CN117940431A

CN117940431A - Compound, light-emitting material, and light-emitting element

Info

Publication number: CN117940431A
Application number: CN202280062390.8A
Authority: CN
Inventors: 赛达力木·伊吾热衣木江; U·巴里加帕里; 比嘉琢哉; 绵引裕太; 铃木善丈; 山下正贵
Original assignee: Kyushu University NUC
Current assignee: Kyushu University NUC
Priority date: 2021-09-16
Filing date: 2022-09-13
Publication date: 2024-04-26
Also published as: KR20240068056A; WO2023042814A1; JPWO2023042814A1

Abstract

The compound represented by the following general formula is useful as a light-emitting material. R ¹～R¹⁰ represents a hydrogen atom, a deuterium atom or a substituent, but 1 or2 of R ¹～R¹⁰ represent a cyano group, and 1 to 4 of R ¹～R¹⁰ represent a donor group bonded in a 5-membered ring.

Description

Compound, light-emitting material, and light-emitting element

Technical Field

The present invention relates to a compound useful as a light-emitting material and a light-emitting element using the same.

Background

Research is actively being conducted to improve the light emission efficiency of light emitting elements such as organic electroluminescent elements (organic EL elements). In particular, there has been much effort in improving the luminous efficiency by newly developing and combining an electron transporting material, a hole transporting material, a light emitting material, and the like constituting an organic electroluminescent element. Among them, studies on organic electroluminescent devices using delayed fluorescent materials have also been made.

The delayed fluorescent material is a material that emits fluorescence when returning from an excited triplet state to a ground state after an intersystem crossing from the excited triplet state to the excited singlet state occurs in the excited state. Fluorescence generated by this approach is observed later than fluorescence from an excited singlet state (normal fluorescence) generated directly from the ground state, and is therefore referred to as delayed fluorescence. Here, for example, in the case where a luminescent compound is excited by injection of a carrier, the probability of occurrence of an excited singlet state and an excited triplet state is 25% to 75% in total, and therefore, there is a limit in improving the luminous efficiency by fluorescence from only the excited singlet state that is directly generated. On the other hand, in the delayed fluorescent material, in addition to the excited singlet state, the excited triplet state can be used for fluorescence emission by passing through the above-described pathway of intersystem crossing, and therefore, a high emission efficiency can be obtained compared with a usual fluorescent material.

After this principle is clarified, various delayed fluorescent materials have been found through various studies. However, it is not just a material that emits delayed fluorescence but is immediately useful as a light-emitting material. Among the delayed fluorescent materials, there are many problems in terms of practicality because durability is poor when an organic light emitting element is manufactured. In addition, the driving voltage is high or the light emission efficiency is low in the case of manufacturing an organic electroluminescent element. Therefore, in practice, there are many delayed fluorescent materials which have room for improvement in terms of practical use. Further, there is also pointed out that there is a problem in phthalonitrile compounds known as delayed fluorescent materials. For example, 2CzPN having the following structure is a material that emits delayed fluorescence, but has problems such as low light emission efficiency and low durability (refer to non-patent document 1).

[ Chemical formula 1]

Technical literature of the prior art

Non-patent literature

Non-patent document 1: organic Electronics 14 (2013) 2721-2726

Disclosure of Invention

Technical problem to be solved by the invention

Although such problems are pointed out, it is difficult to sufficiently clarify the relationship between the chemical structure and the characteristics of the delayed fluorescent material. Therefore, it is difficult to widen the chemical structure of a compound useful as a light-emitting material in the present situation, and there are many points of uncertainty.

Under such circumstances, the present inventors have conducted studies with a view to providing a compound more useful as a light-emitting material for a light-emitting element. Further, intensive studies have been made with a view to deriving general formulae of compounds more useful as light-emitting materials and making them broader.

Means for solving the technical problems

As a result of intensive studies to achieve the above object, the present inventors have found that a compound having a structure satisfying specific conditions among cyanophenanthrene derivatives is useful as a light-emitting material. The present invention has been made in view of such an observation, and specifically has the following structure.

[1] A compound represented by the following general formula (1).

[ Chemical formula 2]

[ In the general formula (1), R ¹～R¹⁰ each independently represents a hydrogen atom, a deuterium atom or a substituent. Wherein 1 or 2 of R ¹～R¹⁰ represent cyano groups, and 1 to 4 of R ¹～R¹⁰ represent donor groups bonded in a 5-membered ring.

R ¹ and R ²、R² and R ³、R³ and R ⁴、R⁴ and R ⁵、R⁵ and R ⁶、R⁶ and R ⁷、R⁷ and R ⁸、R⁸ and R ⁹、R⁹ and R ¹⁰、R¹⁰ and R ¹ may be bonded to each other to form a cyclic structure. ]

[2] The compound according to [1], wherein the donor group bonded with a 5-membered ring is a substituted or unsubstituted ring-condensed indol-1-yl group.

[3] The compound according to [1], wherein the donor group bonded with a 5-membered ring is a substituted or unsubstituted ring-fused carbazole-9-yl.

[4] The compound according to [1], wherein the donor group bonded with a 5-membered ring is a ring-fused carbazole-9-yl substituted with a substituent.

[5] The compound according to [1], wherein the donor group bonded with a 5-membered ring is a ring-fused carbazole-9-yl substituted with an aryl group or a heteroaryl group.

[6] The compound according to [1], wherein the donor group bonded with a 5-membered ring is a ring-fused carbazole-9-yl substituted with an aryl group.

[7] The compound according to any one of [3] to [6], wherein the ring-fused carbazole-9-yl is a carbazole-9-yl group obtained by fusing a ring having 1 or more atoms selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom as ring skeleton constituent atoms.

[8] The compound according to any one of [3] to [6], wherein the ring-fused carbazole-9-yl is a carbazole-9-yl obtained by fusing a ring having 1 or more atoms selected from the group consisting of an oxygen atom and a sulfur atom as ring skeleton constituent atoms.

[9] The compound according to any one of [3] to [8], wherein 2 of R ¹～R¹⁰ are cyano groups and 2 of R ¹～R¹⁰ are substituted or unsubstituted cyclofused carbazol-9-yl groups.

[10] The compound according to any one of [3] to [9], wherein 2 of R ¹～R¹⁰ are the same substituted or unsubstituted ring-fused carbazol-9-yl.

[11] The compound according to any one of [3] to [10], wherein 2 of R ¹～R¹⁰ are cyano groups and 1 of R ¹～R¹⁰ is a substituted or unsubstituted cyclofused carbazol-9-yl group.

[12] The compound according to any one of [1] to [11], wherein R ⁹ and R ¹⁰ are cyano.

[13] The compound according to any one of [1] to [11], wherein R ² and R ⁷ are cyano.

[14] The compound according to any one of [1] to [13], which has a line-symmetrical structure.

[15] A light-emitting material composed of the compound according to any one of [1] to [14 ].

[16] A delayed phosphor composed of the compound according to any one of [1] to [14 ].

[17] A film comprising the compound of any one of [1] to [14 ].

[18] An organic semiconductor element comprising the compound of any one of [1] to [14 ].

[19] An organic light-emitting element comprising the compound of any one of [1] to [14 ].

[20] The organic light-emitting element according to [19], wherein,

The element has a layer comprising the compound, the layer further comprising a host material.

[21] The organic light-emitting element according to [20], wherein,

In addition to the compound and the host material, the layer comprising the compound also comprises a delayed fluorescent material having a lowest excited singlet energy below the host material and above the compound.

[22] The organic light-emitting element according to [20], wherein,

The element has a layer containing the compound, the layer further containing a light-emitting material having a structure different from that of the compound.

[23] The organic light-emitting element according to any one of [20] to [22], wherein an amount of light emitted from the compound is largest among materials contained in the element.

[24] The organic light-emitting element according to [22], wherein,

The amount of light emitted from the luminescent material is greater than the amount of light emitted from the compound.

[25] The organic light-emitting element according to any one of [19] to [24], which is an organic electroluminescent element.

[26] The organic light-emitting element according to any one of [19] to [24], which emits delayed fluorescence.

Effects of the invention

The compound of the present invention is useful as a light-emitting material. Further, the compound of the present invention includes a compound that emits delayed fluorescence. The organic light-emitting element using the compound of the present invention includes an element having high light-emitting efficiency, an element having high durability, and an element having low driving voltage.

Drawings

Fig. 1 is a schematic cross-sectional view showing an example of a layer structure of an organic electroluminescent element.

Detailed Description

The following describes the present invention in detail. The following description of the constituent elements may be based on the representative embodiments or specific examples of the present invention, but the present invention is not limited to such embodiments or specific examples. In the present specification, the numerical range indicated by "to" means a range including the numerical values described before and after "to" as the lower limit value and the upper limit value. In addition, part or all of hydrogen atoms present in the molecule of the compound used in the present invention may be replaced with deuterium atoms (² H, deuterium D). In the chemical structural formula in the present specification, a hydrogen atom is represented by H or a representation thereof is omitted. For example, when an atom bonded to a carbon atom constituting a ring skeleton of a benzene ring is omitted, it is assumed that the atom is bonded to the carbon atom constituting the ring skeleton at a position H indicated by the omitted atom. In the chemical structural formula in the present specification, deuterium atoms are denoted as D.

[ Compound represented by the general formula (1) ]

[ Chemical formula 3]

General formula (1)

In the general formula (1), R ¹～R¹⁰ each independently represents a hydrogen atom, a deuterium atom, or a substituent.

1 Or 2 of R ¹～R¹⁰ represent cyano.

In one embodiment of the present invention, the number of cyano groups is 1. For example, only R ¹ is cyano. For example, only R ² is cyano. For example, only R ³ is cyano. For example, only R ⁴ is cyano. For example, only R ⁹ is cyano.

In one embodiment of the present invention, the number of cyano groups is 2. For example, 1 of R ¹～R⁴ and R ¹⁰ is cyano, and 1 of R ⁵～R⁹ is cyano. For example, 1 of R ¹、R² and R ¹⁰ is cyano, and 1 of R ⁷～R⁹ is cyano. For example, 1 of R ² and R ¹⁰ is cyano, and 1 of R ⁷ and R ⁹ is cyano. For example, 1 of R ¹～R⁴ is cyano and 1 of R ⁵～R⁸ is cyano. For example, 1 of R ¹～R³ is cyano and 1 of R ⁶～R⁸ is cyano. For example, group 1 of R1 and R ⁸、R² and R ⁷、R³ and R ⁶、R⁹ and R ¹⁰ are cyano groups. In a preferred embodiment of the present invention, R ⁹ and R ¹⁰ are cyano. In a preferred embodiment of the present invention, R ² and R ⁷ are cyano. In one embodiment of the invention, R ¹ and R ⁸ are cyano. In one embodiment of the invention, R ³ and R ⁶ are cyano.

In the general formula (1), 1 to 4 of R ¹～R¹⁰ represent donor groups bonded in a 5-membered ring.

Preferably 1 to 3 of R ¹～R¹⁰ are donor groups bonded in a5 membered ring, more preferably 1 or 2 of R ¹～R¹⁰ are donor groups bonded in a5 membered ring.

In one embodiment of the invention, only 1 of R ¹～R¹⁰ is a donor group bonded in a 5-membered ring. In one embodiment of the present invention, only 1 of R1 to R ⁴ and R ⁵～R⁸ is a donor group bonded in a 5-membered ring. For example, only R ¹ or R ⁸ is a donor group bonded in a5 membered ring. For example, only R ² or R ⁷ is a donor group bonded in a5 membered ring. For example, only R ³ or R ⁶ is a donor group bonded in a5 membered ring. For example, only R ⁴ or R ⁵ is a donor group bonded in a5 membered ring. In one embodiment of the invention, only R ⁹ or R ¹⁰ is a donor group bonded in a 5-membered ring. For example, only R ⁴ or R ⁵ is a donor group bonded in a5 membered ring. In one embodiment of the invention, R ⁹ and R ¹⁰ are cyano groups and only 1 of R ¹～R⁴ is a donor group bonded in a5 membered ring. In one embodiment of the invention, R ⁹ and R ¹⁰ are cyano groups and R ¹ is only a donor group bonded in a 5-membered ring. In a preferred embodiment of the invention, R ⁹ and R ¹⁰ are cyano groups and only R ² is a donor group bonded in a 5-membered ring. In a preferred embodiment of the invention, R ⁹ and R ¹⁰ are cyano groups and only R ³ is a donor group bonded in a 5-membered ring. In one embodiment of the invention, R ⁹ and R ¹⁰ are cyano groups and R ⁴ is only a donor group bonded in a 5-membered ring.

In one embodiment of the invention, 2 of R ¹～R¹⁰ are donor groups bonded in a 5 membered ring. In a preferred embodiment of the invention, 2 donor groups bonded in a 5-membered ring are identical. In one embodiment of the invention, 2 of R ¹～R⁸ are donor groups bonded in a 5 membered ring. In one aspect of the invention, 1 of R ¹～R⁴ and 1 of R ⁵～R⁸ are donor groups bonded in a 5 membered ring. In one embodiment of the invention, 1 of R ² and R ³ and 1 of R ⁶ and R ⁷ are donor groups bonded in a 5 membered ring. In one embodiment of the invention, 1 of R ¹～R⁸ and 1 of R ⁹ and R ¹⁰ are donor groups bonded in a 5 membered ring. For example, R ¹ and R ⁸ are donor groups bonded in a 5 membered ring. For example, R ² and R ⁷ are donor groups bonded in a 5 membered ring. For example, R ³ and R ⁶ are donor groups bonded in a 5 membered ring. For example, R ⁹ and R ¹⁰ are donor groups bonded in a 5 membered ring. In one embodiment of the invention, R ⁹ and R ¹⁰ are cyano groups and R ¹ and R ⁸ are donor groups bonded in a 5 membered ring. In a preferred embodiment of the invention, R ⁹ and R ¹⁰ are cyano groups and R ² and R ⁷ are donor groups bonded in a 5-membered ring. In a preferred embodiment of the invention, R ⁹ and R ¹⁰ are cyano groups and R ³ and R ⁶ are donor groups bonded in a 5-membered ring. In a preferred embodiment of the invention, R ⁹ and R ¹⁰ are cyano groups and R ² and R ³ are donor groups bonded in a 5-membered ring.

In one embodiment of the invention, 3 of R ¹～R¹⁰ are donor groups bonded in a 5 membered ring. In a preferred embodiment of the invention, 3 donor groups bonded in a 5-membered ring are identical. In one embodiment of the invention, 3 of R ¹～R⁸ are donor groups bonded in a 5 membered ring. In one embodiment of the invention, 3 of R ¹～R⁴ are donor groups bonded in a 5 membered ring. In one embodiment of the present invention, 2 of R1 to R ⁴ and 1 of R ⁵～R⁸ are donor groups bonded in a 5-membered ring. For example, R ²、R³ and R ⁴ are donor groups bonded in a 5 membered ring. For example, R ²、R³ and R ⁶ are donor groups bonded in a 5 membered ring. For example, R ²、R³ and R ⁷ are donor groups bonded in a 5 membered ring. In a preferred embodiment of the invention, R ⁹ and R ¹⁰ are cyano groups and R ²、R³ and R ⁴ are donor groups bonded in a 5-membered ring. In one embodiment of the invention, R ⁹ and R ¹⁰ are cyano groups and R ²、R³ and R ⁶ are donor groups bonded in a 5 membered ring. In one embodiment of the invention, R ⁹ and R ¹⁰ are cyano groups and R ²、R³ and R ⁷ are donor groups bonded in a 5 membered ring. In one embodiment of the invention, 4 of R ¹～R¹⁰ are donor groups bonded in a 5 membered ring. In a preferred embodiment of the invention, the 4 donor groups bonded by the 5-membered ring are identical. In one embodiment of the invention, 2 of R ¹～R⁴ and 2 of R ⁵～R⁸ are donor groups bonded in a 5 membered ring. For example, R ²、R³、R⁶ and R ⁷ are donor groups bonded in a 5 membered ring. For example, R ¹、R³、R⁶ and R ⁸ are donor groups bonded in a 5 membered ring. In one embodiment of the invention, R ⁹ and R ¹⁰ are cyano groups and R ²、R³、R⁶ and R ⁷ are donor groups bonded in a 5 membered ring. In one embodiment of the invention, R ⁹ and R ¹⁰ are cyano groups and R ¹、R³、R⁶ and R ⁸ are donor groups bonded in a 5 membered ring.

A donor group bonded to a 5-membered ring is a group bonded to any one of 5 atoms constituting a ring skeleton of the 5-membered ring, and the Hammett's sigma p value is negative. Here, "hamite σp value" is proposed by l.p. hammett, which is a value that quantifies the influence of a substituent on the reaction rate or balance of a para-substituted benzene derivative. Specifically, the following formula holds between the substituent in the para-substituted benzene derivative and the reaction rate constant or equilibrium constant:

log(k/k₀)＝ρσp

Or (b)

log(K/K₀)＝ρσp

A constant (σp) specific to the substituent in (a). In the above formula, K ₀ represents a rate constant of a benzene derivative having no substituent, K represents a rate constant of a benzene derivative substituted with a substituent, K ₀ represents an equilibrium constant of a benzene derivative having no substituent, K represents an equilibrium constant of a benzene derivative substituted with a substituent, and ρ represents a reaction constant determined by the kind and condition of the reaction. For the description relating to the "sigma p value of hamite" and the numerical values of the substituents in the present invention, reference can be made to the description relating to the sigma p value of Hansch, c.et al, chem.rev.,91,165-195 (1991).

The donor group bonded with a 5-membered ring is preferably a group bonded with a nitrogen atom constituting the ring skeleton of a 5-membered ring. Preferably 5 membered ring pi conjugation. For example, a donor group of pi-conjugated 5-membered ring containing 1 nitrogen atom as a ring skeleton constituting atom of a 5-membered ring and bonded thereto, or a donor group of pi-conjugated 5-membered ring containing 2 nitrogen atoms as a ring skeleton constituting atom of a 5-membered ring and bonded thereto with one of the nitrogen atoms can be cited. More specifically, there can be mentioned a substituted or unsubstituted indol-1-yl group, a substituted or unsubstituted condensed cyclic indol-1-yl group, a substituted or unsubstituted carbazole-9-yl group, a substituted or unsubstituted condensed cyclic carbazole-9-yl group, a substituted or unsubstituted benzimidazol-1-yl group, a substituted or unsubstituted condensed cyclic benzimidazol-1-yl group and the like. As used herein, "ring fused" refers to a state in which the rings are fused. For example, if it is a ring-fused carbazole-9-yl group, it means that the ring is fused to at least one of 2 benzene rings constituting the carbazole. The condensed ring may be any one of an aromatic hydrocarbon ring, an aromatic heterocyclic ring, an aliphatic hydrocarbon ring and an aliphatic heterocyclic ring, and may be a ring in which these are further condensed. Aromatic hydrocarbon rings and aromatic heterocyclic rings are preferred. The aromatic hydrocarbon ring may include a substituted or unsubstituted benzene ring. The benzene ring may be further condensed with another benzene ring or a heterocyclic ring such as a pyridine ring. The aromatic heterocycle represents a ring exhibiting aromaticity, preferably a 5-to 7-membered ring, containing a heteroatom as a ring skeleton constituting atom, and for example, a 5-membered ring or a 6-membered ring can be used. In one embodiment of the present invention, a furan ring, a thiophene ring, or a pyrrole ring may be used as the aromatic heterocycle. In one embodiment of the present invention, the fused ring is a furan ring of a substituted or unsubstituted benzofuran, a thiophene ring of a substituted or unsubstituted benzothiophene, or a pyrrole ring of a substituted or unsubstituted indole. Further, a substituent selected from the substituent group E is preferably bonded to the nitrogen atom of the pyrrole ring, and an aryl group which may be substituted with an alkyl group or an aryl group is more preferably substituted.

The donor group bonded in a 5-membered ring is preferably a group represented by the following general formula (2).

[ Chemical formula 4]

General formula (2)

In the general formula (2), Z ¹ represents C-R ¹¹ or N, Z ² represents C-R ¹² or N, Z ³ represents C-R ¹³ or N, and Z ⁴ represents C-R14 or N. Z ⁵ represents C or N, ar represents a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted aromatic heterocyclic ring. R ¹¹ and R ¹²、R¹² and R ¹³、R¹³ and R14 can be bonded to each other to form a cyclic structure.

In Z ¹～Z⁴, the number of N is preferably 0 to 3, more preferably 0 to 2. In one embodiment of the present invention, the number of N in Z ¹～Z⁴ is 1. In one embodiment of the present invention, the number of N in Z ¹～Z⁴ is 0.

R ¹¹ to R14 each independently represent a hydrogen atom, a deuterium atom or a substituent.

The substituents may be selected, for example, from substituent groups a, B, C, D, E, and E. When 2 or more of R ¹¹～R¹⁴ represent substituents, these 2 or more substituents may be the same or different. Preferably, 0 to 2 of R ¹¹～R¹⁴ are substituents, for example, 1 substituent or 0 substituent (R ¹¹～R¹⁴ is a hydrogen atom or a deuterium atom).

R ¹¹ and R ¹²、R¹² and R ¹³、R¹³ and R14 can be bonded to each other to form a cyclic structure. The cyclic structure may be any of an aromatic hydrocarbon ring, an aromatic heterocyclic ring, an aliphatic hydrocarbon ring, and an aliphatic heterocyclic ring, and may be a ring formed by fusing them. Aromatic hydrocarbon rings and aromatic heterocyclic rings are preferred. The aromatic hydrocarbon ring may include a substituted or unsubstituted benzene ring. The benzene ring may be further condensed with another benzene ring or a heterocyclic ring such as a pyridine ring. The aromatic heterocycle represents a ring exhibiting aromaticity, preferably a 5-to 7-membered ring, containing a heteroatom as a ring skeleton constituting atom, and for example, a 5-membered ring or a 6-membered ring can be used. In one embodiment of the present invention, a furan ring, a thiophene ring, or a pyrrole ring may be used as the aromatic heterocycle. In a preferred embodiment of the present invention, the cyclic structure is a furan ring of a substituted or unsubstituted benzofuran, a thiophene ring of a substituted or unsubstituted benzothiophene, a pyrrole ring of a substituted or unsubstituted indole. The benzofurans, benzothiophenes, indoles described herein may be unsubstituted, substituted with substituents selected from substituent group a, substituted with substituents selected from substituent group B, substituted with substituents selected from substituent group C, substituted with substituents selected from substituent group D, or substituted with substituents selected from substituent group E. The nitrogen atom constituting the pyrrole ring of indole is preferably bonded to a substituted or unsubstituted aryl group, and the substituent thereof may include, for example, a substituent selected from any one of substituent groups a to E. The cyclic structure may be a substituted or unsubstituted cyclopentadiene ring. In one embodiment of the present invention, 1 group of R ¹¹ and R ¹²、R¹², R ¹³、R¹³ and R ¹⁴ are bonded to each other to form a cyclic structure. In one embodiment of the present invention, R ¹¹ and R ¹²、R¹² and R ¹³、R¹³ and R ¹⁴ are not bonded to each other to form a cyclic structure.

In the general formula (2), Z ⁵ represents C or N, and Ar represents a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted aromatic heterocyclic ring. In one embodiment of the present invention, Z ⁵ is C and Ar is a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted aromatic heterocycle. In one embodiment of the invention, Z ⁵ is N and Ar is a substituted or unsubstituted aromatic heterocycle.

Examples of the aromatic hydrocarbon ring that can be used for Ar include benzene rings. The benzene ring may be further condensed with another benzene ring or a heterocyclic ring such as a pyridine ring. The aromatic heterocycle that Ar may use is preferably a 5-to 7-membered ring, and for example, a 5-membered ring or a 6-membered ring can be used. In one embodiment of the present invention, as the aromatic heterocycle, a furan ring, a thiophene ring, a pyrrole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, or a pyrazine ring can be used. In one embodiment of the present invention, Z ⁵ is C and the aromatic heterocycle is a furan ring of a substituted or unsubstituted benzofuran, a thiophene ring of a substituted or unsubstituted benzothiophene, a pyridine ring of a substituted or unsubstituted quinoline, or a pyridine ring of a substituted or unsubstituted isoquinoline. In one embodiment of the present invention, Z ⁵ is N and the aromatic heterocycle is an azole ring of a substituted or unsubstituted indole or an imidazole ring of a substituted or unsubstituted benzimidazole. The benzofurans, benzothiophenes, quinolines, isoquinolines, indoles, benzimidazoles described herein may be unsubstituted, substituted with a substituent selected from substituent group a, substituted with a substituent selected from substituent group B, substituted with a substituent selected from substituent group C, substituted with a substituent selected from substituent group D, or substituted with a substituent selected from substituent group E.

When Z ⁵ in the general formula (2) is C, a group represented by the following general formula (3) is preferable.

[ Chemical formula 5]

General formula (3)

In the general formula (3), Z ¹ represents C-R ¹¹ or N, Z ² represents C-R ¹² or N, Z ³ represents C-R ¹³ or N, Z ⁴ represents C-R ¹⁴ or N, Z ⁶ represents C-R ¹⁶ or N, Z ⁷ represents C-R ¹⁷ or N, Z ⁸ represents C-R ¹⁸ or N, and Z ⁹ represents C-R ¹⁹ or N. In addition, R ¹¹ and R ¹²、R¹² and R ¹³、R¹³ and R ¹⁴、R¹⁶ and R ¹⁷、R¹⁷ and R ¹⁸、R¹⁸ and R ¹⁹ may be bonded to each other to form a cyclic structure.

Regarding Z ¹～Z⁴、R¹¹～R¹⁴ in the general formula (3), reference can be made to the corresponding description of the general formula (2). Z ⁶～Z⁹、R¹⁶～R¹⁹ in the general formula (3) corresponds in turn to Z ¹～Z⁴、R¹¹～R¹⁴ in the general formula (2), for which reference can be made to the description of Z ¹～Z⁴、R¹¹～R¹⁴ of the general formula (2).

In one embodiment of the present invention, the number of N in Z ¹～Z⁴、Z⁶～Z⁹ is preferably 0 to 2, more preferably 0 or 1. In one embodiment of the present invention, the number of N in Z ¹～Z⁴、Z⁶～Z⁹ is 1. In a preferred embodiment of the present invention, the number of N in Z ¹～Z⁴、Z⁶～Z⁹ is 0. When 0, represents a substituted or unsubstituted carbazol-9-yl group. The carbazol-9-yl group may be unsubstituted, substituted with a substituent selected from the substituent group A, substituted with a substituent selected from the substituent group B, substituted with a substituent selected from the substituent group C, substituted with a substituent selected from the substituent group D, or substituted with a substituent selected from the substituent group E. In a preferred embodiment of the invention, the donor group bonded in a 5-membered ring is a carbazol-9-yl group substituted with a group comprising at least 1 substituted or unsubstituted aryl group, for example a carbazol-9-yl group substituted with at least 1 substituted or unsubstituted aryl group. In one embodiment of the present invention, at least one of the 2-and 7-positions is a substituted or unsubstituted aryl group. In one embodiment of the present invention, at least one of the 3-and 6-positions is a substituted or unsubstituted aryl group. The aryl groups described herein may be unsubstituted, substituted with a substituent selected from substituent group a, substituted with a substituent selected from substituent group B, substituted with a substituent selected from substituent group C, substituted with a substituent selected from substituent group D, or substituted with a substituent selected from substituent group E.

The donor group bonded with a 5-membered ring may be the following group: which is a substituted or unsubstituted indol-1-yl group, and a ring is condensed on an indole ring constituting the indol-1-yl group, thereby forming a condensed ring having a ring number of 4 or more. Hereinafter, in this specification, a group satisfying this condition is referred to as "ring-condensed indol-1-yl".

In the ring-condensed indol-1-yl group, the ring condensed with the benzene ring or pyrrole ring constituting the indol-1-yl group may be 1 polycyclic ring, or may be 2 or more polycyclic rings or monocyclic rings. For example, in the case of 2 fusions, 1 fused to a benzene ring and 1 fused to a pyrrole ring are preferred. The fused 2 rings may be the same or different. The fused ring having 4 or more, 5 or more, or 6 or more rings, preferably 5 or more rings, can be formed by fusing the ring with the indole ring. For example, a compound forming a condensed ring having a ring number of 4, a compound forming a condensed ring having a ring number of 5, a compound forming a condensed ring having a ring number of 6, a compound forming a condensed ring having a ring number of 8 may be used.

The ring may be fused to only the 2,3 position (b), to only the 4,5 position (e), to only the 5,6 position (f), to only the 6,7 position (g), and to both the 4,5 position (e) and the 6,7 position (g) of the indole ring. And, any 1 of the 4, 5-position (e), 5, 6-position (f), 6, 7-position (g) may be condensed with the 2, 3-position (b) (refer to the following formula, which represents a bonding position).

[ Chemical formula 6]

The ring directly condensed with the benzene ring or pyrrole ring constituting the indol-1-yl group (condensed is a polycyclic ring, and when condensed, means a ring directly condensed with only the ring constituting the polycyclic ring), may be any of an aromatic hydrocarbon ring, an aromatic heterocyclic ring, an aliphatic hydrocarbon ring, and an aliphatic heterocyclic ring. It is preferable that 1 or more rings selected from the group consisting of benzene rings and aromatic heterocyclic rings are directly condensed.

The heterocyclic ring as described herein is a ring comprising heteroatoms. The hetero atom is preferably selected from an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom, more preferably from an oxygen atom, a sulfur atom and a nitrogen atom. In a preferred form, the heteroatom is an oxygen atom. In a preferred alternative, the heteroatom is a sulfur atom. In a preferred further embodiment, the heteroatom is a nitrogen atom. The number of hetero atoms included in the ring skeleton constituting atoms of the heterocycle is 1 or more, preferably 1 to 3, more preferably 1 or 2. In a preferred embodiment, the number of heteroatoms is 1. When the number of heteroatoms is 2 or more, they are preferably the same heteroatom, but may be constituted of different kinds of heteroatoms. For example, more than 2 heteroatoms may each be a nitrogen atom. The ring skeleton constituent atoms other than the hetero atoms are carbon atoms. The number of ring skeleton constituting a heterocyclic ring directly condensed with the benzene ring constituting the indol-1-yl group is preferably 4 to 8, more preferably 5 to 7, still more preferably 5 or 6. In a preferred embodiment, the number of ring members constituting the heterocyclic ring is 5. Preferably, there are 2 or more conjugated double bonds in the heterocycle, preferably by heterocycle fusion to extend the conjugated system of the indole ring (that is, preferably having aromatic character). Preferable examples of the heterocyclic ring include a furan ring, a thiophene ring, and a pyrrole ring.

On the ring directly condensed with the benzene ring or pyrrole ring constituting the indol-1-yl group, other rings may be further condensed. The condensed ring may be a single ring or a condensed ring. Examples of the condensed ring include an aromatic hydrocarbon ring, an aromatic heterocyclic ring, an aliphatic hydrocarbon ring, and an aliphatic heterocyclic ring.

In a preferred embodiment of the invention, at least 1 heterocycle is directly fused to the benzene or pyrrole ring constituting the indol-1-yl group. In a preferred embodiment of the present invention, the condensed ring constituting the ring-condensed indol-1-yl group contains 2 or more heterocyclic rings. For example, a case where 2 heterocycles are included or a case where 3 heterocycles are included can be cited.

Examples of the aromatic hydrocarbon ring in the present specification include benzene rings. Examples of the aromatic heterocycle include a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a pyrazole ring, and an imidazole ring. Examples of the aliphatic hydrocarbon ring include cyclopentane ring, cyclohexane ring and cycloheptane ring. Examples of the aliphatic heterocyclic ring include a piperidine ring, a pyrrolidine ring, and an imidazoline ring. Specific examples of the condensed ring include naphthalene ring, anthracene ring, phenanthrene ring, pyran ring, tetracene ring, indole ring, isoindole ring, benzimidazole ring, benzotriazole ring, quinoline ring, isoquinoline ring, quinazoline ring, quinoxaline ring, and cinnoline ring.

In a preferred embodiment of the invention, the cyclic fused indol-1-yl is benzofuranfused indol-1-yl, benzothiophene fused indol-1-yl, indol fused indol-1-yl or silane indene fused indol-1-yl. In a more preferred mode of the invention, the indol-1-yl group is a benzofuran-fused indol-1-yl group, a benzothiophene-fused indol-1-yl group or an indol-fused indol-1-yl group.

In the present invention, as the benzofuran-condensed indol-1-yl group, a substituted or unsubstituted benzofuran [2,3-e ] indol-1-yl group may be employed. Also, substituted or unsubstituted benzofuran [3,2-e ] indol-1-yl may be employed. Also, substituted or unsubstituted benzofuran [2,3-f ] indol-1-yl may be employed. Also, substituted or unsubstituted benzofuran [3,2-f ] indol-1-yl may be employed. Also, substituted or unsubstituted benzofuran [2,3-g ] indol-1-yl may be employed. Also, substituted or unsubstituted benzofuran [3,2-g ] indol-1-yl may be employed. The fused ring constituting these groups may or may not be further fused with a ring.

In the present invention, as the benzofuran-condensed indol-1-yl group, a substituted or unsubstituted benzofuran [2,3-a ] carbazol-9-yl group may be employed. And, substituted or unsubstituted benzofuran [3,2-a ] carbazol-9-yl groups may also be employed. And, substituted or unsubstituted benzofuran [2,3-b ] carbazol-9-yl groups may also be employed. And, substituted or unsubstituted benzofuran [3,2-b ] carbazol-9-yl groups may also be employed. And, substituted or unsubstituted benzofuran [2,3-c ] carbazol-9-yl groups may also be employed. And, substituted or unsubstituted benzofuran [3,2-c ] carbazol-9-yl groups may also be employed. The fused ring constituting these groups may or may not be further fused with a ring.

As a preferable benzofuran-condensed indol-1-yl group, a group having any of the following structures may be substituted or unsubstituted. For example, a group substituted with an aryl group such as a phenyl group or a group substituted at the 3-position of a carbazole ring can be preferably exemplified. The benzene ring in the following structure may or may not be further condensed with a ring. The wavy line indicates the bonding position.

[ Chemical formula 7]

It is also possible to use carbazol-9-yl in which the benzofuran ring is fused in the 2-and 3-positions. Specifically, the hydrogen atom in the following structure may be substituted or unsubstituted. The benzene ring in the following structure may or may not be further condensed with a ring.

[ Chemical formula 8]

In the present invention, as the benzothiophene-fused indol-1-yl group, a substituted or unsubstituted benzothiophene [2,3-e ] indol-1-yl group may be employed. Also, substituted or unsubstituted benzothieno [3,2-e ] indol-1-yl groups may be employed. Also, substituted or unsubstituted benzothieno [2,3-f ] indol-1-yl groups may be employed. Also, substituted or unsubstituted benzothieno [3,2-f ] indol-1-yl groups may be employed. Also, substituted or unsubstituted benzothieno [2,3-g ] indol-1-yl may be employed. Also, substituted or unsubstituted benzothieno [3,2-g ] indol-1-yl groups may be employed. The fused ring constituting these groups may or may not be further fused with a ring.

In the present invention, as the benzothiophene-fused indol-1-yl group, a substituted or unsubstituted benzothiophene [2,3-a ] carbazol-9-yl group may be employed. Also, substituted or unsubstituted benzothieno [3,2-a ] carbazol-9-yl groups may be employed. Also, substituted or unsubstituted benzothieno [2,3-b ] carbazol-9-yl groups may be employed. Also, substituted or unsubstituted benzothieno [3,2-b ] carbazol-9-yl groups may be employed. Also, substituted or unsubstituted benzothieno [2,3-c ] carbazol-9-yl groups may be employed. Also, substituted or unsubstituted benzothieno [3,2-c ] carbazol-9-yl groups may be employed. The fused ring constituting these groups may or may not be further fused with a ring.

Preferred benzothiophene-fused indol-1-yl groups include those having any of the following structures, and hydrogen atoms in the following structures may be substituted or unsubstituted. For example, a group substituted with an aryl group such as a phenyl group or a group substituted at the 3-position of a carbazole ring can be preferably exemplified. The benzene ring in the following structure may or may not be further condensed with a ring.

[ Chemical formula 9]

2 Carbazol-9-yl fused to the 2,3 position of the benzothiophene ring may also be used. Specifically, the hydrogen atom in the following structure may be substituted or unsubstituted. The benzene ring in the following structure may or may not be further condensed with a ring.

[ Chemical formula 10]

In the present invention, as the indole fused indol-1-yl group, a substituted or unsubstituted indolo [2,3-e ] indol-1-yl group may be used. Also, substituted or unsubstituted indolo [3,2-e ] indol-1-yl groups may be employed. Also, substituted or unsubstituted indolo [2,3-f ] indol-1-yl groups may be employed. Also, substituted or unsubstituted indolo [3,2-f ] indol-1-yl groups may be employed. Also, substituted or unsubstituted indolo [2,3-g ] indol-1-yl may be employed. Also, substituted or unsubstituted indolo [3,2-g ] indol-1-yl may be employed. The fused ring constituting these groups may or may not be further fused with a ring.

In the present invention, as the indole fused indol-1-yl group, a substituted or unsubstituted indolo [2,3-a ] carbazol-9-yl group may be used. Also, substituted or unsubstituted indolo [3,2-a ] carbazol-9-yl groups may be employed. Also, substituted or unsubstituted indolo [2,3-b ] carbazol-9-yl may be used. Also, substituted or unsubstituted indolo [3,2-b ] carbazol-9-yl may be used. Also, substituted or unsubstituted indolo [2,3-c ] carbazol-9-yl groups may be employed. Also, substituted or unsubstituted indolo [3,2-c ] carbazol-9-yl groups may be employed. The fused ring constituting these groups may or may not be further fused with a ring.

As a preferable indole fused indol-1-yl group, there may be mentioned a group having any of the following structures, and a hydrogen atom in the following structure may be substituted or unsubstituted. For example, a group substituted with an aryl group such as a phenyl group or a group substituted at the 3-position of a carbazole ring can be preferably exemplified. The benzene ring in the following structure may or may not be further condensed with a ring.

[ Chemical formula 11]

In a preferred embodiment of the invention, the benzofuran-fused indol-1-yl, benzothiophene-fused indol-1-yl, indol-fused indol-1-yl and silane indene-fused indol-1-yl may be substituted with substituted or unsubstituted aryl groups. Preferably substituted with a substituted or unsubstituted phenyl group. As the substituent of the aryl group or phenyl group described herein, a group selected from any one of the substituent groups a to E may be selected, and it may be preferable to select from the substituent group E. Also, aryl and phenyl groups described herein are also preferably unsubstituted. In a preferred embodiment of the invention, the ring-fused indol-1-yl is benzofuran-fused indol-1-yl substituted with a substituted or unsubstituted aryl group.

Specific examples of the donor group bonded in a 5-membered ring that can be used in the general formula (1) are shown below. However, the donor groups bonded in a 5-membered ring used in the present invention are not limitedly explained by the following specific examples. In the following specific examples, ph represents a phenyl group, D represents a deuterium atom, and x represents a bonding position. The methyl group is omitted. Thus, for example, D2 represents 3-methylcarbazol-9-yl.

[ Chemical formula 12-1]

[ Chemical formula 12-2]

[ Chemical formula 12-3]

[ Chemical formula 12-4]

[ Chemical formula 12-5]

[ Chemical formula 12-6]

[ Chemical formula 12-7]

[ Chemical formula 12-8]

[ Chemical formula 12-9]

[ Chemical formulas 12-10]

[ Chemical formulas 12-11]

[ Chemical formulas 12-12]

[ Chemical formulas 12-13]

[ Chemical formulas 12-14]

[ Chemical formulas 12-15]

[ Chemical formulas 12-16]

[ Chemical formulas 12-17]

In R ¹～R¹⁰ in the general formula (1), a group which is not a cyano group nor a donor group bonded with a 5-membered ring (hereinafter, referred to as "residual R ¹～R¹⁰") is a hydrogen atom, a deuterium atom, or a substituent which is not a cyano group nor a donor group bonded with a 5-membered ring (hereinafter, referred to as "residual substituent").

The remaining R ¹～R¹⁰ may be all hydrogen atoms or deuterium atoms, for example, may be all hydrogen atoms, for example, may be all deuterium atoms. In the remaining R ¹～R¹⁰, the number of the remaining substituents is preferably 0 to 6, for example, may be in the range of 0 to 4, may be in the range of 0 to 3, and may be in the range of 0 to 2.

The remaining substituents may be selected from the following substituent group a, may be selected from the following substituent group B, may be selected from the following substituent group C, may be selected from the following substituent group D, and may be selected from the following substituent group E. In one aspect of the invention, the other substituent is a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl. In a preferred form of the invention, the other substituent is a substituted or unsubstituted aryl group, for example a phenyl group which may be substituted with an alkyl or aryl group.

The "aryl" and "heteroaryl" may be a single ring or a condensed ring formed by condensing 2 or more rings. In the case of fused rings, the number of fused rings is preferably 2 to 6, and can be selected from 2 to 4, for example. Specific examples of the ring include benzene ring, pyridine ring, pyrimidine ring, triazine ring, naphthalene ring, anthracene ring, phenanthrene ring, triphenylene ring, quinoline ring, pyrazine ring, quinoxaline ring, and naphthyridine ring. Specific examples of the arylene group or heteroarylene group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 2-pyridyl group, a 3-pyridyl group and a 4-pyridyl group. The substituents for aryl and heteroaryl groups may be selected from the following substituent groups a, B, C, D, and E.

In the general formula (1), R ¹ and R ²、R² and R ³、R³ and R ⁴、R⁴ and R ⁵、R⁵ and R ⁶、R⁶ and R ⁷、R⁷ and R ⁸、R⁸ and R ⁹、R⁹ and R ¹⁰、R¹⁰ and R ¹ may be bonded to each other to form a cyclic structure. Regarding the description and specific examples of the ring structure described herein, reference can be made to the description and specific examples of the condensed ring in the description of the "ring condensed".

In one embodiment of the present invention, at least 1 of R ¹ and R ²、R² and R ³、R³ and R ⁴、R⁵ and R ⁶、R⁶ and R ⁷、R⁷ and R ⁸、R⁹ and R ¹⁰ are bonded to each other to form a cyclic structure. In one embodiment of the present invention, at least 1 of R ¹ and R ²、R² and R ³、R³ and R ⁴、R⁵ and R ⁶、R⁶ and R ⁷、R⁷ and R ⁸ are bonded to each other to form a cyclic structure. In one embodiment of the present invention, R ⁹ and R ¹⁰ are bonded to each other to form a cyclic structure. In one embodiment of the present invention, R ⁴ and R ⁵、R⁸ and R ⁹、R¹⁰ and R ¹ are not bonded to each other to form a cyclic structure. In one embodiment of the present invention, R ⁸ and R ⁹、R⁹ and R ¹⁰、R¹⁰ and R ¹ are not bonded to each other to form a cyclic structure. In one embodiment of the present invention, R ³ and R ⁴、R⁴ and R ⁵、R⁵ and R ⁶ are not bonded to each other to form a cyclic structure. In one embodiment of the present invention, R ³ and R ⁴、R⁴ and R ⁵、R⁵ and R ⁶、R⁸ and R ⁹、R⁹ and R ¹⁰、R¹⁰ and R ¹ are not bonded to each other to form a cyclic structure. In one embodiment of the present invention, R ¹ and R ²、R² and R ³、R³ and R ⁴、R⁴ and R ⁵、R⁵ and R ⁶、R⁶ and R ⁷、R⁷ and R ⁸、R⁸ and R ⁹、R¹⁰ and R ¹ are not bonded to each other to form a cyclic structure. In one embodiment of the present invention, R ¹ and R ²、R² and R ³、R³ and R ⁴、R⁴ and R ⁵、R⁵ and R ⁶、R⁶ and R ⁷、R⁷ and R ⁸、R⁸ and R ⁹、R⁹ and R ¹⁰、R¹⁰ and R ¹ are not bonded to each other to form a cyclic structure.

The compound represented by the general formula (1) preferably does not contain a metal atom, and may be a compound composed of only atoms selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom, an oxygen atom, and a sulfur atom. In a preferred embodiment of the present invention, the compound represented by the general formula (1) is composed of only atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms and oxygen atoms. The compound represented by the general formula (1) may be a compound composed of only atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms, and sulfur atoms. The compound represented by the general formula (1) may be a compound composed of only atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, and nitrogen atoms. The compound represented by the general formula (1) may be a compound composed of only atoms selected from the group consisting of carbon atoms, hydrogen atoms, and nitrogen atoms. Further, the compound represented by the general formula (1) may be a compound containing deuterium atoms and not containing hydrogen atoms. For example, the compound represented by the general formula (1) may be a compound composed of only atoms selected from the group consisting of carbon atoms, deuterium atoms, nitrogen atoms, oxygen atoms, and sulfur atoms.

In one embodiment of the present invention, the compound represented by the general formula (1) has a symmetrical structure. For example, it may have a line-symmetrical structure. When having a line-symmetrical structure, R ¹ and R ⁸ of the general formula (1) are the same, R ² and R ⁷ are the same, R ³ and R ⁶ are the same, R ⁴ and R ⁵ are the same, and R ⁹ and R ¹⁰ are the same. In one embodiment of the present invention, the compound represented by the general formula (1) has an asymmetric structure.

In the present specification, "substituent group a" means a group selected from a group consisting of a hydroxyl group, a halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group (for example, 1 to 40 carbon atoms), an alkoxy group (for example, 1 to 40 carbon atoms), an alkylthio group (for example, 1 to 40 carbon atoms), an aryl group (for example, 6 to 30 carbon atoms), an aryloxy group (for example, 6 to 30 carbon atoms), an arylthio group (for example, 6 to 30 carbon atoms), a heteroaryl group (for example, 5 to 30 ring skeleton constituting atoms), a heteroaryloxy group (for example, 5 to 30 ring skeleton constituting atoms), a heteroarylthio group (for example, 5 to 30 ring skeleton constituting atoms), an acyl group (for example, 1 to 40 carbon atoms), an alkenyl group (for example, 1 to 40 carbon atoms), an alkynyl group (for example, 1 to 40 carbon atoms), an alkoxycarbonyl group (for example, 1 to 40 carbon atoms), an aryloxycarbonyl group (for example, 1 to 40 carbon atoms), a heteroaryloxycarbonyl group (for example, 1 to 40 carbon atoms), a silyl group (for example, 1 to 40 carbon atoms), and a nitro group (for example, 1 to 40 trialkylsilyl groups).

In the present specification, the "substituent group B" means 1 group or a combination of 2 or more groups selected from the group consisting of an alkyl group (for example, 1 to 40 carbon atoms), an alkoxy group (for example, 1 to 40 carbon atoms), an aryl group (for example, 6 to 30 carbon atoms), an aryloxy group (for example, 6 to 30 carbon atoms), a heteroaryl group (for example, 5 to 30 ring skeleton constituent atoms), a heteroaryloxy group (for example, 5 to 30 ring skeleton constituent atoms), and a diarylamino group (for example, 0 to 20 carbon atoms).

In the present specification, the "substituent group C" means 1 group or a group formed by combining 2 or more groups selected from the group consisting of an alkyl group (for example, 1 to 20 carbon atoms), an aryl group (for example, 6 to 22 carbon atoms), a heteroaryl group (for example, 5 to 20 ring skeleton constituent atoms), and a diarylamino group (for example, 12 to 20 carbon atoms).

In the present specification, the "substituent group D" means 1 group or a group formed by combining 2 or more groups selected from the group consisting of an alkyl group (for example, having 1 to 20 carbon atoms), an aryl group (for example, having 6 to 22 carbon atoms), and a heteroaryl group (for example, having 5 to 20 ring skeleton constituent atoms).

In the present specification, the "substituent group E" means 1 group or a combination of 2 or more groups selected from the group consisting of an alkyl group (for example, having 1 to 20 carbon atoms) and an aryl group (for example, having 6 to 22 carbon atoms).

In the present specification, a substituent described as "substituent" or "substituted or unsubstituted" may be selected from, for example, substituent group a, substituent group B, substituent group C, substituent group D, or substituent group E.

Specific examples of the compound represented by the general formula (1) are shown below. The compounds represented by the general formula (1) that can be used in the present invention should not be interpreted as being limited to these specific examples.

In table 1, the structures of compounds 1 to 30 are shown by determining R ¹～R¹⁰ of the general formula (1) for each compound, respectively. In table 2, the structures of compounds 1 to 1008962 are shown by showing R ¹～R¹⁰ of a plurality of compounds in each segment. For example, in the case of compounds 1 to 447 in table 2, R ¹、R³～R⁸ is fixed to H (hydrogen atom), and R ⁹ and R ¹⁰ are fixed to CN (cyano group). The compounds R ² to D447 were designated as compounds 1 to 447 in this order. In the case of compounds 448 to 894, R ¹、R²、R⁴～R⁸ is fixed to H (hydrogen atom), and R ⁹ and R ¹⁰ are fixed to CN (cyano group). The compounds represented by R ³ as D1 to D447 were successively represented by compounds 448 to 894. Similarly, compounds 895 to 1788 and compound 806025 ～ 806918 were also identified. In the compounds 1789 to 201597, R ¹、R³～R⁶、R⁸ is fixed to H (hydrogen atom), and R ⁹ and R ¹⁰ are fixed to CN (cyano group). And, compound numbers are labeled in the following ways: the compounds in which R ² was D1 and R ⁷ was D1 to D447 were used as compounds 1789 to 2235, the compounds in which R ² was D2 and R ⁷ was D1 to D447 were used as compounds 2236 to 2681, the compounds in which R ² was D3 and R ⁷ was D1 to D447 were used as compounds 2682 to 3128, and the compounds in which R ² was D447 and R ⁷ was D1 to D447 were used as compounds 201151 ～ 201597. Similarly, compound 201598 ～ 806024, compound 806919 ～ 1006727 were also identified. In the compound 1006728 ～ 1007174, the compounds in which R ²、R³ and R ⁴ are the same and D1 to D447 are in this order were referred to as compound 1006728 ～ 1007174. Similarly, compound 1007175 ～ 1008962 was also identified. Here, R ²、R³ and R ⁷ are the same in compound 1007175 ～ 1007621, R ²、R³ and R ⁶ are the same in compound 1007622 ～ 1008068, R ²、R³、R⁶ and R ⁷ are the same in compound 1008069 ～ 1008515, and R ¹、R³、R⁶ and R ⁸ are the same in compound 1008516 ～ 1008962.

In tables 1 and 2, the structures of the compounds 1 to 1008962 are individually determined, and are specifically disclosed in the present specification. The compounds 1 to 30 are identified in both tables 1 and 2.

TABLE 1

No.

R¹

R²

R³

R⁴

R⁵

R⁶

R⁷

R⁸

R⁹

R¹⁰

1

H

D1

H

CN

2

H

D2

H

CN

3

H

D3

H

CN

4

H

D4

H

CN

5

H

D5

H

CN

6

H

D6

H

CN

7

H

D7

H

CN

8

H

D8

H

CN

9

H

D9

H

CN

10

H

D10

H

CN

11

H

D11

H

CN

12

H

D12

H

CN

13

H

D13

H

CN

14

H

D14

H

CN

15

H

D15

H

CN

16

H

D16

H

CN

17

H

D17

H

CN

18

H

D18

H

CN

19

H

D19

H

CN

20

H

D20

H

CN

21

H

D21

H

CN

22

H

D22

H

CN

23

H

D23

H

CN

24

H

D24

H

CN

25

H

D25

H

CN

26

H

D26

H

CN

27

H

D27

H

CN

28

H

D28

H

CN

29

H

D29

H

CN

30

H

D30

H

CN

The compounds in which all hydrogen atoms present in the molecules of the above-mentioned compounds 1 to 1008962 are replaced with deuterium atoms are disclosed as compounds 1 (D) to 1008962 (D). In the case where a rotamer exists in the compound represented by the general formula (1), the rotamer mixture and each rotamer separated are also referred to as rotamers disclosed in the present specification.

In the present invention, the compounds described in each section of table 2 can be selected as groups, respectively. For example, a total of 18 groups can be selected individually for each of the collars that select compounds 1 to 447 as 1 group and compounds 448 to 894 as another 1 group.

The molecular weight of the compound represented by the 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 the compound represented by the general formula (1) is used, for example, by vapor deposition. The lower limit of the molecular weight is the molecular weight of the smallest compound represented by the general formula (1).

The compound represented by the general formula (1) can be formed into a film by a coating method regardless of the molecular weight. When the coating method is used, a film can be formed even with a compound having a relatively large molecular weight. The compound represented by the general formula (1) has an advantage of being easily dissolved in an organic solvent. Therefore, the compound represented by the general formula (1) is easily applicable to a coating method, and is easily purified to improve purity.

It is also possible to consider that the present invention is applied to use a compound containing a plurality of structures represented by the general formula (1) in the molecule as a light-emitting material.

For example, a polymer obtained by pre-existing a polymerizable group in a structure represented by the general formula (1) and polymerizing the polymerizable group can be considered as a light-emitting material. For example, it is conceivable to prepare a monomer containing a polymerizable functional group in any one of the positions in the general formula (1), polymerize it alone or copolymerize it together with other monomers, thereby obtaining a polymer having a repeating unit, and use the polymer as a light-emitting material. Alternatively, it is also conceivable to obtain a dimer or trimer by coupling compounds having a structure represented by the general formula (1) to each other, and use these as a light-emitting material.

As an example of the polymer having a repeating unit including a structure represented by the general formula (1), a polymer including 2 structures represented by any one of the following general formulas can be given.

[ Chemical formula 13]

In the above general formula, Q represents a group including a structure represented by general formula (1), and L ¹ and L ² represent a linking group. The number of carbon atoms of the linking group is preferably 0 to 20, more preferably 1 to 15, and still more preferably 2 to 10. The linking group is preferably a linking group having a structure represented by-X ¹¹-L¹¹ -. Here, X ¹¹ represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom. L ¹¹ represents a linking group, preferably a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, more preferably a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms or a substituted or unsubstituted phenylene group.

In the above formula, R ¹⁰¹、R¹⁰²、R¹⁰³ and R ¹⁰⁴ each independently represent a substituent. The alkyl group is preferably a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, or a halogen atom, more preferably a substituted alkyl group having 1 to 3 carbon atoms, an unsubstituted alkoxy group having 1 to 3 carbon atoms, a fluorine atom, or a chlorine atom, and still more preferably a substituted alkyl group having 1 to 3 carbon atoms, or an unsubstituted alkoxy group having 1 to 3 carbon atoms.

The linking groups represented by L ¹ and L ² can be bonded to any of the positions in general formula (1) constituting Q. More than 2 linking groups may be linked to 1Q to form a cross-linked structure or a network structure.

Specific examples of the structure of the repeating unit include a structure represented by the following formula.

[ Chemical formula 14]

Polymers having repeating units comprising these formulae can be synthesized by: hydroxyl groups are introduced into any one of the positions in the general formula (1) in advance, and the following compounds are reacted as linking groups to introduce polymerizable groups, and the polymerizable groups are polymerized.

[ Chemical formula 15]

The polymer having a structure represented by the general formula (1) in the molecule may be a polymer composed only of a repeating unit having a structure represented by the general formula (1), or may be a polymer having a repeating unit having a structure other than the above. The repeating unit having the structure represented by the general formula (1) contained in the polymer may be one kind or 2 or more kinds. The repeating unit having no structure represented by the general formula (1) may be a repeating unit derived from a monomer commonly used for copolymerization. For example, a repeating unit derived from a monomer having an ethylenic unsaturated bond such as ethylene or styrene can be given.

In one embodiment, the compound represented by the general formula (1) is a light-emitting material.

In one embodiment, the compound represented by the general formula (1) is a compound capable of emitting delayed fluorescence.

In one embodiment of the present invention, the compound represented by the general formula (1) is capable of emitting light in the UV region, blue, green, yellow, orange, red region (e.g., about 420nm to about 500nm, about 500nm to about 600nm, or about 600nm to about 700 nm) or near infrared region in the visible spectrum when excited by heat or an electronic device.

In one embodiment of the present invention, the compound represented by the general formula (1) is capable of emitting light in the red or orange region (e.g., about 620nm to about 780nm, about 650 nm) in the visible spectrum when excited by heat or an electronic device.

In one embodiment of the present invention, the compound represented by the general formula (1) is capable of emitting light in the orange or yellow region (e.g., about 570nm to about 620nm, about 590nm, about 570 nm) of the visible spectrum when excited by heat or an electronic device.

In one embodiment of the present invention, the compound represented by the general formula (1) is capable of emitting light in the green region (e.g., about 490nm to about 575nm, about 510 nm) of the visible spectrum when excited by heat or an electronic device.

In one embodiment of the present invention, the compound represented by the general formula (1) is capable of emitting light in the blue region (e.g., about 400nm to about 490nm, about 475 nm) of the visible spectrum when excited by heat or an electronic device.

In one embodiment of the present invention, the compound represented by the general formula (1) is capable of emitting light in the ultraviolet spectrum region (for example, 280 to 400 nm) when excited by heat or an electronic device.

In one embodiment of the present invention, the compound represented by the general formula (1) is capable of emitting light in the infrared spectrum region (for example, 780nm to 2 μm) when excited by heat or an electronic device.

In a preferred embodiment of the present invention, the compound represented by the general formula (1) emits light in a region of 520nm or more when excited by heat or electrons. In a preferred embodiment of the invention, light in the green region is emitted in particular at 520nm or more and less than 560 nm. In another preferred embodiment of the present invention, the light is emitted at 560nm to 640 nm.

In one embodiment of the present invention, an organic semiconductor device using the compound represented by the general formula (1) can be produced. The organic semiconductor element described herein may be an optically interposed organic light element or an optically non-interposed organic element. The organic light-emitting element may be an organic light-emitting element that emits light, an organic light-receiving element that receives light, or an element that generates energy movement in the element by light. In one embodiment of the present invention, an organic light element such as an organic electroluminescent element or a solid-state imaging element (e.g., CMOS image sensor) can be produced using the compound represented by the general formula (1). In one embodiment of the present invention, a CMOS (complementary metal oxide semiconductor) or the like using a compound represented by the general formula (1) can be produced.

The electron characteristics of a chemical substance library of small molecules can be calculated using quantum chemical calculations based on the well-known ab-rule. For example, as a basis group, the Hartree-Fock equation (TD-DFT/B3 LYP/6-31G) was analyzed using a time-dependent density functional theory using a set of functions known as a 3-parameter, lee-Yang-Parr mixed functional of 6-31G and beck (beck), and molecular fragments (portions) having HOMO above a specific threshold and LUMO below a specific threshold could be screened.

Thus, for example, the donor moiety ("D") can be selected in the presence of HOMO energy (e.g., ionization potential) of greater than-6.5 eV. Further, for example, when LUMO energy (e.g., electron affinity) of-0.5 eV or less is present, the acceptor moiety ("a") can be selected. The bridge moiety ("B") is, for example, a strong conjugated system capable of tightly confining the acceptor and donor moieties to unique steric structures, thereby preventing duplication between the pi conjugated systems of the donor and acceptor moieties.

In one embodiment, the library of compounds is screened using more than 1 of the following characteristics.

1. Luminescence around a specific wavelength

2. Triplet states above the calculated specific energy level

3.ΔE _ST value below a specific value

4. Quantum yield above a particular value

HOMO level

Lumo level

In one embodiment, the difference between the lowest excited singlet state and the lowest excited triplet state (Δe _ST) in 77K is less than about 0.5eV, less than about 0.4eV, less than about 0.3eV, less than about 0.2eV, or less than about 0.1eV. In one embodiment, the ΔE _ST value is less than about 0.09eV, less than about 0.08eV, less than about 0.07eV, less than about 0.06eV, less than about 0.05eV, less than about 0.04eV, less than about 0.03eV, less than about 0.02eV, or less than about 0.01eV.

In one embodiment, the compound represented by formula (1) represents a quantum yield of greater than 25%, e.g., 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 more.

[ Method of synthesizing Compound represented by the general formula (1) ]

The compound represented by the general formula (1) contains a novel compound.

The compound represented by the general formula (1) can be synthesized by combining known reactions. For example, a cyanophenanthrene substituted with a substituted or unsubstituted carbazol-9-yl group can be synthesized by reacting a phenanthrene having a cyano group and a halogen atom with a substituted or unsubstituted carbazole. For details of the reaction conditions, reference can be made to the synthesis examples described below.

[ Structure Using the Compound represented by the general formula (1) ]

In one embodiment, the compound is dispersed in combination with the compound represented by the general formula (1), covalently bonded to the compound, coated with the compound, and used together with 1 or more materials (e.g., small molecules, polymers, metals, metal complexes, etc.) supporting or associated with the compound to form a solid film or layer. For example, the compound represented by the general formula (1) can be combined with an electroactive material to form a thin film. In some cases, the compound represented by the general formula (1) may also be combined with a hole-transporting polymer. In some cases, the compound represented by the general formula (1) may also be combined with an electron transport polymer. In some cases, the compound represented by the general formula (1) may be combined with a hole-transporting polymer and an electron-transporting polymer. In some cases, the compound represented by the general formula (1) may also be combined with a copolymer having both a hole transporting portion and an electron transporting portion. By the above embodiment, electrons and/or holes formed in the solid thin film or layer can be made to interact with the compound represented by the general formula (1).

[ Formation of film ]

In one embodiment, the thin film containing the compound represented by the general formula (1) can be formed by a wet process. In the wet process, a solution in which a composition containing the compound of the present invention is dissolved is applied to a surface, and a thin film is formed after the solvent is removed. Examples of the wet process include spin coating, slit coating, inkjet (spray) printing, gravure printing, offset printing, and flexography, but are not limited thereto. In the wet process, an appropriate organic solvent capable of dissolving the composition containing the compound of the present invention is selected and used. In one embodiment, a substituent (e.g., an alkyl group) that improves solubility in an organic solvent can be introduced into the compound contained in the composition.

In one embodiment, the thin film comprising the compound of the present invention can be formed by a dry process. In one embodiment, a vacuum deposition method may be used as the dry process, but the present invention is not limited thereto. In the case of using the vacuum vapor deposition method, the compound constituting the thin film may be co-deposited from a single vapor deposition source, or co-deposited from a single vapor deposition source mixed with the compound. When a single vapor deposition source is used, a mixed powder of powders of the compounds may be used, a compression molded product obtained by compressing the mixed powder may be used, or a mixture obtained by heating, melting and cooling the respective compounds may be used. In one embodiment, the co-evaporation is performed under a condition that the evaporation rates (weight reduction rates) of the plurality of compounds included in the single evaporation source are uniform or substantially uniform, whereby a thin film having a composition ratio corresponding to the composition ratio of the plurality of compounds included in the evaporation source can be formed. If a plurality of compounds are mixed as vapor deposition sources in the same composition ratio as the formed thin film, a thin film having a desired composition ratio can be formed easily. In one embodiment, the temperature at which the weight reduction rate of each compound by co-evaporation is the same can be determined, and this temperature can be used as the temperature at the time of co-evaporation.

[ Examples of the use of the Compound represented by the general formula (1) ]

The compound represented by the general formula (1) is useful as a material for an organic light-emitting element. Particularly preferably used for organic light emitting diodes and the like.

An organic light emitting diode:

One mode of the present invention refers to the use of the compound represented by the general formula (1) of the present invention in the form of a light-emitting material of an organic light-emitting device. In one embodiment, the compound represented by the general formula (1) of the present invention can be effectively used as a light emitting material in a light emitting layer of an organic light emitting device. In one embodiment, the compound represented by the general formula (1) contains delayed fluorescence (delayed phosphor) that emits delayed fluorescence. In one embodiment, the present invention provides a delayed phosphor having a structure represented by general formula (1). In one embodiment, the present invention refers to the use of the compound represented by the general formula (1) as a delayed phosphor. In one embodiment, the compound represented by the general formula (1) of the present invention can be used as a host material and can be used together with one or more light-emitting materials, which may be a fluorescent material, a phosphorescent material, or TADF. In one embodiment, the compound represented by the general formula (1) can also be used as a hole transporting material. In one embodiment, the compound represented by the general formula (1) can be used as an electron transporting material. In one embodiment, the present invention refers to a method of generating delayed fluorescence from a compound represented by the general formula (1). In one embodiment, an organic light emitting device including a compound as a light emitting material emits delayed fluorescence and exhibits high light emitting efficiency.

In one embodiment, the light emitting layer includes a compound represented by the general formula (1), and the compound represented by the general formula (1) is oriented parallel to the substrate. In one embodiment, the substrate is a film forming surface. In one embodiment, the orientation of the compound represented by the general formula (1) on the film-forming surface affects or determines the propagation direction of light emitted by the aligned compound. In one embodiment, by arranging in the propagation direction of light emitted by the compound represented by the general formula (1), the light extraction efficiency from the light emitting layer is improved.

One aspect of the present invention relates to an organic light emitting device. In one embodiment, an organic light emitting device includes a light emitting layer. In one embodiment, the light-emitting layer contains a compound represented by the general formula (1) as a light-emitting material. In one embodiment, the organic light emitting device is an organic photoluminescent device (organic PL device). In one embodiment, the organic light emitting device is an organic electroluminescent device (organic EL device). In one embodiment, the compound represented by the general formula (1) assists light emission of other light emitting materials contained in the light emitting layer (as a so-called auxiliary dopant). In one embodiment, the compound represented by the general formula (1) contained in the light emitting layer is at its lowest excited singlet state energy level, which is contained between the lowest excited singlet state energy level of the host material contained in the light emitting layer and the lowest excited singlet state energy level of another light emitting material contained in the light emitting layer.

In one embodiment, the organic photoluminescent device comprises at least one light emitting layer. In one embodiment, an organic electroluminescent device comprises at least an anode, a cathode, and an organic layer between the anode and the cathode. In one embodiment, the organic layer comprises at least a light emitting layer. In one embodiment, the organic layer comprises only the light emitting layer. In one embodiment, the organic layer includes one or more organic layers other than the light emitting layer. Examples of the organic layer include a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, and an exciton blocking layer. In an embodiment, the hole transport layer may be a hole injection and transport layer having a hole injection function, and the electron transport layer may be an electron injection and transport layer having an electron injection function. An example of an organic electroluminescent device is shown in fig. 1.

Light emitting layer:

In one embodiment, the light emitting layer is a layer in which holes and electrons injected from the anode and cathode, respectively, are recombined to form excitons. In one embodiment, the layer emits light.

In one embodiment, only a light-emitting material is used as the light-emitting layer. In one embodiment, the light emitting layer comprises a light emitting material and a host material. In one embodiment, the light-emitting material is one or more compounds represented by the general formula (1). In one embodiment, in order for the organic electroluminescent device and the organic photoluminescent device to exhibit high luminous efficiency, singlet excitons and triplet excitons generated in the light emitting material are confined in the light emitting material. In one embodiment, a host material is used in addition to the light-emitting material in the light-emitting layer. In one embodiment, the host material is an organic compound. In one embodiment, the organic compound has an excited singlet state energy and an excited triplet state energy, at least one of which is higher than those of the light emitting material of the present invention. In one embodiment, singlet excitons and triplet excitons generated in the light emitting material of the present invention are bound in the molecules of the light emitting material of the present invention. In one embodiment, singlet and triplet excitons are sufficiently constrained to promote luminous efficiency. In an embodiment, singlet excitons and triplet excitons are not sufficiently constrained, but higher luminous efficiency is still obtained, i.e., host materials capable of achieving higher luminous efficiency may be used in the present invention without particular limitation. In one embodiment, luminescence occurs in the luminescent material in the luminescent layer of the device of the invention. In an embodiment, the emitted light includes both fluorescence and delayed fluorescence. In one embodiment, the emitted light comprises light emitted from a host material. In one embodiment, the emitted light consists of light emitted from the host material. In one embodiment, the emitted light includes light emitted from the compound represented by the general formula (1) and light emitted from the host material. In one embodiment, TADF molecules and host materials are used. In one embodiment, TADF is an auxiliary dopant and excites a host material in a singlet energy lower than that in the light emitting layer and excites a light emitting material in a singlet energy higher than that in the light emitting layer.

When the compound represented by the general formula (1) is used as an auxiliary dopant, various compounds can be employed as a light-emitting material (preferably, a fluorescent material). As such a light-emitting material, a light-emitting material composed of an anthracene (anthracene) derivative, an naphthacene (TETRACENE) derivative, an naphthacene (NAPHTHACENE) derivative, a pyrene derivative, a perylene derivative, a light-emitting material containing a light-emitting material,Derivatives, rubrene derivatives, coumarin derivatives, pyran derivatives, stilbene derivatives, fluorene derivatives, anthracene (anthryl) derivatives, pyrrole methylene derivatives, terphenyl (TERPHENYLENE) derivatives, fluoranthene (Fluoranthene) derivatives, amine derivatives, quinacridone derivatives, oxadiazole derivatives, malononitrile derivatives, carbazole derivatives, julolidine (Julolidine) derivatives, thiazole derivatives, derivatives with metals (Al, zn), and the like. These exemplary backbones may or may not have substituents. Further, these example skeletons may be combined with each other.

The following exemplifies a light emitting material that can be used in combination with an auxiliary dopant having a structure represented by the general formula (1).

[ Chemical formula 16-1]

[ Chemical formula 16-2]

[ Chemical formula 16-3]

In addition, the compounds described in paragraphs 0220 to 0239 of WO2015/022974 may be particularly preferably used as the light-emitting material used together with an auxiliary dopant having a structure represented by the general formula (1).

In one embodiment, when a host material is used, the amount of the compound of the present invention in the form of 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 the present invention in the form of 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 the present invention in the form of 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 the present invention in the form of 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 the present invention in the form of a light-emitting material contained in the light-emitting layer is 10% by weight or less.

In one embodiment, the host material in the light-emitting layer is an organic compound that includes a hole transport function and an electron transport function. In one embodiment, the host material in the light emitting layer is an organic compound that prevents an increase in the wavelength of the emitted light. In one embodiment, the host material in the light-emitting layer is an organic compound having a high glass transition temperature.

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

[ chemical formula 17-1]

[ Chemical formula 17-2]

In one embodiment, the light emitting layer comprises more than 2 structurally different TADF molecules. For example, a light-emitting layer including 3 materials having high excited singlet energy levels in the order of host material, 1 st TADF molecule, and 2 nd TADF molecule can be provided. At this time, the difference Δe _ST between the lowest excited singlet energy level of the 1 st TADF molecule and the 2 nd TADF molecule and the lowest excited triplet energy level of 77K is preferably 0.3eV or less, more preferably 0.25eV or less, more preferably 0.2eV or less, more preferably 0.15eV or less, further preferably 0.1eV or less, further preferably 0.07eV or less, still further preferably 0.05eV or less, still further preferably 0.03eV or less, and particularly preferably 0.01eV or less. The concentration of 1 st TADF molecules in the light-emitting layer is preferably greater than the concentration of 2 nd TADF molecules. And, the concentration of the host material in the light emitting layer is preferably greater than the concentration of the 2 nd TADF molecule. The concentration of the 1 st TADF molecules in the light-emitting layer may be greater than or less than the concentration of the host material, or the same. In one embodiment, the composition in the light emitting layer may be set as follows: the host material is 10 to 70 wt%, the 1 st TADF molecule is 10 to 80 wt% and the 2 nd TADF molecule is 0.1 to 30 wt%. In one embodiment, the composition in the light emitting layer may be set as follows: the host material is 20 to 45 wt%, the 1 st TADF molecule is 50 to 75 wt%, and the 2 nd TADF molecule is 5 to 20 wt%. In one embodiment, the light emission quantum yield Φpl1 (a) caused by light excitation of the co-deposited film of the 1 st TADF molecule and the host material (concentration of the 1 st TADF molecule in the co-deposited film=a wt%) and the light emission quantum yield Φpl2 (a) caused by light excitation of the co-deposited film of the 2 nd TADF molecule and the host material (concentration of the 2 nd TADF molecule in the co-deposited film=a wt%) satisfy the relational expression of Φpl1 (a) > Φpl2 (a). In one embodiment, the light emission quantum yield Φpl2 (B) caused by light excitation of the co-deposited film of the 2 nd TADF molecule and the host material (concentration of the 2 nd TADF molecule in the co-deposited film=b wt%) and the light emission quantum yield Φpl2 (100) caused by light excitation of the individual film of the 2 nd TADF molecule satisfy the relational expression of Φpl2 (B) > Φpl2 (100). In one embodiment, the light emitting layer can comprise 3 structurally different TADF molecules. The compound of the present invention may be any one of a plurality of TADF compounds contained in the light-emitting layer.

In an embodiment, the light emitting layer can be composed of a material selected from the group consisting of a host material, an auxiliary dopant, and a light emitting material. In one embodiment, the light emitting layer does not contain a metal element. In an embodiment, the light emitting layer can be composed of a material composed of only 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 can be formed of a material composed of only atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms, and oxygen atoms. Alternatively, the light-emitting layer can be formed of a material composed of only 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 the present invention, the TADF material may be a known delayed fluorescent material. Preferred delayed fluorescent materials may include 0008 to 0048 and 0095 to 0133 of WO2013/154064, 0007 to 0047 and 0073 to 0085 of WO 2013/01954, 0007 to 0033 and 0059 to 0066 of WO 2013/01955, 0008 to 0071 and 0118 to 0133 of WO2013/081088, 0009 to 0046 and 0093 to 0134 of Japanese patent application publication No. 2013-256490, 0008 to 0020 and 0038 to 0040 of Japanese patent application publication No. 2013-116975, 0007 to 0032 and 0079 to 0084 of WO2013/133359, 0008 to 0034 and 0101 to 0121 of WO 2013/437, and 0101 to 0121 of WO 2013/437; the compounds contained in the general formulae described in paragraphs 0007 to 0041 and 0060 to 0069 of Japanese patent application laid-open No. 2014-9252, paragraphs 0008 to 0048 and 0067 to 0076 of Japanese patent application laid-open No. 2017-119663, paragraphs 0013 to 0025 of Japanese patent application laid-open No. 2017-119664, paragraphs 0012 to 0025 of Japanese patent application laid-open No. 2017-222623, paragraphs 0010 to 0050 of Japanese patent application laid-open No. 2017-226838, paragraphs 0012 to 0043 of Japanese patent application laid-open No. 2018-100411, and paragraphs 0016 to 0044 of WO2018/047853, are particularly exemplified compounds and can emit delayed fluorescence. And, in addition, the processing unit, the light-emitting materials of the publication Nos. 2013-253121, 2013/133359, WO2014/034535, WO2014/115743, WO2014/122895, WO2014/126200, WO2014/136758, WO2014/133121, WO2014/136860, WO2014/196585, WO2014/189122, WO 2014/1681101, WO2015/008580, WO2014/203840, WO2015/002213, WO2015/016200, WO2015/019725, WO 201470/072725, WO2015/108049, WO2015/080182, WO2015/072537, WO 2015/136240, WO2014/196585, WO2014/189122, WO2014/168101, WO 2012012015/203180, WO 2012012015/203714, WO 2015/12913720, WO 2015/12914, WO 13720, WO 2015/129137202, WO 13720, and the light-emitting materials can be preferably used. In addition, the above-mentioned publications described in this paragraph are incorporated herein by reference as part of this document.

The components of the organic electroluminescent element and the layers other than the light-emitting layer will be described below.

A substrate:

in some embodiments, the organic electroluminescent element of the present invention is supported by a substrate, wherein the substrate is not particularly limited and may be any of those substrates that have been commonly used in organic electroluminescent elements, such as those formed of glass, transparent plastic, quartz, and silicon.

Anode:

in some embodiments, the anode of the organic electroluminescent device is made of a metal, an alloy, a conductive compound, or a combination thereof. In some embodiments, the metal, alloy, or conductive compound has a large work function (above 4 eV). In some embodiments, the metal is Au. In some embodiments, the conductive transparent material may be selected from CuI, indium Tin Oxide (ITO), snO ₂, and ZnO. In some embodiments, an amorphous material such as IDIXO (In ₂O₃ -ZnO) or the like capable of forming a transparent conductive film is used. In some embodiments, the anode is a thin film. In some embodiments, the thin film is made by evaporation or sputtering. In some embodiments, the film is patterned by photolithography. In some embodiments, when a pattern may not require high precision (e.g., above about 100 μm), the pattern may be formed with a mask having a desired shape upon evaporation or sputtering of the electrode material. In some embodiments, when a material (e.g., an organic conductive compound) can be coated, wet film forming methods, such as printing and coating methods, are used. In some embodiments, the transmittance of the anode is greater than 10% and the sheet resistance of the anode is less than hundreds of ohms per square when the emitted light passes through the anode. In some embodiments, the anode has a thickness of 10 to 1,000nm. In some embodiments, the anode has a thickness of 10 to 200nm. In some embodiments, the thickness of the anode varies depending on the material used.

And (3) cathode:

In some embodiments, the cathode is fabricated from a metal (4 eV or less) with a small work function of the electrode material (referred to as an electron injecting metal), an alloy, a conductive compound, or a combination thereof. In some embodiments, the electrode material is selected from sodium, sodium-potassium alloy, magnesium, lithium, magnesium-copper mixture, magnesium-silver mixture, magnesium-aluminum mixture, magnesium-indium mixture, aluminum-aluminum oxide (Al ₂O₃) mixture, indium, lithium-aluminum mixture, and rare earth metal. In some embodiments, a mixture of an electron injection metal and a 2 nd metal is used, the 2 nd metal being a stable metal having a work function greater than the electron injection metal. In some embodiments, the mixture is selected from the group consisting of magnesium-silver mixtures, magnesium-aluminum mixtures, magnesium-indium mixtures, aluminum-aluminum oxide (Al ₂O₃) mixtures, lithium-aluminum mixtures, and aluminum. In some embodiments, the mixture increases electron injection characteristics and durability against oxidation. In some embodiments, the cathode is fabricated by forming the electrode material into a thin film by evaporation or sputtering. In some embodiments, the cathode has a sheet resistance of less than several hundred ohms per square. In some embodiments, the cathode has a thickness in the range of 10nm to 5 μm. In some embodiments, the cathode has a thickness in the range of 50 to 200 nm. In some embodiments, any one of the anode and the cathode of the organic electroluminescent element is transparent or translucent in order to transmit the emitted light. In some embodiments, the transparent or translucent electroluminescent element enhances the brightness of the emitted light.

In some embodiments, the cathode is formed with a conductive transparent material as described for the anode to form a transparent or translucent cathode. In some embodiments, the element comprises an anode and a cathode that are both transparent or translucent.

And (2) an injection layer:

The injection layer is a layer between the electrode and the organic layer. In some embodiments, the injection layer reduces a driving voltage and enhances light emission luminance. In some embodiments, the injection layer includes a hole injection layer and an electron injection layer. The injection layer can be disposed between the anode and the light emitting layer or the hole transporting layer, and between the cathode and the light emitting layer or the electron transporting layer. In some embodiments, an injection layer is present. In some embodiments, no implanted layer is present.

Examples of preferred compounds that can be used as the hole injecting material are included below.

[ Chemical formula 18]

Next, a preferable compound which can be used as an electron injection material is exemplified.

[ Chemical formula 19]

Barrier layer:

The blocking layer is a layer capable of suppressing diffusion of charges (electrons or holes) and/or excitons in the light emitting layer to the outside of the light emitting layer. In some embodiments, an electron blocking layer is between the light emitting layer and the hole transporting layer, and inhibits electrons from passing through the light emitting layer toward the hole transporting layer. In some embodiments, a hole blocking layer is between the light emitting layer and the electron transport layer and inhibits holes from passing through the light emitting layer toward the electron transport layer. In some embodiments, the blocking layer inhibits excitons from diffusing outside the light emitting layer. In some embodiments, the electron blocking layer and the hole blocking layer constitute an exciton blocking layer. The term "electron blocking layer" or "exciton blocking layer" as used herein includes a layer having the function of both an electron blocking layer and an exciton blocking layer.

Hole blocking layer:

The hole blocking layer functions as an electron transport layer. In some embodiments, the hole blocking layer inhibits holes from reaching the electron transport layer while transporting electrons. In some embodiments, the hole blocking layer enhances the probability of recombination of electrons and holes in the light emitting layer. The material for the hole blocking layer may be the same material as described for the electron transport layer.

Examples of preferred compounds that can be used for the hole blocking layer are included below.

[ Chemical formula 20]

Electron blocking layer:

Holes are transported by the electron blocking layer. In some embodiments, the electron blocking layer inhibits electrons from reaching the hole transport layer while transporting holes. In some embodiments, the electron blocking layer enhances the probability of recombination of electrons and holes in the light emitting layer. The material for the electron blocking layer may be the same material as described for the hole transport layer.

Specific examples of preferred compounds that can be used as the electron blocking material are included below.

[ Chemical formula 21]

Exciton blocking layer:

The exciton blocking layer inhibits diffusion of excitons generated via recombination of holes and electrons in the light emitting layer to the electron transport layer. In some embodiments, the exciton blocking layer enables efficient confinement (confinement) of excitons in the light-emitting layer. In some embodiments, the luminous efficiency of the device is enhanced. In some embodiments, the exciton blocking layer is adjacent to the light emitting layer on either of the anode side and the cathode side and on both sides. In some embodiments, when the exciton blocking layer is on the anode side, the layer may be between and adjacent to the hole transport layer and the light emitting layer. In some embodiments, when the exciton blocking layer is on the cathode side, the layer may be between and adjacent to the light emitting layer and the cathode. In some embodiments, a hole injection layer, an electron blocking layer, or the same layer is between the anode and an exciton blocking layer adjacent to the light emitting layer on the anode side. In some embodiments, a hole injection layer, an electron blocking layer, a hole blocking layer, or the same layer is between the cathode and an exciton blocking layer adjacent to the light emitting layer on the cathode side. In some embodiments, the exciton blocking layer comprises an excited singlet state energy and an excited triplet state energy, at least one of which is higher than the excited singlet state energy and the excited triplet state energy, respectively, of the light emitting material.

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 an injection or transport property of holes and a blocking property of electrons. 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 may be used in the present invention include, but are not limited to, triazole derivatives, oxadiazole derivatives, imidazole derivatives, carbazole derivatives, indolocarbazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, dihydropyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene (stillene) derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers (especially thiophene oligomers), or combinations thereof. In some embodiments, the hole transporting material is selected from porphyrin compounds, aromatic tertiary amines, 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 the hole transport material are included below.

[ Chemical formula 22]

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 need only have a function of transporting electrons, which are injected from the cathode into the light emitting layer. In some embodiments, the electron transport material also functions as a hole blocking material. Examples of electron transport layers that may be used in the present invention include, but are not limited to, nitro-substituted fluorene derivatives, dibenzoquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylmethane derivatives, anthraquinone dimethanes, anthrone derivatives, oxadiazole derivatives, oxazole derivatives, oxazine 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 polymeric material. Specific examples of preferred compounds that can be used as the electron transport material are included below.

[ Chemical formula 23]

Examples of the compound include compounds which are preferable as materials that can be added to each organic layer. For example, addition as a stabilizing material or the like can be considered.

[ Chemical formula 24]

Preferred materials that can be used for the organic electroluminescent element are specifically exemplified, but the materials that can be used in the present invention are not limitedly explained by the exemplified compounds below. Further, even a compound exemplified as a material having a specific function can be used as a material having another function.

The device comprises:

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 screens, computer monitors, mobile phones, and tablet computers.

In some embodiments, an electronic device includes an OLED having an anode, a cathode, and at least one organic layer including a light emitting layer between the anode and the cathode.

In some embodiments, the compositions described herein may be incorporated into a variety of photosensitive or photoactivated devices, such as OLED or photovoltaic devices. In some embodiments, the compositions may be suitable for facilitating charge transfer or energy transfer within a device and/or for use as hole transport materials. Examples of the device include an Organic Light Emitting Diode (OLED), an Organic Integrated Circuit (OIC), an organic field effect transistor (O-FET), an organic thin film transistor (O-TFT), an organic light emitting transistor (O-LET), an organic solar cell (O-SC), an organic photodetector, an organic photoreceptor, an organic field-quench device (O-FQD), a light emitting electrochemical cell (LEC), and an organic laser diode (O-laser).

Bulb or lamp:

In some embodiments, an electronic device comprises 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 comprises OLEDs of different colors. In some embodiments, the device comprises an array comprising OLED combinations. In some embodiments, the combination of OLEDs is a combination of 3 colors (e.g., RGB). In some embodiments, the combination of OLEDs is a combination of colors that are not red, green, or blue (e.g., orange and yellow-green). In some embodiments, the combination of OLEDs is a combination of 2, 4, or more than 4 colors.

In some embodiments, the device is an OLED lamp, the OLED lamp having:

A circuit board having a 1 st surface having a mounting surface and a2 nd surface opposite thereto, and defining at least one opening;

At least one OLED disposed on the mounting surface and having a structure in which the at least one OLED includes an anode, a cathode, and at least one organic layer including a light emitting layer between the anode and the cathode and emits light;

a housing for a circuit substrate; and

At least one connector is disposed at an end of the housing, and the housing and the connector define a package adapted to be mounted to a lighting device.

In some embodiments, an OLED lamp includes a plurality of OLEDs mounted on a circuit board such that light is emitted in multiple directions. In some embodiments, a portion of the light emitted in the 1 st direction is deflected to be emitted in the 2 nd direction. In some embodiments, the reflector is used to deflect light emitted in the 1 st direction.

A display or screen:

In some embodiments, the light emitting layer of the present invention may be used in a screen or display. In some embodiments, methods including, but not limited to, vacuum evaporation, deposition, evaporation, or Chemical Vapor Deposition (CVD) are used to deposit the compounds of the present invention onto a substrate. In some embodiments, the substrate is a photographic negative (photoplate) structure suitable for double sided etching, providing unique aspect ratio pixels. The screen (which may also be referred to as a mask) is used in a method of manufacturing an OLED display. The corresponding artwork pattern design promotes extremely steep and narrow tie-bars (tie-bars) between pixels in the vertical direction and larger sweep bevel openings in the horizontal direction. Thereby allowing for the pixel tight patterning required for high definition displays while optimizing chemical vapor deposition onto the TFT backplane.

The internal patterning of the pixels allows the construction of 3-dimensional pixel openings with aspect ratio variations in the horizontal and vertical directions. Furthermore, the use of imaged "stripes" or halftone circles within the pixel regions inhibits etching in certain areas until such time as these certain patterns are undercut and leave the substrate. At this time, all pixel regions are processed at the same etching rate, but the depth varies depending on the halftone pattern. Changing the size and spacing of the halftone patterns allows etching to be suppressed at different rates within the pixel, allowing localized deeper etching required to form steep vertical bevel angles.

A preferred material for the vapor deposition mask is constant-gauge steel (invar). Constant-gauge steel is a metal alloy that is cold rolled into long sheets in a steelworks. Constant-gauge steel cannot be electrodeposited onto a spinning mandrel as a nickel mask. A suitable and low cost method for forming the opening region in the evaporation mask is a wet chemical etching-based method.

In some embodiments, the screen or display pattern is a matrix of pixels on a substrate. In some embodiments, the screen or display pattern is fabricated using photolithography (lithographic), such as photolithography (photolithography) and e-beam lithography. In some embodiments, the screen or display pattern is fabricated using wet chemical etching. In further embodiments, the screen or display pattern is fabricated using plasma etching.

The manufacturing method of the device comprises the following steps:

OLED displays are typically manufactured by forming a larger motherboard and then cutting the motherboard into unit panels. In general, each cell board on the motherboard is formed by: a Thin Film Transistor (TFT) including an active layer and source/drain electrodes is formed on a base substrate, a planarization film is coated on the TFT, and a pixel electrode, a light emitting layer, a counter electrode, and an encapsulation layer are sequentially formed and cut from the mother substrate.

In another aspect of the present invention, there is provided a method of manufacturing an Organic Light Emitting Diode (OLED) display, the method including:

Forming a barrier layer on a base substrate of a motherboard;

Forming a plurality of display units from a unit of a unit panel on the barrier layer;

forming an encapsulation layer on each of the display units of the unit panels; and

And a step of coating an organic film on the interface portion between the unit plates.

In some embodiments, the barrier layer is an inorganic film formed of, for example, siNx, and an edge portion of the barrier layer is covered with an organic film formed of polyimide or acryl. In some embodiments, the organic film aids in gently cutting the master into unit panels.

In some embodiments, a 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 include a Thin Film Transistor (TFT), 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 portion is formed of the same material as that of the planarization film and is formed at the same time as the planarization film is formed. In some embodiments, the light emitting unit is connected to the TFT layer with a passivation layer, a planarization film, and an encapsulation layer therebetween, and the encapsulation layer covers and protects the light emitting unit. In some embodiments of the method of manufacture, the organic film contacts neither the display unit nor the encapsulation layer.

Each of the organic film and the planarization film may include any one of polyimide and acryl. 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 mounting a carrier substrate formed of a glass material onto one surface of a base substrate formed of polyimide before forming the barrier layer on the other surface, and separating the carrier substrate from the base substrate before cutting along the interface portion. In some embodiments, the OLED display is a flexible display.

In some implementations, the passivation layer is an organic film disposed on the TFT layer to cover the TFT layer. In some embodiments, the planarization film is an organic film formed on the passivation layer. In some embodiments, the planarization film is formed of polyimide or acryl, as is an organic film formed on an edge portion of the barrier layer. In some embodiments, the planarization film and the organic film are formed simultaneously when the OLED display is manufactured. In some embodiments, the organic film may be formed on an edge portion of the barrier layer such that a portion of the organic film directly contacts the base substrate and the remaining portion of the organic film contacts the barrier layer while surrounding the edge portion of the barrier layer.

In some embodiments, the light emitting layer has a pixel electrode, an opposite electrode, and an organic light emitting layer disposed between the pixel electrode and the opposite electrode. In some embodiments, the pixel electrode is connected to a source/drain electrode of the TFT layer.

In some embodiments, when a voltage is applied to the pixel electrode via the TFT layer, an appropriate voltage is formed between the pixel electrode and the opposite electrode, whereby the organic light emitting layer emits light, thereby forming an image. Hereinafter, an image forming unit having a TFT layer and a light emitting unit is referred to as a display unit.

In some embodiments, the encapsulation layer that covers the display unit and prevents external moisture from penetrating may be formed to have a thin film encapsulation structure in which organic films and inorganic films are alternately laminated. In some embodiments, the encapsulation layer has a film encapsulation structure in which a plurality of films are laminated. In some embodiments, the organic film coated on 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 directly contacts the base substrate, and a remaining portion of the organic film contacts the barrier layer while surrounding an edge portion of the barrier layer.

In one embodiment, the OLED display is flexible and uses a soft base substrate formed of polyimide. In some embodiments, the base substrate is formed on a carrier substrate formed of a glass material, and then the carrier substrate is separated.

In some embodiments, a barrier layer is formed on a surface of the base substrate on a side opposite the carrier substrate. In one embodiment, the barrier layer is patterned according to the size of each cell plate. For example, a barrier layer is formed according to the size of each cell plate while a base substrate is formed over the entire surface of the motherboard, thereby forming a groove at an interface portion between the cell plate barrier layers. Each cell plate may be cut along the grooves.

In some embodiments, the method of manufacturing further comprises a step of cutting along the interface portion, wherein a groove is formed in the barrier layer, at least a portion of the organic film is formed in the groove, and the groove does not penetrate into the base substrate. In some embodiments, a TFT layer of each unit plate is formed, and a passivation layer (i.e., an inorganic film) and a planarization film (i.e., an organic film) are disposed on the TFT layer to cover the TFT layer. The grooves at the interface portion are covered with an organic film formed of, for example, polyimide or acryl, while forming a planarization film formed of, for example, polyimide or acryl. This is when cracking is prevented from occurring by allowing the organic film to absorb an impact that is generated when each unit plate is cut along the groove at the interface portion. That is, if the entire barrier layer is completely exposed without an organic film, an impact generated when each unit plate is cut along the groove at the interface portion is transferred to the barrier layer, thereby increasing the risk of cracking. However, in one embodiment, since the grooves at the interface portion between the barrier layers are covered with the organic film, and the organic film absorbs the impact that would otherwise be transferred to the barrier layers, each cell plate can be gently cut, and cracks can be prevented from occurring in the barrier layers. In one embodiment, the organic film and the planarizing film covering the recess at the interface portion are spaced apart from each other. For example, if an organic film and a planarization film are connected to each other as a single layer, the organic film and the planarization film are spaced apart from each other such that the organic film is spaced apart from the display unit because external moisture may penetrate into the display unit via the planarization film and a portion of the remaining organic film.

In some embodiments, a display unit is formed by forming a light emitting unit, and an encapsulation layer is disposed on the display unit to cover the display unit. Thereby, after the motherboard is completely manufactured, the carrier substrate supporting the base substrate is separated from the base substrate. In some implementations, when the laser beam is emitted toward the carrier substrate, the carrier substrate is separated from the base substrate due to a difference in thermal expansion coefficient between the carrier substrate and the base substrate.

In some embodiments, the motherboard is cut into unit boards. In some embodiments, the motherboard is cut along the interface portion between the unit boards by using a cutter. In some embodiments, since the grooves at the interface portion along which the motherboard is cut are covered with an organic film, the organic film absorbs impact during cutting. In some embodiments, cracking may be prevented from occurring in the barrier layer during dicing.

In some embodiments, the method reduces the defect rate of the product and stabilizes its quality.

Another aspect is an OLED display having: a barrier layer formed on the base substrate; a display unit formed on the barrier layer; an encapsulation layer formed on the display unit; and an organic film coated on an edge portion of the barrier layer.

Examples

The features of the present invention will be described in more detail below with reference to synthesis examples and examples. The materials, processing contents, processing steps, and the like described below can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed in a limited manner by the following examples. The light emission characteristics were evaluated by using a source meter (2400 series, manufactured by Keithley corporation), a semiconductor parameter analyzer (Agilent Technologies Japan, manufactured by ltd.: E5273A), an optical power meter measuring device (Newport Corporation: 1930C), a spectrometer (USB 2000, manufactured by Ocean Optics corporation), a spectroradiometer (TOPCON CORPORATION: SR-3), and a streak camera (Hamamatsu Photonics K.K. C4334). The energy of HOMO and LUMO was measured by an atmospheric photoelectron spectroscopy (RIKEN KEIKI co., ltd. AC-3, etc.).

In the following synthesis examples, the compounds contained in the general formula (1) were synthesized.

Synthesis example 1

[ Chemical formula 25]

Intermediate a

A solution of 2-fluoro-9, 10-phenanthrenequinone (3.85 g,17.0 mmol) and potassium cyanide (0.055 g,0.85 mmol) in dimethylformamide (10 mL) was stirred under nitrogen for 30 minutes, trimethylcyanosilane (6.4 mL,51.0 mmol) was added, and stirred at room temperature for 3 hours. Then, dry acetonitrile (60 mL) and phosphorus tribromide (2.4 mL,25.5 mmol) were added, warmed to 50 ℃ and stirred overnight. The mixture was returned to room temperature, quenched with ammonia, extracted with dichloromethane, and dried over anhydrous magnesium sulfate. It was concentrated under reduced pressure, and the obtained solid was purified by silica gel column chromatography to obtain intermediate a (2.10 g,8.6mmol, yield 51%).

¹H NMR(400MHz,CDCl₃)δ8.77(dd,J＝9.6,4.8Hz,1H),8.69(d,J＝8.4,1H),8.40(d,J＝7.6Hz,1H),8.04(dd,J＝8.4,2.0Hz,1H),7.96-7.92(m,1H),7.87-7.83(m,1H),7.69-7.64(m,1H).

ASAP mass spectrometry: theoretical value 246.06, observed value 247.98.

Compound 15

To a solution of 5H-benzofuran [3,2-c ] carbazole (1.01 g,4.0 mmol) and potassium carbonate (0.69 g,5.0 mmol) in dimethylformamide (40 mL) was added intermediate a (0.5 g,2.0 mmol) under nitrogen and stirred overnight at 150 ℃. The mixture was returned to room temperature, quenched with water, and the precipitated solid was filtered and washed with methanol. The obtained solid was purified by silica gel column chromatography to obtain compound 15 (0.42 g,0.86mmol, yield 43%).

¹H NMR(400MHz,CDCl₃)δ9.00(d,J＝8.8Hz,1H),8.82(d,J＝8.4Hz,1H),8.68(d,J＝2.0Hz,1H),8.61-8.59(m,1H),8.46(d,J＝8.4Hz,1H),8.21(dd,J＝9.6,2.0Hz,1H),8.03-7.90(m,4H),7.75(d,J＝8.4Hz,1H),7.56-7.45(m,5H),7.40(t,J＝7.6Hz,1H).

ASAP mass spectrometry: theoretical value 483.14, observed value 484.13.

Compound 185

To a solution of 7H-bis-benzofuran [3,2-c:2',3' -g ] carbazole (0.83 g,2.4 mmol) and potassium carbonate (0.55 g,4.0 mmol) in dimethylformamide (50 mL) under nitrogen was added intermediate a (0.5 g,2.0 mmol), and stirred at 150℃for 5 hours. The mixture was returned to room temperature, quenched with water, and the precipitated solid was filtered and washed with methanol. The obtained solid was purified by silica gel column chromatography to obtain compound 185 (0.76 g,1.3mmol, yield 67%).

¹H NMR(400MHz,DMSO)δ9.06(d,J＝8.8Hz,1H),8.86(d,J＝8.0Hz,1H),8.75(d,J＝2.4Hz,1H),8.49(dd,J＝8.4,2.0Hz,1H),8.25(dd,J＝8.8,2.0Hz,1H),8.06-8.02(m,5H),7.97-7.93(m,3H),7.55-7.41(m,6H).

ASAP mass spectrometry: theoretical value 573.15, observed value 574.26.

Synthesis example 2

[ Chemical formula 26]

Intermediate b

A solution of 3-fluoro-9, 10-phenanthrenequinone (2.19 g,9.7 mmol) and potassium cyanide (0.031 g,0.48 mmol) in dimethylformamide (5 mL) was stirred under nitrogen for 30 minutes, trimethylcyanosilane (3.6 mL,29.1 mmol) was added, and stirred at room temperature for 3 hours. Then, dry acetonitrile (30 mL) and phosphorus tribromide (1.4 mL,14.5 mmol) were added, warmed to 50 ℃ and stirred overnight. The mixture was returned to room temperature, quenched with ammonia, extracted with dichloromethane, and dried over anhydrous magnesium sulfate. It was concentrated under reduced pressure, and the obtained solid was purified by silica gel column chromatography to obtain intermediate b (0.88 g,3.6mmol, yield 37%).

ASAP mass spectrometry: theoretical value 246.06, observed value 247.76.

Compound 632

To a solution of 7H-bis-benzofuran [3,2-c:2',3' -g ] carbazole (1.0 g,2.8 mmol) and potassium carbonate (0.67 g,4.8 mmol) in dimethylformamide (50 mL) was added intermediate b (0.6 g,2.4 mmol) under nitrogen, and the mixture was stirred at 150℃for 5 hours. The mixture was returned to room temperature, quenched with water, and the precipitated solid was filtered and washed with methanol. The obtained solid was purified by silica gel column chromatography to obtain compound 632 (0.77 g,1.3mmol, yield 55%).

¹H NMR(400MHz,DMSO)δ9.43(d,J＝9.2Hz,1H),9.21(d,J＝8.0Hz,1H),8.58(d,J＝2.0Hz,1H),8.44(dd,J＝9.2,2.4Hz,1H),8.37(dd,J＝8.4,1.2Hz,1H),8.28(d,J＝8.4Hz,2H),8.22-8.21(m,2H),8.15-8.11(m,1H),8.07-8.04(m,1H),7.99-7.96(m,2H),7.64-7.54(m,4H),7.48-7.44(m,2H).

ASAP mass spectrometry: theoretical value 573.15, observed value 574.24.

Compound 894

To a solution of 10, 15-dihydro-15-phenyl-benzofuran [3,2-a ] indolo [3,2-c ] carbazole (0.55 g,1.32 mmol) and potassium carbonate (0.31 g,2.2 mmol) in dimethylformamide (50 mL) under nitrogen was added intermediate b (0.28 g,1.1 mmol) and stirred at 150℃for 6 hours. The mixture was returned to room temperature, quenched with water, and the precipitated solid was filtered and washed with methanol. The obtained solid was purified by silica gel column chromatography to obtain compound 894 (0.26 g,0.41mmol, yield 37%).

¹H NMR(400MHz,DMSO)δ9.20(d,J＝2.0Hz,1H),8.60-8.58(m,1H),8.35-8.15(m,5H),7.95-7.93(m,1H),7.87-7.82(m,2H),7.74-7.67(m,5H),7.63-7.59(m,2H),7.48-7.39(m,3H),7.28(d,J＝8.4Hz,1H),7.07-7.03(m,1H),6.82-6.78(m,1H),6.23(d,J＝8.4Hz,1H).

ASAP mass spectrometry: theoretical value 648.20, observed value 649.64.

Synthesis example 3

[ Chemical formula 27]

Intermediate c

A solution of 2, 7-fluoro-9, 10-phenanthrenequinone (3.1 g,12.7 mmol) and potassium cyanide (0.04 g,0.63 mmol) in dimethylformamide (12 mL) was stirred under nitrogen for 30 minutes, trimethylcyanosilane (4.77 mL,38.1 mmol) was added, and stirred at room temperature for 3 hours. Then, dry acetonitrile (72 mL) and phosphorus tribromide (1.5 mL,15.2 mmol) were added, warmed to 50 ℃ and stirred overnight. The mixture was returned to room temperature, quenched with ammonia, extracted with dichloromethane, and dried over anhydrous magnesium sulfate. It was concentrated under reduced pressure, and the obtained solid was purified by silica gel column chromatography to obtain intermediate c (0.71 g,2.68mmol, yield 21%).

¹H NMR(400MHz,CDCl₃)δ8.70(dd,J＝9.2,4.8Hz,2H),8.05(dd,J＝8.8,2.8Hz,2H),7.71-7.67(m,2H)

ASAP mass spectrometry: theoretical value 246.05, observed value 264.02.

Compound 21949

To a solution of 12H 1 benzothieno [2,3-a ] carbazole (1.0 g,3.78 mmol) and potassium carbonate (1.04 g,7.55 mmol) in nitrobenzene (16 mL) under nitrogen was added intermediate c (0.4 g,1.51 mmol) and stirred overnight at 195 ℃. The mixture was returned to room temperature, hexane was added, the precipitated solid was filtered, and hexane cleaning was performed. The obtained solid was purified by silica gel column chromatography to obtain compound 21949 (0.12 g,0.16mmol, yield 11%).

¹H NMR(400MHz,DMSO)δ9.19(d,J＝8.8Hz,2H),8.76(d,J＝2.0Hz,2H),8.37-8.25(m,8H),8.53-7.46(m,5H),8.45-7.40(m,5H),7.17-7.14(m,4H).

ASAP mass spectrometry: theoretical value 770.16, observed value 771.42.

Compound 34941

To a solution of 5, 12-dihydro-12-phenylindolo [3,2-a ] carbazole (3.1 g,9.46 mmol) and cesium carbonate (6.0 g,18.5 mmol) in nitrobenzene (40 mL) under nitrogen was added intermediate c (1.0 g,3.7 mmol) and stirred at 195℃for 1 hour. The mixture was returned to room temperature, hexane was added, the precipitated solid was filtered, and hexane cleaning was performed. The obtained solid was purified by silica gel column chromatography to obtain compound 34941 (0.77 g,0.86mmol, yield 23%).

¹H NMR(400MHz,DMSO)δ9.49(d,J＝9.2Hz,2H),8.50(d,J＝2.0Hz,2H),8.41(dd,J＝8.4,1.6Hz,2H),8.34(d,J＝8.4Hz,2H),8.23(d,J＝7.6Hz,2H),7.74-7.66(m,10H),7.51-7.47(m,4H),7.38-7.23(m,8H),6.79(t,J＝4.4Hz,2H),5.87(d,J＝8.4Hz,2H).

ASAP mass spectrometry: theoretical value 888.30, observed value 890.40.

Compound 35837

To a solution of 5, 7-dihydro-5-phenylindolo [2,3-b ] carbazole (0.2 g,0.6 mmol) and potassium carbonate (0.19 g,1.35 mmol) in nitrobenzene (3 mL) under nitrogen was added intermediate c (0.072 g,0.27 mmol) and stirred at 195℃for 1 hour. The mixture was returned to room temperature, hexane was added, the precipitated solid was filtered, and hexane cleaning was performed. The obtained solid was purified by silica gel column chromatography to obtain compound 35837 (0.11 g,0.12mmol, yield 45%).

¹H NMR(400MHz,DMSO)δ8.83-8.80(m,4H),8.69(d,J＝2.0Hz,2H),8.25(d,J＝7.6Hz,4H),8.18(dd,J＝8.8,2.0Hz,2H),7.67-7.60(m,8H),7.51-7.31

ASAP mass spectrometry: theoretical value 888.30, observed value 889.56.

Compound 8061

To a solution of 5H-benzofuran [3,2-c ] carbazole (0.284 g,1.2 mmol) and potassium carbonate (0.15 g,1.2 mmol) in dimethylformamide (10 mL) under nitrogen was added intermediate c (0.1 g,0.37 mmol) and stirred at 150℃for 2H. The mixture was returned to room temperature, quenched with water, and the precipitated solid was filtered and washed with methanol. The obtained solid was purified by silica gel column chromatography to obtain compound 8061 (0.14 g,0.19mmol, yield 51%).

¹H NMR(400MHz,DMSO)δ9.36(d,J＝8.0Hz,1H),9.28(s,1H),8.49-8.39(m,4H),8.21-8.15(m,4H),8.05-8.03(m,2H),8.87-7.85(m,2H),7.66-7.43(m,12H).

ASAP mass spectrometry: theoretical value 738.21, observed value 739.25.

Synthesis example 4

[ Chemical formula 28]

Intermediate d

A solution of 2-fluoro-5-formylbenzonitrile (4.3 g,19.0 mmol), copper powder (2.9 g,47.5 mmol) and copper (I) 2-thiophenecarboxylic acid (0.9 g,4.75 mmol) in dimethyl sulfoxide (100 mL) was stirred at 50℃overnight under nitrogen flow. Then, the mixture was returned to room temperature, quenched with water, extracted with ethyl acetate, and dried with anhydrous magnesium sulfate. It was concentrated under reduced pressure, and the obtained solid was purified by silica gel column chromatography to obtain intermediate d (2.36 g,7.7mmol, yield 82%).

¹H NMR(400MHz,CDCl₃)δ9.76(s,2H),8.26(d,J＝6.4Hz,2H),7.16(d,J＝8.8Hz,2H).

ASAP mass spectrometry: theoretical value 296.04, observed value 297.18.

Intermediate e

A toluene solution (70 mL) of intermediate d (2.3 g,7.7 mmol) and p-toluenesulfonyl hydrazide (p-toluenesulfonylhydrazide) (2.9 g,15.8 mmol) was stirred at 60℃for 30 minutes under nitrogen flow and toluene (150 mL) was added to return to room temperature. Then, add to the reaction mass(2.3 G), lithium t-butoxide (1.8 g,23.1 mmol), rhodium (II) acetate (dimer) (0.05 g,0.11 mmol), toluene (180 mL) and stirred at 90℃for 2 hours. Then, the mixture was returned to room temperature, and subjected to short column chromatography (ethyl acetate) based on silica gel, thereby obtaining a crude product. This was purified by silica gel column chromatography to obtain intermediate e (1.84 g,6.97mmol, yield 91%).

¹H NMR(400MHz,CDCl₃)δ8.30-8.27(m，4H)，7.81(s，2H).

ASAP mass spectrometry: theoretical value 264.05, observed value 265.02.

Compound 434559

To a solution of 5, 12-dihydro-12-phenylindolo [3,2-a ] carbazole (1.4 g,4.18 mmol) and potassium carbonate (0.78 g,5.7 mmol) in dimethylformamide (50 mL) was added intermediate e (0.5 g,1.9 mmol) under a nitrogen flow and stirred at 150℃for 1 hour. The mixture was returned to room temperature, quenched with water, and the precipitated solid was filtered and washed with methanol. The obtained solid was purified by silica gel column chromatography to obtain compound 434559 (1.57 g,1.76mmol, yield 92%).

¹H NMR(400MHz,DMSO)δ8.74(s,2H),8.64(s,2H),8.14-8.06(m,6H),7.64-7.53(m,10H),7.34-7.27(m,6H),7.18-7.13(m,2H),7.08-7.04(m,4H),6.78-6.74(m,2H),5.86(d,J＝8.4Hz,2H).

ASAP mass spectrometry: theoretical value 888.30, observed value 889.75.

Synthesis example 5

[ Chemical formula 29]

Intermediate f

To a mixture of 2-bromo-4, 5-difluorobenzaldehyde (6.6 g,44.0 mmol), 2-formylphenylboronic acid (8.8 g,40.0 mmol), tetrakis triphenylphosphine palladium (2.31 g,2.0 mmol) and potassium carbonate (11.0 g,80.0 mmol) was added a previously degassed mixed solution of tetrahydrofuran (225 mL)/water (75 mL) under a nitrogen stream, the temperature was raised to 80℃and the reaction was allowed to proceed overnight. After the reaction, the mixture was cooled to room temperature, water was added thereto, and filtration and extraction were performed. The obtained mixture was purified by silica gel column chromatography to obtain 4, 5-difluoro- [1,1 '-biphenyl ] -2,2' -dicarboxaldehyde f (9.30 g, yield 94.5%).

¹H NMR(400MHz,CDCl₃)δ9.76(s,1H),9.53(d,J＝4.0Hz,1H),7.98(d,J＝8.0Hz,1H),7.93(t,J＝8.0Hz,1H),7.67(m,3H),7.41(d,J＝8.0Hz,1H).

ASAP mass spectrometry: theoretical value 246.21, observed value 246.94.

Intermediate g

To a mixture of 4, 5-difluoro- [1,1 '-biphenyl ] -2,2' -dicarboxaldehyde f (9.30 g,38.0 mmol), copper (I) chloride (0.375 g,3.8 mmol) was added dimethyl sulfoxide (200 mL). To this solution was added dropwise 70% t-butyl hydroperoxide solution (26 mL,189 mmol) while stirring at room temperature for 10 minutes. After the reaction, the mixture was cooled to room temperature, water was added thereto, and filtration and extraction were performed. After purifying the obtained mixture by silica gel column chromatography, recrystallization was performed, whereby 2, 3-difluoro-9, 10-phenanthrenequinone g (6.1 g, yield 66%) was obtained.

¹H NMR(400MHz,CDCl₃)δ8.20(d,J＝8.0Hz,1H),7.99(t,J＝8.0Hz,1H),7.79(m,3H),7.51(t,J＝8.0Hz,1H).

ASAP mass spectrometry: theoretical value 244.20, observed value 244.99.

Intermediate h

A solution of 2, 3-difluoro-9, 10-phenanthrenequinone g (3.0 g,12.29 mmol) and potassium cyanide (0.080 g,1.23 mmol) in dimethylformamide (30 mL) was stirred under nitrogen flow for 30 min, trimethylcyanosilane (4.6 mL,36.9 mmol) was added and stirred at room temperature for 3 h. Then, dry acetonitrile (200 mL) and phosphorus tribromide (3.5 mL,36.9 mmol) were added, warmed to 70 ℃ and stirred overnight. The mixture was returned to room temperature, quenched with ammonia, extracted with dichloromethane, and dried over anhydrous magnesium sulfate. It was concentrated under reduced pressure, and the obtained solid was purified by silica gel column chromatography to obtain intermediate h (1.64 g,6.2mmol, yield 50%).

¹H NMR(400MHz,CDCl₃)δ8.59(d,J＝7.8Hz,1H),8.52(dd,J＝11.5,7.3Hz,1H),8.43(dd,J＝9.2,0.9Hz,1H),8.19(dd,J＝10.1,7.8Hz,1H),7.98(td,J＝7.3,1.4Hz,1H),7.91(td,J＝7.3,1.4Hz,1H).

ASAP mass spectrometry: theoretical value 264.23, observed value 265.10.

Compound 806951

To a solution of 5H-2-phenylbenzofuran [3,2-c ] carbazole (2.52 g,7.57 mmol) and potassium carbonate (1.25 g,9.08 mmol) in dimethylformamide (100 mL) was added intermediate H (0.800 g,3.03 mmol) under nitrogen and stirred at 140℃for 4H. The mixture was returned to room temperature, quenched with water, and the precipitated solid was filtered and washed with methanol. The obtained solid was purified by silica gel column chromatography to obtain compound 806951 (1.72 g,1.92mmol, yield 64%).

¹H NMR(400MHz,CDCl₃)δ9.33(d,J＝2.8Hz,1H),8.97(dd,J＝3.7,1.4Hz,1H),8.75(t,J＝6.0Hz,1H),8.50(d,J＝8.2,1H),8.43(d,J＝6.4,2H),8.02-7.92(m,2H),7.86(d,J＝7.8,1H),7.82(dd,J＝7.3,3.2Hz,1H),7.69-7.52(m,8H),7.46-7.22(m,15H).

ASAP mass spectrometry: theoretical value 891.00, observed value 891.59.

Compound 806993

To a solution of 5, 12-dihydro-12-phenylindolo [3,2-a ] carbazole (2.45 g,7.38 mmol) and potassium carbonate (1.43 g,10.3 mmol) in dimethylformamide (100 mL) was added intermediate h (0.780 g,2.95 mmol) under nitrogen and stirred at 150℃for 9 hours. The mixture was returned to room temperature, quenched with water, and the precipitated solid was filtered and washed with methanol. The obtained solid was purified by silica gel column chromatography to obtain compound 806993 (0.598 g, 0.6755 mmol, yield 22.9%).

¹H NMR(400MHz,CDCl₃)δ9.32(d,J＝4.6Hz,1H),8.97(d,J＝3.7Hz,1H),8.52-8.46(m,1H),8.03-7.89(m,4H),7.76-7.7.69(m,2H),7.66-7.51(m,3H),7.39-7.21(m,9H),7.19-7.11(m,3H),7.02-6.96(m,1H),6.82-6.75(m,1H),6.72-6.62(m,3H),6.61-6.54(m,1H),6.61-6.54(m,1H),6.51-6.39(m,2H),5.86(d,J＝8.2Hz,1H),5.61-5.48(m,2H).

ASAP mass spectrometry: theoretical value 889.03, observed value 889.68.

Synthesis example 5

[ Chemical formula 30]

Intermediate i

To a mixture of 3,4, 5-trifluorobenzaldehyde (25.0 g,156 mmol), N-bromosuccinimide (27.8 g,156 mmol), palladium (II) acetate (7.01 g,31.2 mmol), 2-amino-4-nitrobenzoic acid (14.2 g,78.1 mmol), silver trifluoroacetate (3.45 g,15.6 mmol) and p-toluenesulfonic acid monohydrate (29.7 g,156 mmol) was added a mixed solution of dichloromethane (500 mL)/trifluoroacetic acid (500 mL) under nitrogen flow, the temperature was raised to 90℃and the mixture was reacted overnight. After the reaction, the mixture was cooled to room temperature, filtered and extracted. The obtained mixture was purified by silica gel column chromatography to obtain intermediate i (13.0 g, yield 34.8%).

¹H NMR(400MHz,CDCl₃)δ10.25(s,1H)，7.64(t,J＝8.8Hz,1H)

ASAP mass spectrometry: theoretical value 237.94, observed value 239.07.

Intermediate j

To a mixture of intermediate i (13.0 g,54.4 mmol), 2-formylphenylboronic acid (8.97 g,59.8 mmol), bis (triphenylphosphine) palladium (II) dichloride (1.91 g,2.72 mmol) and potassium carbonate (15.0 g,109 mmol) was added a mixed solution of toluene (540 mL)/ethanol (360 mL)/water (180 mL) under a nitrogen stream, the temperature was raised to 90℃and the reaction was allowed to proceed overnight. After the reaction, the mixture was cooled to room temperature, water was added thereto, and filtration and extraction were performed. The obtained mixture was purified by silica gel column chromatography to obtain intermediate j (3.94 g, yield 27.4%).

¹H NMR(400MHz,CDCl₃)δ9.94(s,1H),9.58(d,J＝3.2Hz,1H),8.08-8.04(m,1H),7.76-7.67(m,3H),7.35(dd,J＝9.4,5.7Hz,1H).

ASAP mass spectrometry: theoretical value 264.04, observed value 265.06.

Intermediate k

To a mixture of intermediate j (3.94 g,14.9 mmol) and copper (I) chloride (0.295 g,2.98 mmol) was added dimethyl sulfoxide (150 mL). To this solution was added dropwise 70% t-butyl hydroperoxide solution (6.13 mL,44.7 mmol) and stirred at room temperature for 16 hours. After the reaction, water was added to the mixture to carry out filtration and extraction. After purifying the obtained mixture by silica gel column chromatography, recrystallization was performed, thereby obtaining intermediate k (0.97 g, yield 25%).

¹H NMR(400MHz,CDCl₃)δ8.39(d,J＝8.2Hz,1H),8.26(d,J＝7.8Hz,1H),7.91(t,8.2Hz,1H),7.78(t,7.8Hz,1H),7.56(t,J＝7.6Hz,1H)

ASAP mass spectrometry: theoretical value 262.02, observed value 263.01.

Intermediate m

A solution of intermediate k (1.55 g,5.91 mmol) and potassium cyanide (0.038 g,0.59 mmol) in dimethylformamide (7 mL) was stirred under nitrogen for 30 min, trimethylcyanosilane (2.22 mL,17.7 mmol) was added, and stirred at room temperature for 3 h. Then, dry acetonitrile (42 mL) and phosphorus tribromide (1.68 mL,17.7 mmol) were added, warmed to 80 ℃ and stirred overnight. The mixture was returned to room temperature, quenched with ammonia, extracted with dichloromethane, and dried over anhydrous magnesium sulfate. It was concentrated under reduced pressure, and the obtained solid was purified by silica gel column chromatography to obtain intermediate m (0.18 g,0.64mmol, yield 10%).

¹H NMR(400MHz,CDCl₃)δ9.15-9.12(m,1H),8.48(dd,J＝8.2,1.4Hz,1H),8.12-8.07(m,1H),8.04-7.99(m,1H),7.95(td,J＝7.6,1.2Hz,1H).

ASAP mass spectrometry: theoretical value 282.04, observed value 283.11.

Compound 1006742

To a solution of 5H-benzofuran [3,2-c ] carbazole (0.42 g,1.6 mmol) and potassium carbonate (0.25 g,1.8 mmol) in nitrobenzene (16 mL) under nitrogen was added intermediate m (0.13 g,0.46 mmol) and stirred at 190℃for 16H. The mixture was returned to room temperature, quenched with water, and the precipitated solid was filtered and washed with methanol. The obtained solid was purified by silica gel column chromatography to obtain compound 1006742 (0.060 g,0.060mmol, yield 13%).

¹H NMR(400MHz,CDCl₃)δ9.11(t,J＝1.8Hz,1H),8.43(d,J＝8.2Hz,1H),8.23-8.15(m,2H),7.87-7.57(m,7H),7.52-7.28(m,9H),7.24-6.78(m,15H).

ASAP mass spectrometry: theoretical value 993.27, observed value 994.65.

Example 1 preparation and evaluation of films

The compound 15 and mCBP were vapor-deposited from different vapor deposition sources on a quartz substrate by a vacuum vapor deposition method under a vacuum degree of less than 1×10 ^-3 Pa, whereby a thin film having a concentration of 20 wt% of the compound 15 was formed at a thickness of 100 nm.

Compounds 185, 632, 894, 21949, 34941, 35837, 8061, 434559, 806951 were used in place of compound 15, respectively, and a thin film was formed in the same manner.

When each of the formed films was irradiated with excitation light of 300nm, the maximum luminescence wavelength (. Lamda.max) and the photoluminescence quantum yield (PLQY) were measured. The energy of HOMO and the energy of LUMO were also measured. The results are shown in Table 3.

TABLE 3

Example 2 fabrication and evaluation of organic electroluminescent device

Each thin film was laminated on a glass substrate on which an anode composed of Indium Tin Oxide (ITO) having a film thickness of 50nm was formed by a vacuum deposition method at a vacuum degree of 5.0×10 ^-5 Pa. First, HAT-CN with a thickness of 10nm was formed on ITO, and NPD with a thickness of 30nm was formed thereon. Next, tris-PCz was formed to a thickness of 10nm, and EBL1 was further formed to a thickness of 5 nm. Subsequently, EBL1 and compound 15 were co-evaporated from different vapor deposition sources to form a 40nm thick layer, which was used as a light-emitting layer. The concentration of the compound 15 in the light-emitting layer was 40 mass%. Next, after SF3-TRZ having a thickness of 10nm was formed, liq and SF3-TRZ were co-evaporated from different evaporation sources to form a layer having a thickness of 30 nm. The concentrations of Liq and SF3-TRZ in this layer were 30 mass% and 70 mass%, respectively. Further, a cathode was formed by forming Liq at a thickness of 2nm, followed by aluminum (Al) deposition at a thickness of 100nm, and was used as an organic electroluminescent element.

185, 632, 806951, 806993 And 8061 were used instead of the compound 15, respectively, and organic electroluminescent elements were fabricated in the same order.

The driving voltage at 2mA/cm ², the maximum External Quantum Efficiency (EQE), and the time required for the emission intensity to decrease to 95% of the initial emission at the time of continuous energization at 5.5mA/cm ² were measured for each of the organic electroluminescent elements produced (LT 95). The results are shown in Table 4.LT95 is shown as the relative value when compound 632 is set to 1.

TABLE 4

The organic electroluminescent element using the compound 8061 also showed a high EQE of 9.7%.

The compound represented by the general formula (1) has a high photoluminescence quantum yield and is excellent as a light-emitting material. The organic electroluminescent element using the compound represented by the general formula (1) has high luminous efficiency, low driving voltage and long life.

[ Chemical formula 31]

Symbol description

1-Substrate, 2-anode, 3-hole injection layer, 4-hole transport layer, 5-luminescent layer, 6-electron transport layer, 7-cathode.

Claims

1. A compound represented by the following general formula (1),

[ Chemical formula 1]

In the general formula (1), R ¹～R¹⁰ each independently represents a hydrogen atom, a deuterium atom or a substituent, wherein 1 or 2 of R ¹～R¹⁰ represent cyano groups, 1 to 4 of R ¹～R¹⁰ represent donor groups bonded in a 5-membered ring,

R ¹ and R ²、R² and R ³、R³ and R ⁴、R⁴ and R ⁵、R⁵ and R ⁶、R⁶ and R ⁷、R⁷ and R ⁸、R⁸ and R ⁹、R⁹ and R ¹⁰、R¹⁰ and R ¹ may be bonded to each other to form a cyclic structure.

2. The compound according to claim 1, wherein,

The donor group bonded with a 5-membered ring is a substituted or unsubstituted ring fused indol-1-yl group.

3. The compound according to claim 1, wherein,

The donor group bonded with a 5-membered ring is a substituted or unsubstituted ring-fused carbazole-9-yl.

4. The compound according to claim 1, wherein,

The donor group bonded by the 5-membered ring is a ring-condensed carbazole-9-yl substituted by a substituent.

5. The compound according to claim 1, wherein,

The donor group bonded with a 5-membered ring is a ring-fused carbazole-9-yl substituted with an aryl or heteroaryl group.

6. The compound according to claim 1, wherein,

The donor group bonded by a 5-membered ring is a ring-fused carbazole-9-yl substituted by aryl.

7. The compound according to claim 3, wherein,

The ring-fused carbazole-9-yl group is a carbazole-9-yl group obtained by fusing a ring having 1 or more atoms selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom as ring skeleton constituent atoms.

8. The compound according to claim 3, wherein,

The ring-fused carbazole-9-yl group is a carbazole-9-yl group obtained by fusing a ring having 1 or more atoms selected from the group consisting of an oxygen atom and a sulfur atom as ring skeleton constituent atoms.

9. The compound according to claim 3, wherein,

2 Of R ¹～R¹⁰ are cyano groups and 2 of R ¹～R¹⁰ are substituted or unsubstituted ring-fused carbazole-9-yl groups.

10. The compound according to claim 3, wherein,

2 Of R ¹～R¹⁰ are the same substituted or unsubstituted ring-fused carbazol-9-yl.

11. The compound according to claim 3, wherein,

2 Of R ¹～R¹⁰ are cyano groups and 1 of R ¹～R¹⁰ are substituted or unsubstituted ring-fused carbazole-9-yl groups.

12. The compound according to claim 1, wherein,

R ⁹ and R ¹⁰ are cyano.

13. The compound according to claim 1, wherein,

R ² and R ⁷ are cyano.

14. The compound of claim 1, having a line symmetrical structure.

15. A luminescent material consisting of the compound according to any one of claims 1 to 14.

16. A delayed phosphor composed of the compound according to any one of claims 1 to 14.

17. A membrane comprising the compound of any one of claims 1 to 14.

18. An organic semiconductor element comprising the compound according to any one of claims 1 to 14.

19. An organic light-emitting element comprising the compound according to any one of claims 1 to 14.

20. The organic light-emitting device of claim 19, wherein,

21. The organic light-emitting device of claim 20, wherein,

22. The organic light-emitting device of claim 20, wherein,

23. The organic light-emitting device of claim 20, wherein,

The amount of light emitted from the compound is greatest among the materials contained in the element.

24. The organic light-emitting device of claim 22 wherein,

25. The organic light-emitting element according to any one of claims 19 to 24, which is an organic electroluminescent element.

26. The organic light-emitting element according to any one of claims 19 to 24, which emits delayed fluorescence.