07, 132.50, 130.67, 129.44, 129.36, 128.44, 127.78, 127.26, 126.40, 125.46, 125.01, 121.45, 120.84, 109.62, 109.27. HRMS (MALDI): m / z calcd. for C 49 H 29 N3: 659.2356 ([M] +), obsd. 659.2343.

[0129] (Synthesis Example 6) Synthesis of Compound 6

[0130] In a 50 mL two-necked round-bottom flask containing a magnetic stirring bar, add intermediate I-2 (263 mg, 0.47 mmol, 1.10 equivalents) and CS. ２ CO ３ (174 mg, 1.28 mmol, 3.00 equivalents) and 10 mL of dry DMF were added sequentially. After stirring at room temperature under an argon atmosphere for 30 minutes, intermediate I-5 (200 mg, 0.46 mmol, 1.00 equivalent) in 5 mL of dry DMF was added dropwise. Next, the mixture was stirred in an oil bath at 130°C for 4 hours under the same inert atmosphere, the reaction was stopped with water, the precipitate was filtered and washed with excess water. Next, the filtered solid was extracted with dichloromethane, and the mixture was dried over sodium sulfate. The obtained crude product was purified by flash column chromatography (hexane:dichloromethane = 8:2), and precipitated from hot toluene / hexane to obtain compound 6 (320 mg) as a pale yellow powder in 76% yield. 1 H NMR (CDCl3, 495 MHz, rt) δ 8.17 (2H, m), 8.07-8.05 (2H, d, J = 7.92 Hz), 8.00-7.98 (3H, m), 7.87-7.79 (8H, m), 7.69-7.65 (4H, m), 7.52-7.43 (9H, m), 7.37-7.29 (5H, m), 7.05-6.95 (6H, m), 6.81-6.77 (2H, m), 6.62 (2H, s). 13 C{ 1 ¹H} NMR (CDCl3, 125 MHz, 50 oC) δ 140.93, 140.87, 140.29, 140.07, 139.88, 129.36, 139.07, 138.40, 138.32, 137.65, 134.49, 132.21, 131.05, 130.72, 129.79, 129.15, 128.04, 127.43, 126.74, 126.07, 125.94, 125.90, 124.94, 126.65, 124.39, 121.80, 121.35, 121.32, 121.22, 120.44, 120.12, 110.28, 110.19, 110.11, 109.67, 108.84. HRMS (MALDI): m / z calcd. for C 73 H 44 N5: 990.3591 ([M] +), obsd. 990.3598.

[0131] (Synthesis Example 7) Synthesis Intermediate I-6 of Compound 7

[0132] In a 50 mL two-necked round-bottom flask containing a magnetic stirring bar, add intermediate I-2 (640 mg, 1.14 mmol, 1.00 equivalent), CS ２ CO ３ (466 mg, 3.43 mmol, 3.00 equivalent) and 15 mL of dry DMF were added sequentially. After stirring at room temperature under an argon atmosphere for 30 minutes, 2,3,5,6-tetrafluorobenzonitrile (200 mg (162.5 mL), 1.14 mmol, 1.00 equivalent) in 10 mL of dry DMF was added dropwise. Next, the mixture was stirred in an oil bath at 130°C for 4 hours under the same inert atmosphere, the reaction was stopped with water, the precipitate was filtered and washed with excess water. Next, the filtered solid was extracted with dichloromethane, and the mixture was dried over sodium sulfate. Next, the crude product obtained was purified by column chromatography (hexane:dichloromethane = 8:2), and then slowly precipitated / recrystallized from excess hexane with vigorous stirring to obtain a yellow powdery intermediate I-6 (600 mg) in 75% yield. 11H NMR (CDCl3, 495 MHz, rt) δ 8.28 (2H, s), 8.11-8.10 (2H, d, J = 7.42 Hz), 7.79-7.68 (5H, m), 7.53-7.41 (8H, m), 7.34-7.31 (3H, m), 7.25-7.21 (3H, m), 6.93-6.91 (2H, d, J = 8.41 Hz), 6.56 (2H, m). 19 19F NMR (495 MHz, CDCl3) δ -112.81 (2F). 13 13C{ 1 1H} NMR (CDCl3, 125 MHz, 50 o 13C) δ 141.43, 141.28, 140.63, 140.18, 139.36, 134.60, 132.50, 130.75, 129.61, 129.29, 127.86, 127.42, 126.70, 126.11, 125.37, 121.92, 121.65, 120.90, 110.44, 109.01. HRMS (MALDI): m / z calcd. for C 49 1H 28 19F2N3: 696.2245 ([M] +), obsd. 696.2219

[0133] Compound 7

[0134] Carbazole (132 mg, 0.79 mmol, 2.20 equivalents), sodium hydride (60% in mineral oil, 31.6 mg, 0.79 mmol, 2.20 equivalents), and dry DMF (10 mL) were sequentially added at 0°C to a 50 mL two-necked round-bottom flask containing a magnetic stirrer. After stirring at 0°C for 30 minutes under an argon atmosphere, intermediate I-6 (250 mg, 0.36 mmol, 1.00 equivalent) in dry DMF (10 mL) was added dropwise. Next, the mixture was stirred at room temperature under the same inert atmosphere for 4 hours, the reaction was quenched with water, the precipitate was filtered and washed with water. The filtered solid was then extracted with dichloromethane, and the mixture was dried over sodium sulfate. The crude product obtained was purified by flash column chromatography (hexane:chloroform = 8:2), and precipitated and recrystallized from hot toluene / hexane / methanol to obtain compound 7 (310 mg) as a greenish-yellow powder in 87% yield. 1 H NMR (CDCl3, 495 MHz, rt) δ 8.35 (1H, s), 8.21 (2H, m), 8.06-8.03 (4H, t, J = 7.42, 7.92 Hz), 7.88-7.85 (4H, m), 7.78-7.71 (6H, m), 7.58-7.56 (2H, d, J = 8.91 Hz), 7.51-7.41 (10H, m), 7.33-7.31 (2H, d, J = 7.92 Hz), 7.04-7.01 (4H, t, J = 6.93, 7.42 Hz), 6.98-6.90 (6H, m), 6.67 (2H, m). 13 C{ 1 ¹H} NMR (CDCl3, 125 MHz, 50 oC) δ 140.86, 140.74, 140.19, 139.76, 139.70, 139.43, 137.49, 136.11, 134.44, 132.47, 130.81, 130.72, 129.74, 129.53, 127.89, 127.41, 126.76, 126.19, 126.14, 126.09, 125.14, 125.00, 123.96, 121.81, 121.58, 121.47, 121.12, 121.06, 120.52, 120.35, 110.16, 109.03, 108.81. HRMS (MALDI): m / z calcd. for C 73 H 44 N5: 990.3591 ([M] +), obsd. 990.3560.

[0135] (Synthesis Example 8) Synthesis of Compound 8

[0136] In a 50 mL two-necked round-bottom flask containing a magnetic stirring bar, add intermediate I-2 (315 mg, 0.56 mmol, 1.00 equivalent), CS ２ CO ３ (230 mg, 1.69 mmol, 3.00 equivalents) and 10 mL of dry DMF were added sequentially. After stirring at room temperature under an argon atmosphere for 30 minutes, intermediate I-7 (200 mg, 0.56 mmol, 1.00 equivalent) in 10 mL of dry DMF was added dropwise. Next, the mixture was stirred in an oil bath at 140°C for 24 hours under the same inert atmosphere, the reaction was stopped with water, the precipitate was filtered and washed with excess water. Next, the filtered solid was extracted with chloroform, and the mixture was dried over sodium sulfate. The resulting crude product was purified by flash column chromatography (hexane:dichloromethane = 8:2), and precipitated from hot toluene / hexane to obtain compound 8 (179 mg) as a pale yellow powder in 36% yield. 1H NMR (CDCl3, 495 MHz, rt) δ 9.13-9.11 (1H, d, J = 8.41 Hz), 8.33-8.32 (2H, d, J = 5.44 Hz), 8.12-8.04 (3H, m), 7.78-7.77 (2H, d, J = 7.42 Hz), 7.63-7.61 (1H, d, J = 8.41 Hz), 7.52-7.37 (10H, m), 7.32-7.29 (2H, t, J = 7.92, 8.41 Hz), 7.25-7.19 (5H, m), 7.11-7.09 (2H, m), 7.03-7.00 (1H, m), 6.68-6.65 (1H, m). HRMS (MALDI): m / z calcd. for C 63 H 29 D 10 N5: 875.3982 ([M] +), obsd. 875.3947.

[0137] (Synthesis Example 9) Synthesis of Compound 9

[0138] In a 50 mL two-necked round-bottom flask containing a magnetic stirring bar, add intermediate I-2 (256 mg, 0.46 mmol, 1.00 equivalent), CS ２ CO ３ (187 mg, 1.37 mmol, 3.00 equivalents) and 10 mL of dry DMF were added sequentially. After stirring at room temperature under an argon atmosphere for 30 minutes, intermediate I-8 (200 mg, 0.46 mmol, 1.00 equivalent) in 10 mL of dry DMF was added dropwise. Next, the mixture was stirred in an oil bath at 140°C for 12 hours under the same inert atmosphere, the reaction was quenched with water, the precipitate was filtered and washed with excess water. Next, the filtered solid was extracted with chloroform, and the mixture was dried over sodium sulfate. The resulting crude product was purified by flash column chromatography (hexane:dichloromethane = 8:2), and precipitated from hot toluene / hexane to obtain compound 9 (306 mg) in a pale green powder in 70% yield. 1H NMR (CDCl3, 495 MHz, rt) δ 10.01-10.00 (1H, m), 7.94-7.93 (2H, m), 7.72-7.67 (4H, m), 7.61-7.59 (1H, d, J = 7.42 Hz), 7.55-7.54 (1H, d, J = 7.42 Hz), 7.46-7.39 (8H, m), 7.35-7.28 (2H, m), 7.13-7.04 (4H, m), 6.83-6.79 (2H, m), 6.70-6.68 (1H, d, J = 7.92 Hz), 6.64-6.62 (1H, d, J = 7.92 Hz). HRMS (MALDI): m / z calcd. for C 68 H 28 D 15 N6: 958.4717 ([M] +), obsd. 958.4688.

[0139] (Synthesis Example 10) Synthesis of Compound 10

[0140] In a 50 mL two-necked round-bottom flask containing a magnetic stirring bar, add intermediate I-2 (134 mg, 0.24 mmol, 1.10 equivalents) and CS. ２ CO ３ (89 mg, 0.65 mmol, 3.0 equivalents) and dry DMF (10 mL) were added sequentially. After stirring at room temperature for 30 minutes under an inert atmosphere, 2,6-difluoropyridine (25 mg, 0.22 mmol, 1.00 equivalent) was added dropwise. The mixture was stirred in an oil bath at 150°C for 16 hours, then cooled and quenched with an excess of water. Next, the solid was filtered, washed with water, and extracted with an excess of ethyl acetate. Next, the solution was dried over sodium sulfate and evaporated to dryness. An excess of methanol was added to the oily mixture, stirred at room temperature for about 20 minutes, and filtered to obtain compound 10 (100 mg) as a white solid in 72% yield. 1H NMR (CDCl3, 495 MHz, rt) δ 8.27-8.23 (m, 2H), 8.14-8.13 (d, 2H, J = 7.42 Hz), 7.78-7.61 (m, 4H), 7.70-7.65 (dd, 4H, J = 7.42, 7.42 HRMS (MALDI): m / z calcd. for C 47 H 29 N3: 635.2356 ([M] +), obsd. 635.2359.

[0141] (Synthesis Example 11) Synthesis Intermediate I-9 of Compound 11

[0142] In a 50 mL two-necked round-bottom flask containing a magnetic stirring bar, add intermediate I-2 (436 mg, 0.77 mmol, 1.00 equivalent), CS ２ CO ３ (317 mg, 2.33 mmol, 3.00 equivalents) and 20 mL of dry DMF were added sequentially. After stirring at room temperature under an argon atmosphere for 30 minutes, 150 mg, 0.77 mmol, 1.00 equivalent of 2,3,4,5,6-pentafluorobenzonitrile (10 mL of dry DMF) was added dropwise. Next, the mixture was stirred in an oil bath at 80°C for 4 hours under the same inert atmosphere, the reaction was then quenched with water, the precipitate was filtered and washed with water, and subsequently extracted with chloroform and dichloromethane. The resulting crude product was purified by flash column chromatography (hexane:dichloromethane = 8:3), and precipitated / recrystallized from dichloromethane / hexane to obtain intermediate I-9 (405 mg) as a pale greenish-yellow powder in 73% yield. 1H NMR (CDCl3, 495 MHz, rt) δ 8.25 (s, 2H), 8.08 (d, 2H, J = 7.70 Hz), 7.73-7.68 (m, 4H), 7.52-7.43 (m, 9H), 7.36-7.31 (m, 3H), 7.20-7.16 (m, 2H), 6.93 (d, 1H, J = 8.20 Hz), 6.87 (d, 1H, J = 8.5 Hz), 6.53 (s, 2H). 19 F NMR (495 MHz, CDCl3) δ: -111.17 (1F), -129.46 (1F), 136.25 (1F). HRMS (MALDI): m / z calcd. for C 49 H 26 F3N3: 713.3073 ([M] +), obsd. 713.3393.

[0143] Compound 11

[0144] In a 50 mL two-necked round-bottom flask equipped with a magnetic stirring bar, carbazole (225 mg, 1.34 mmol, 3.20 equivalents), sodium hydride (60% in mineral oil, 55.5 mg, 1.39 mmol, 3.30 equivalents), and dry DMF (10 mL) were sequentially added at 0°C. After stirring at 0°C for 30 minutes under an argon atmosphere, intermediate I-9 (300 mg, 0.42 mmol, 1.00 equivalent) in dry DMF (10 mL) was added dropwise. Next, the mixture was stirred at room temperature for 6 hours under the same inert atmosphere, the reaction was quenched with water, the precipitate was filtered and washed with water, and then extracted with chloroform. The resulting crude product was purified by column chromatography (hexane:chloroform = 8:2), and precipitated / recrystallized from hot toluene / hexane / methanol to obtain compound 11 (276 mg) as a yellow powder in 57% yield. 1H NMR (CDCl3, 495 MHz, rt) δ 8.14 (s, 1H), 8.01 (s, 1H), 7.97-7.94 (m, 3H), 7.86-7.83 (m, 1H), 7.76 (t,1H, J = 7.70 Hz), 7.67-7.58 (m, 4H), 7.52-7.39 (m, 12H), 7.36-7.28 (m, 4H), 7.21 (d, 1H, J = 7.70 Hz), 7.13 (dd, 2H, J = 7.90, 7.90 Hz), 7.05-6.76 (m, 12H), 6.71-6.45 (m, 6H), 6.36-6.33 (m, 1H), 6.28 (t, 1H, J = 7.70 Hz). HRMS (MALDI): m / z calcd. for C 85 H 51 N6: 1155.4169 ([M] +), obsd. 1155.4196.

[0145] (Synthesis Example 12) Synthesis intermediate I-10 of compound 12

[0146] In a 50 mL two-necked flask, combine intermediate I-2 (824 mg, 1.47 mmol, 1.00 equivalent) and Cs ２ CO ３ (600 mg, 4.41 mmol, 3.00 equivalents) was added to 20 mL of dry DMF and stirred at room temperature for 30 minutes under an argon atmosphere. 4-(4-cyanophenyl)-2,3,5,6-tetrafluorobenzonitrile (406 mg, 1.47 mmol, 1.00 equivalent) dissolved in 10 mL of DMF was slowly added dropwise. The mixture was heated to 100°C and stirred for 16 hours. Water was added, and the resulting precipitate was filtered. After further washing with water, it was extracted with chloroform. After removing the solvent, the mixture was purified by column chromatography (hexane / chloroform, 1:1) to obtain intermediate I-10 (539 mg) as a yellow solid in 46% yield. MS (MALDI): m / z calcd. for C 56 H 30 F2N4: 796.24 ([M] + ), obsd. 796.41.

[0147] Compound 12

[0148] Under an argon atmosphere, at 0°C, carbazole (85 mg, 0.51 mmol, 2.20 equivalents), sodium hydride (60% in mineral oil, 20.5 mg, 0.51 mmol, 2.20 equivalents), and dry DMF (10 mL) were added sequentially. After stirring at 0°C for 30 minutes, intermediate I-10 (183 mg, 0.23 mmol, 1.00 equivalent) dissolved in dry DMF (5 mL) was slowly added dropwise. The mixture was then stirred at room temperature for 4 hours. Water was added to the reaction, the resulting precipitate was filtered and washed with water, and then extracted with chloroform. The crude product was purified by column chromatography (hexane / chloroform, 1:1) to obtain compound 12 (203 mg) as a yellow powder in 81% yield. MS (MALDI): m / z calcd. for C 80 H 46 N6: 1090.38 ([M] + ), obsd. 1090.26.

[0149] (Synthesis Example 13) Synthesis of Compound 13

[0150] In a 10 mL two-necked round-bottom flask containing a magnetic stirring bar, add intermediate I-2 (34.60 mg, 61.71 μmol, 2.10 equivalents), CS ２ CO ３ (24 mg, 176.33 μmol, 6.00 equivalents), dry DMF (6 mL) was added sequentially. After stirring at room temperature under an argon atmosphere for 45 minutes, 9-(4-cyano-2,3,5,6-tetrafluorophenyl)-9H-carbazole (10 mg, 29.39 μmol, 1.00 equivalent) in dry DMF (1 mL) was added dropwise. Next, the mixture was stirred in an oil bath at 150°C for 24 hours under the same inert atmosphere. The reaction was then stopped with water, the precipitate was filtered and washed with water, and extracted with chloroform. Next, the crude product was purified by column chromatography (hexane:chloroform = 8:3), and precipitated / recrystallized from hot toluene / hexane / methanol to obtain compound 13 (8.5 mg) as a yellow powder in 21% yield. 1H NMR (CDCl3, 495 MHz, rt) δ 8.22 (m, 2H), 8.00-7.94 (m, 3H), 7.85-7.69 (m, 10H), 7.62-7.55 (m, 5H), 7.47-7.28 (m, 22H), 7.13-7.11 (m, 4H), 7.05-7.03 (m, 2H), 6.94-6.92 (d, 2H, J = 8.41 Hz), 6.87 (s, 2H), 6.68-6.65 (m, 4H), 6.52-6.44 (m, 3H), 6.25-6.22 (t, 1H). HRMS (MALDI): m / z calcd. for C 103 H 61 N6: 1381.4952 ([M] +), obsd. 1381.4977.

[0151] (Synthesis Example 14) Synthesis of Compound 14

[0152] In a 50 mL two-necked flask under an argon atmosphere, intermediate I-2 (824 mg, 1.47 mmol, 1.00 equivalent), compound I-11 (877 mg, 1.47 mmol, 1.00 equivalent), and Cs were added. ２ CO ３ (600 mg, 4.41 mmol, 3.00 equivalents) and 10 mL of DMF were added. The mixed solution was heated to 100°C and stirred for 16 hours. Water was added, and the resulting precipitate was filtered. After further washing with water, it was extracted with chloroform. After removing the solvent, the solution was purified by column chromatography (hexane / chloroform, 1:3) to obtain compound 14 (722 mg) as a yellow solid in 44% yield. MS (MALDI): m / z calcd. for C 78 H 28 D 20 N8: 1116.53 ([M] + ), obsd. 1116.73.

[0153] (Example 1) Fabrication and evaluation of a thin film on a quartz substrate by vacuum deposition at a vacuum level of 1 × 10 －３ Compound 1 was deposited under conditions of less than Pa, forming a neat thin film consisting solely of compound 1 with a thickness of 100 nm. Separately, a vacuum deposition method was used on a quartz substrate to create a film with a vacuum of 1 × 10⁻⁶. －３Compound 1 and H1 were deposited from different deposition sources under conditions below Pa, forming a 100 nm thick doped thin film with a compound 1 concentration of 30 wt%. Neat and doped thin films were similarly formed using compounds 2-5, 9 and comparative compounds 1 and 2 instead of compound 1. When forming the doped thin film of comparative compound 1, H2 was used instead of H1. No significant difference was observed in the following measurement results whether H1 or H2 was used. The HOMO and LUMO energies were measured using each formed neat thin film. Delayed fluorescence was observed when each formed doped thin film was irradiated with 300 nm excitation light, so the emission peak wavelength and delayed fluorescence lifetime (τ2) were measured. The measurement results are summarized in the table below. It was confirmed that compounds represented by general formula (1) have short delayed fluorescence lifetimes and do not easily accumulate triplet excitons.

[0154]

[0155] (Example 2) Fabrication and evaluation of organic electroluminescent elements A glass substrate on which an anode made of indium tin oxide (ITO) with a film thickness of 100 nm was formed was used to deposit each thin film by vacuum deposition at a vacuum of 1 × 10⁻⁶ －６The layers were stacked using Pa. First, HATCN was formed to a thickness of 10 nm on ITO, and then NPD was formed to a thickness of 30 nm on top of it. Next, TrisPCz was formed to a thickness of 10 nm on top of that, and then PTCz was formed to a thickness of 5 nm on top of that. Then, H1 and compound 1 were co-deposited from different deposition sources to form a 40 nm thick light-emitting layer. At this time, the concentration of compound 1 was 30 wt%. On top of that, SF3TRZ was formed to a thickness of 10 nm, and then SF3TRZ and Liq were co-deposited from different deposition sources to form a 30 nm thick layer. At this time, the SF3TRZ:Liq (weight ratio) was 7:3. Furthermore, Liq was formed to a thickness of 2 nm, and then aluminum (Al) was deposited to a thickness of 100 nm to form the cathode. An organic electroluminescent device was fabricated by the above procedure. Organic electroluminescent elements were fabricated in the same manner using compound 2 and comparative compound 1 instead of compound 1. When forming the elements of comparative compound 1, H2 was used instead of H1. When each fabricated organic electroluminescent element was energized, delayed fluorescence was observed. The amount of light emitted from the elements was greatest from compound 1, compound 2, and comparative compound 1. The time (LT95) until the light emission intensity reached 95% of the initial level when each element was energized at 1000 nits was measured. The results are shown in the table below. LT95 is shown as a relative value with comparative compound 1 as the reference (i.e., "1"). It was confirmed that the compound represented by general formula (1) has a long element lifetime.

[0156]

[0157] In the manufacturing process of the organic electroluminescent element described above, an organic electroluminescent element was fabricated in the same manner using compound 7 instead of compound 1. When the fabricated organic electroluminescent element was energized, delayed fluorescence was observed. The amount of light emitted from the element was greatest from compound 7. The external quantum efficiency (EQE) was measured when the element using compound 7 and the element using the comparative compound 1 fabricated above were emitted at 1000 nits, and the time (LT80) until the emission intensity became 80% of the initial emission intensity was also measured. The results are shown in the table below. LT80 is shown as a relative value with comparative compound 1 as the reference (i.e., "1"). It was confirmed that the compound represented by general formula (1) has high luminescence efficiency and a long element lifetime.

[0158]

[0159] In the above-described process for manufacturing organic electroluminescent elements, organic electroluminescent elements were fabricated in the same manner using compound 12 and comparative compound 3 instead of compound 1. When each fabricated organic electroluminescent element was energized, delayed fluorescence was observed. The amount of light emitted from the elements was greatest from compound 12 and comparative compound 3. When the external quantum efficiency (EQE) of each element was measured at 1000 nits, it was confirmed that the element using compound 12 had a 1.3% higher EQE than the element using comparative compound 3.

[0160]

[0161] These results indicate that forming a ring structure with Ter according to general formula (1) extends the device lifetime and improves the luminous efficiency.

[0162] (Example 3) Fabrication and Evaluation of Organic Electroluminescent Element An organic electroluminescent element was fabricated using the same procedure as in Example 2, except that the light-emitting layer in Example 3 was formed by co-depositing H1, compound 1, and ET1 from different deposition sources to create a 30 nm thick light-emitting layer. In the light-emitting layer of Example 3, the concentration of H1 was 69.5% by weight, the concentration of compound 1 was 30% by weight, and the concentration of ET1 was 0.5% by weight. Organic electroluminescent elements were fabricated in the same manner using compound 2 and comparative compound 1 instead of compound 1. When each fabricated organic electroluminescent element was energized, delayed fluorescence was observed. The light emission from the elements was greatest from compound 1, compound 2, and comparative compound 1. The time (LT50) until the light emission intensity became 50% of the initial level when each element was energized at 1000 nits was measured. The results are shown in the table below. LT50 is shown as a relative value with comparative compound 1 as the reference (i.e., "1"). Compounds represented by general formula (1) were found to have a long device lifespan.

[0163]

[0164] By using the compound represented by general formula (1), an organic electroluminescent element with excellent properties can be provided. Therefore, the present invention has high industrial applicability.

Claims

1. A compound represented by the following general formula (1). General formula (1) [In general formula (1), Ar represents an arylene group which is substituted with at least one acceptor group and which may also be substituted with substituents other than acceptor groups or with a deuterium atom, or a heteroarylene group which may also be substituted with a deuterium atom or substituent. D １ and D ２ Each of these independently represents a donor group. Ar is D １ When the atom to which it is bonded is designated as the α position, then D is present at the β or γ position of the atom. ２ It bonds with [ ]. Ter represents a terphenyldiyl group which may be substituted with a deuterium atom or a substituent.

2. The compound according to claim 1, wherein the central phenylene group constituting the terphenyldiyl group is a 1,4-phenylene group which may be substituted with a deuterium atom or a substituent.

3. The compound according to claim 2, wherein the phenylene groups at both ends constituting the terphenyldiyl group are 1,2-phenylene groups, each independently substituted with a deuterium atom or a substituent.

4. The compound according to claim 1, wherein the central phenylene group constituting the terphenyldiyl group is a 1,2-phenylene group which may be substituted with a deuterium atom or a substituent.

5. The compound according to claim 4, wherein the phenylene groups at both ends constituting the terphenyldiyl group are 1,4-phenylene groups, each independently substituted with a deuterium atom or a substituent.

6. A phenylene group in which Ar is substituted with at least one acceptor group and may also be substituted with substituents other than acceptor groups or deuterium atoms; a naphthalene diyl group in which Ar is substituted with at least one acceptor group and may also be substituted with substituents other than acceptor groups or deuterium atoms; a pyridinediyl group which may be fused and may be substituted with deuterium atoms or substituents; a pyrimidinediyl group which may be fused and may be substituted with deuterium atoms or substituents; a pyridazinediyl group which may be fused and may be substituted with deuterium atoms or substituents. The compound according to claim 1, wherein the compound is a pyrazinediyl group which may be fused and substituted with a deuterium atom or a substituent, a triazinediyl group which may be substituted with a deuterium atom or a substituent, a carbazolediyl group which may be fused and substituted with a deuterium atom or a substituent, a dibenzofranziyl group which may be fused and substituted with a deuterium atom or a substituent, a dibenzothiophendiyl group which may be fused and substituted with a deuterium atom or a substituent, or a dibenzoselediyl group which may be fused and substituted with a deuterium atom or a substituent.

7. The compound according to claim 1, wherein Ar is an arylene group substituted with a condensed aromatic heterocyclic group which may be substituted with a deuterium atom or a substituent and at least one acceptor group, or a heteroarylene group substituted with a condensed aromatic heterocyclic group which may be substituted with a deuterium atom or a substituent.

8. The compound according to claim 1, wherein Ar is an arylene group substituted with at least one acceptor group and which may be substituted with a deuterium atom or an aryl group substituted with a substituent, or a heteroarylene group substituted with a deuterium atom or an aryl group substituted with a substituent.

9. Ar is D １ When the atom to which it is bonded is designated as the α position, the atom at the γ position is D ２ The compound according to claim 1, which binds with [the specified compound].

10. Ar is D １ When the atom to which it is bonded is designated as the α position, the atom at the β position is D ２ The compound according to claim 1, which binds with [the specified compound].

11. The compound according to claim 1, wherein Ar is an arylene group substituted with one or more atoms selected from the group consisting of a cyano group, a silyl group, a halogen atom, a pyridyl group which may be substituted with a deuterium atom or a substituent, a pyrimidyl group which may be substituted with a deuterium atom or a substituent, a pyridazyl group which may be substituted with a deuterium atom or a substituent, a triazyl group which may be substituted with a deuterium atom or a substituent, and an aryl group which is substituted with any of these atoms or groups.

12. D １ and D ２ The compound according to claim 1, wherein each of D and D is an optionally spirocyclized 9H-carbazolediyl group which may be substituted with a deuterium atom or a substituent.

13. D １ and D ２ The compound according to claim 12, wherein Ar is bonded at the 9th position of carbazole.

14. D １ and D ２ The compound according to claim 12, wherein Ter is bound at the 3-position of carbazole.

15. D １ and D ２ The compound according to claim 12, wherein Ter is bound at the 2-position of carbazole.

16. The compound according to claim 1, having at least one deuterium atom.

17. An organic electroluminescent element having a pair of electrodes consisting of an anode and a cathode, and an organic layer disposed between the pair of electrodes, wherein the organic layer contains the compound described in any one of claims 1 to 16.

18. The organic electroluminescent element according to claim 17, wherein the organic layer is a light-emitting layer.

19. A display device or lighting device comprising an organic electroluminescent element as described in claim 17.

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