KR20240068056A - Compounds, light-emitting materials and light-emitting devices - Google Patents

Abstract

Compounds represented by the following general formula are useful as light-emitting materials. R ¹ to R ¹⁰ represent a hydrogen atom, a deuterium atom or a substituent, but 1 or 2 of R ¹ to R ¹⁰ represent a cyano group, and 1 to 4 of R ¹ to R ¹⁰ are bonded to a 5-membered ring. It represents the donor penis.

Description

Compounds, light-emitting materials and light-emitting devices

The present invention relates to compounds useful as light-emitting materials and light-emitting devices using the same.

Research is being actively conducted to increase the luminous efficiency of light-emitting devices such as organic electroluminescence devices (organic EL devices). In particular, various studies have been conducted to increase luminous efficiency by newly developing and combining electron transport materials, hole transport materials, and light emitting materials that constitute organic electroluminescence devices. Among them, research on organic electroluminescence devices using delayed fluorescent materials can also be seen.

The delayed fluorescent material generates inverse intersystem crossing from the triplet excited state to the singlet excited state in the excited state, and then emits fluorescence when returning from the singlet excited state to the ground state. It is a material that radiates. Fluorescence by this route is called delayed fluorescence because it is observed later than fluorescence from a singlet excited state (ordinary fluorescence) generated directly from the ground state. Here, for example, when a luminescent compound is excited by injection of a carrier, the probability of occurrence of a singlet excited state and a triplet excited state is statistically 25%:75%, so the There is a limit to improving luminous efficiency using fluorescence alone. On the other hand, in delayed fluorescent materials, not only singlet excited states but also triplet excited states can be used for fluorescence emission through the above-described reverse intersystem crossing path, so higher luminous efficiency is obtained compared to ordinary fluorescent materials. .

After this principle became clear, various delayed fluorescent materials were discovered through various research. However, if the material emits delayed fluorescence, it is not useful as an immediate light-emitting material. Among delayed fluorescent materials, many of them have poor durability when used as organic light-emitting devices and pose problems in terms of practicality. In addition, when used as an organic electroluminescence element, the driving voltage may be high or the luminous efficiency may be low. Therefore, the reality is that there are many delayed fluorescent materials that have room for improvement in terms of practicality. In addition, it has been pointed out that problems also exist with phthalonitrile-based compounds known as delayed fluorescent materials. For example, 2CzPN, which has the structure below, is a material that emits delayed fluorescence, but has the problems of low luminous efficiency and low durability (see Non-Patent Document 1).

[Formula 1]

Organic Electronics 14(2013) 2721-2726

While it has been pointed out that such problems exist, it is difficult to say that a sufficient explanation has been made regarding the relationship between the chemical structure and properties of delayed fluorescent materials. For this reason, it is currently difficult to generalize the chemical structures of compounds useful as light-emitting materials, and many points are unclear.

Under such circumstances, the present inventors have conducted research with the aim of providing more useful compounds as light-emitting materials for light-emitting devices. In addition, an intensive study was conducted with the goal of deriving and generalizing the general formulas of compounds more useful as light-emitting materials.

As a result of intensive studies to achieve the above object, the present inventors discovered that among cyanophenanthrene derivatives, compounds having a structure that satisfies specific conditions are useful as light-emitting materials. The present invention has been proposed based on this knowledge, and specifically has the following configuration.

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

[Formula 2]

[In General Formula (1), R ¹ to R ¹⁰ each independently represent a hydrogen atom, a deuterium atom, or a substituent. However, 1 or 2 of R ¹ to R ¹⁰ represents a cyano group, and 1 to 4 of R ¹ to R ¹⁰ represents a donor group bonded to a 5-membered ring.

R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , R ¹⁰ and R ¹ may be combined with each other to form a cyclic structure.]

[2] The compound according to [1], wherein the donor group bonded to the 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 to the 5-membered ring is a substituted or unsubstituted ring-condensed carbazol-9-yl group.

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

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

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

[7] The ring-condensed carbazol-9-yl group is a carbazol-9-yl group in which a ring containing at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom as a ring skeleton atom is condensed, [3] The compound according to any one of to [6].

[8] The ring-condensed carbazol-9-yl group is a carbazol-9-yl group in which a ring is condensed with at least one atom selected from the group consisting of an oxygen atom and a sulfur atom as a ring skeleton constituent atom, [3] to [6]. ] Compound according to any one of the above.

[9] In any one of [3] to [8], where two of R ¹ to R ¹⁰ are cyano groups and two of R ¹ to R ¹⁰ are substituted or unsubstituted ring-condensed carbazol-9-yl groups. Compounds described.

[10] The compound according to any one of [3] to [9], wherein two of R ¹ to R ¹⁰ are the same substituted or unsubstituted ring-condensed carbazol-9-yl group.

[11] In any one of [3] to [10], two of R ¹ to R ¹⁰ are cyano groups, and one of R ¹ to R ¹⁰ is a substituted or unsubstituted ring-condensed carbazol-9-yl group. Compounds described.

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

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

[14] The compound according to any one of [1] to [13], which has an axisymmetric structure.

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

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

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

[18] An organic semiconductor device containing the compound according to any one of [1] to [14].

[19] An organic light-emitting device containing the compound according to any one of [1] to [14].

[20] The organic light-emitting device according to [19], wherein the device has a layer containing the compound, and the layer also contains a host material.

[21] The layer containing the compound includes a delayed fluorescent material in addition to the compound and the host material, and the lowest singlet excitation energy of the delayed fluorescent material is lower than that of the host material and higher than that of the compound, [20] The organic light emitting device described in .

[22] The organic light-emitting device according to [20], wherein the device has a layer containing the compound, and the layer also includes a light-emitting material having a structure different from that of the compound.

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

[24] The organic light-emitting device according to [22], wherein the amount of light emitted from the light-emitting material is greater than the amount of light emitted from the compound.

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

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

The compound of the present invention is useful as a light-emitting material. Additionally, the compounds of the present invention include compounds that emit delayed fluorescence. In addition, organic light-emitting devices using the compounds of the present invention include devices with high luminous efficiency, devices with high durability, and devices with low driving voltage.

1 is a schematic cross-sectional view showing an example of the layer structure of an organic electroluminescence device.

Below, the contents of the present invention will be described in detail. The description of the structural requirements described below may be based on representative embodiments or specific examples of the present invention, but the present invention is not limited to such embodiments or specific examples. In addition, in this specification, the numerical range indicated using "~" means a range that includes the numerical values written before and after "~" as the lower limit and upper limit. Additionally, some or all of the hydrogen atoms present in the molecule of the compound used in the present invention may be replaced with deuterium atoms ( ^2H , deuterium D). In the chemical structural formula of this specification, the hydrogen atom is indicated as H or is omitted. For example, when the indication of the atom bonded to the carbon atom forming the ring skeleton of the benzene ring is omitted, H is assumed to be bonded to the carbon atom forming the ring skeleton at the location where the indication is omitted. In the chemical structural formula of this specification, the deuterium atom is indicated as D.

[Compound represented by general formula (1)]

[Formula 3]

In General Formula (1), R ¹ to R ¹⁰ each independently represent a hydrogen atom, a deuterium atom, or a substituent.

One or two of R ¹ to R ¹⁰ represent a cyano group.

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

In one aspect of the invention, the number of cyano groups is two. For example, one of R ¹ to R ⁴ and R ¹⁰ is a cyano group, and one of R ⁵ to R ⁹ is a cyano group. For example, one of R ¹ , R ² and R ¹⁰ is a cyano group, and one of R ⁷ to R ⁹ is a cyano group. For example, one of R ² and R ¹⁰ is a cyano group, and one of R ⁷ and R ⁹ is a cyano group. For example, one of R ¹ to R ⁴ is a cyano group, and one of R ⁵ to R ⁸ is a cyano group. For example, one of R ¹ to R ³ is a cyano group, and one of R ⁶ to R ⁸ is a cyano group. For example, one set of R ¹ and R ⁸ , R ² and R ⁷ , R ³ and R ⁶ , and R ⁹ and R ¹⁰ is a cyano group. In a preferred embodiment of the present invention, R ⁹ and R ¹⁰ are cyano groups. In a preferred aspect of the present invention, R ² and R ⁷ are cyano groups. In one aspect of the invention, R ¹ and R ⁸ are cyano groups. In one aspect of the present invention, R ³ and R ⁶ are cyano groups.

In General Formula (1), 1 to 4 of R ¹ to R ¹⁰ represent a donor group bonded to a 5-membered ring.

It is preferable that 1 to 3 of R ¹ to R ¹⁰ are donor groups bonded to a 5-membered ring, and it is more preferable that 1 or 2 of R ¹ to R ¹⁰ are donor groups bonded to a 5-membered ring.

In one aspect of the present invention, only one of R ¹ to R ¹⁰ is a donor group bonded to a 5-membered ring. In one aspect of the present invention, only one of R ¹ to R ⁴ and R ⁵ to R ⁸ is a donor group bonded to a 5-membered ring. For example, only R ¹ or R ⁸ is a donor group that bonds to a 5-membered ring. For example, only R ² or R ⁷ is a donor group that bonds to a 5-membered ring. For example, only R ³ or R ⁶ is a donor group that bonds to a 5-membered ring. For example, only R ⁴ or R ⁵ is a donor group that bonds to a 5-membered ring. In one aspect of the present invention, only R ⁹ or R ¹⁰ is a donor group bonded to a 5-membered ring. For example, only R ⁴ or R ⁵ is a donor group that bonds to a 5-membered ring. In one aspect of the present invention, R ⁹ and R ¹⁰ are cyano groups, and only one of R ¹ to R ⁴ is a donor group bonded to a 5-membered ring. In one aspect of the present invention, R ⁹ and R ¹⁰ are cyano groups, and only R ¹ is a donor group bonded to a 5-membered ring. In a preferred embodiment of the present invention, R ⁹ and R ¹⁰ are cyano groups, and only R ² is a donor group bonded to a 5-membered ring. In a preferred embodiment of the present invention, R ⁹ and R ¹⁰ are cyano groups, and only R ³ is a donor group bonded to a 5-membered ring. In one aspect of the present invention, R ⁹ and R ¹⁰ are cyano groups, and only R ⁴ is a donor group bonded to a 5-membered ring.

In one aspect of the present invention, two of R ¹ to R ¹⁰ are donor groups bonded to a 5-membered ring. In a preferred embodiment of the present invention, the donor groups bonded to two 5-membered rings are the same. In one aspect of the present invention, two of R ¹ to R ⁸ are donor groups bonded to a 5-membered ring. In one aspect of the present invention, one of R ¹ to R ⁴ and one of R ⁵ to R ⁸ are donor groups bonded to a 5-membered ring. In one aspect of the present invention, one of R ² and R ³ and one of R ⁶ and R ⁷ are donor groups bonded to a 5-membered ring. In one aspect of the present invention, one of R ¹ to R ⁸ and one of R ⁹ and R ¹⁰ are donor groups bonded to a 5-membered ring. For example, R ¹ and R ⁸ are donor groups bonded to a 5-membered ring. For example, R ² and R ⁷ are donor groups bonded to a 5-membered ring. For example, R ³ and R ⁶ are donor groups bonded to a 5-membered ring. For example, R ⁹ and R ¹⁰ are donor groups bonded to a 5-membered ring. In one aspect of the present invention, R ⁹ and R ¹⁰ are cyano groups, and R ¹ and R ⁸ are donor groups bonded to a 5-membered ring. In a preferred embodiment of the present invention, R ⁹ and R ¹⁰ are cyano groups, and R ² and R ⁷ are donor groups bonded to a 5-membered ring. In a preferred embodiment of the present invention, R ⁹ and R ¹⁰ are cyano groups, and R ³ and R ⁶ are donor groups bonded to a 5-membered ring. In a preferred embodiment of the present invention, R ⁹ and R ¹⁰ are cyano groups, and R ² and R ³ are donor groups bonded to a 5-membered ring.

In one aspect of the present invention, three of R ¹ to R ¹⁰ are donor groups bonded to a 5-membered ring. In a preferred embodiment of the present invention, the donor groups bonded to three 5-membered rings are the same. In one aspect of the present invention, three of R ¹ to R ⁸ are donor groups bonded to a 5-membered ring. In one aspect of the present invention, three of R ¹ to R ⁴ are donor groups bonded to a 5-membered ring. In one aspect of the present invention, two of R ¹ to R ⁴ and one of R ⁵ to R ⁸ are donor groups bonded to a 5-membered ring. For example, R ² , R ³ and R ⁴ are donor groups bonded to a 5-membered ring. For example, R ² , R ³ and R ⁶ are donor groups bonded to a 5-membered ring. For example, R ² , R ³ and R ⁷ are donor groups bonded to a 5-membered ring. In a preferred embodiment of the present invention, R ⁹ and R ¹⁰ are cyano groups, and R ² , R ³ and R ⁴ are donor groups bonded to a 5-membered ring. In one aspect of the present invention, R ⁹ and R ¹⁰ are cyano groups, and R ² , R ³ and R ⁶ are donor groups bonded to a 5-membered ring. In one aspect of the present invention, R ⁹ and R ¹⁰ are cyano groups, and R ² , R ³ and R ⁷ are donor groups bonded to a 5-membered ring. In one aspect of the present invention, four of R ¹ to R ¹⁰ are donor groups bonded to a 5-membered ring. In a preferred embodiment of the present invention, the donor groups bonded to four 5-membered rings are the same. In one aspect of the present invention, two of R ¹ to R ⁴ and two of R ⁵ to R ⁸ are donor groups bonded to a 5-membered ring. For example, R ² , R ³ , R ⁶ and R ⁷ are donor groups bonded to a 5-membered ring. For example, R ¹ , R ³ , R ⁶ and R ⁸ are donor groups bonded to a 5-membered ring. In one aspect of the present invention, R ⁹ and R ¹⁰ are cyano groups, and R ² and R ³ , R ⁶ and R ⁷ are donor groups bonded to a 5-membered ring. In one aspect of the present invention, R ⁹ and R ¹⁰ are cyano groups, and R ¹ and R ³ , R ⁶ and R ⁸ are donor groups bonded to a 5-membered ring.

The donor group bonded to the five-membered ring is a group bonded to any of the five atoms constituting the ring skeleton of the five-membered ring, and is a group with a negative Hammett σp value. Here, “Hamet's σp value” was proposed by L. P. Hammett, and quantifies the influence of a substituent on the reaction rate or equilibrium 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/k ₀ )=ρσp

or

log(K/K ₀ )=ρσp

It is a constant (σp) specific to the substituent in . In the above formula, k ₀ is the rate constant of the benzene derivative without a substituent, k is the rate constant of the benzene derivative substituted with a substituent, K ₀ is the equilibrium constant of the benzene derivative without a substituent, and K is the benzene derivative substituted with a substituent. The equilibrium constant of the derivative, ρ, represents the reaction constant determined by the type and conditions of the reaction. For a description of “Hamet's σp value” and the numerical value of each substituent in the present invention, see Hansch, C. et. al., Chem. Please refer to the description regarding the σp value in Rev., 91, 165-195 (1991).

The donor group bonded to the 5-membered ring is preferably a group bonded to the nitrogen atom constituting the ring skeleton of the 5-membered ring. The 5-membered ring is preferably π-conjugated. For example, it contains one nitrogen atom as a ring skeleton constituent atom of a 5-membered ring, a donor group of a π-conjugated 5-membered ring bonded to the nitrogen atom, or a ring skeleton constituent atom of a 5-membered ring that contains two nitrogen atoms, A donor group of a π-conjugated 5-membered ring bonded to one of the nitrogen atoms is included. More specifically, substituted or unsubstituted indol-1-yl group, substituted or unsubstituted ring-condensed indol-1-yl group, substituted or unsubstituted carbazol-9-yl group, substituted or unsubstituted ring-condensed carbazole. -9-yl group, substituted or unsubstituted benzimidazol-1-yl group, substituted or unsubstituted ring condensed benzimidazol-1-yl group, etc. “Ring condensation” as used herein means that the ring is condensed. For example, if it is a ring-condensed carbazol-9-yl group, it means that the ring is condensed in at least one of the two benzene rings constituting carbazole. The condensed ring may be any of an aromatic hydrocarbon ring, an aromatic heterocycle, an aliphatic hydrocarbon ring, and an aliphatic heterocycle, or may be a ring in which these are further condensed. Preferably, it is an aromatic hydrocarbon ring or an aromatic heterocycle. Examples of aromatic hydrocarbon rings include substituted or unsubstituted benzene rings. Another benzene ring may be condensed with the benzene ring, or a heterocycle such as a pyridine ring may be condensed. The aromatic heterocycle refers to a ring showing aromaticity containing heteroatoms as ring skeleton constituent atoms, and is preferably a 5- to 7-membered ring. For example, a 5-membered ring or a 6-membered ring can be adopted. In one aspect of the present invention, a furan ring, a thiophene ring, and a pyrrole ring can be employed as the aromatic heterocycle. In one aspect of the present invention, the condensed 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. Furthermore, it is preferable that a substituent selected from substituent group E is bonded to the nitrogen atom of the pyrrole ring, and it is more preferable that an aryl group that may be substituted by an alkyl group or an aryl group is substituted.

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

[Formula 4]

In general formula (2), Z ¹ represents CR ¹¹ or N, Z ² represents CR ¹² or N, Z ³ represents CR ¹³ or N, and Z ⁴ represents CR ¹⁴ or N. Z ⁵ represents C or N, and Ar represents a substituted or unsubstituted aromatic hydrocarbon ring, or a substituted or unsubstituted aromatic heterocycle. R ¹¹ and R ¹² , R ¹² and R ¹³ , and R ¹³ and R ¹⁴ may be bonded to each other to form a cyclic structure.

Among Z ¹ to Z ⁴ , the number of N is preferably 0 to 3, and more preferably 0 to 2. In one aspect of the present invention, among Z ¹ to Z ⁴ , the number of N is 1. In one aspect of the present invention, among Z ¹ to Z ⁴ , the number of N is 0.

R ¹¹ to R ¹⁴ each independently represent a hydrogen atom, a deuterium atom, or a substituent.

For example, the substituent may be selected from substituent group A, substituent group B, substituent group C, substituent group D, or substituent group E. When two or more of R ¹¹ to R ¹⁴ represent a substituent, the two or more substituents may be the same or different. It is preferable that 0 to 2 of R ¹¹ to R ¹⁴ are substituents, for example, 1 may be a substituent, and 0 may be a substituent (R ¹¹ to R ¹⁴ may be a hydrogen atom or a deuterium atom).

R ¹¹ and R ¹² , R ¹² and R ¹³ , and R ¹³ and R ¹⁴ may be bonded to each other to form a cyclic structure. The cyclic structure may be any of an aromatic hydrocarbon ring, an aromatic heterocycle, an aliphatic hydrocarbon ring, and an aliphatic heterocycle, or may be a ring in which these are condensed. Preferably they are aromatic hydrocarbon rings and aromatic heterocycles. Examples of aromatic hydrocarbon rings include substituted or unsubstituted benzene rings. Another benzene ring may be condensed with the benzene ring, or a heterocycle such as a pyridine ring may be condensed. The aromatic heterocycle refers to a ring showing aromaticity containing heteroatoms as ring skeleton constituent atoms, and is preferably a 5- to 7-membered ring. For example, a 5-membered ring or a 6-membered ring can be adopted. In one aspect of the present invention, a furan ring, a thiophene ring, and a pyrrole ring can be employed 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, or a pyrrole ring of a substituted or unsubstituted indole. The benzofuran, benzothiophene, and indole referred to herein may be unsubstituted, may be substituted with a substituent selected from substituent group A, may be substituted with a substituent selected from substituent group B, or may be substituted with a substituent selected from substituent group C. may be substituted, may be substituted with a substituent selected from substituent group D, or may be substituted with a substituent selected from substituent group E. It is preferable that a substituted or unsubstituted aryl group is bonded to the nitrogen atom constituting the pyrrole ring of indole, and examples of the substituent include 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 aspect of the present invention, one set of R ¹¹ and R ¹² , R ¹² and R ¹³ , and R ¹³ and R ¹⁴ are bonded to each other to form a cyclic structure. In one aspect of the present invention, R ¹¹ and R ¹² , R ¹² and R ¹³ , and R ¹³ and R ¹⁴ are not bonded to each other to form a cyclic structure.

In 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 heterocycle. In one aspect 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 aspect of the present invention, Z ⁵ is N, and Ar is a substituted or unsubstituted aromatic heterocycle.

An example of an aromatic hydrocarbon ring that can be adopted by Ar is a benzene ring. Another benzene ring may be condensed with the benzene ring, or a heterocycle such as a pyridine ring may be condensed. The aromatic heterocycle that Ar can adopt is preferably a 5- to 7-membered ring, for example, a 5-membered ring or a 6-membered ring can be adopted. In one aspect of the present invention, a furan ring, a thiophene ring, a pyrrole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, and a pyrazine ring can be employed as the aromatic heterocycle. In one aspect of the present invention, Z ⁵ is C, and the aromatic heterocycle is a furan ring of substituted or unsubstituted benzofuran, a thiophene ring of substituted or unsubstituted benzothiophene, or a pyridine ring of substituted or unsubstituted quinoline. , or a pyridine ring of substituted or unsubstituted isoquinoline. In one aspect of the present invention, Z ⁵ is N, and the aromatic heterocycle is the pyrrole ring of substituted or unsubstituted indole, or the imidazole ring of substituted or unsubstituted benzimidazole. The benzofuran, benzothiophene, quinoline, isoquinoline, indoline, and benzimidazole mentioned herein may be unsubstituted, may be substituted with a substituent selected from substituent group A, or may be substituted with a substituent selected from substituent group B. may be present, may be substituted with a substituent selected from substituent group C, may be substituted with a substituent selected from substituent group D, or may be substituted with a substituent selected from substituent group E.

When Z ⁵ in General Formula (2) is C, it is preferably a group represented by the following General Formula (3).

[Formula 5]

In general formula (3), Z ¹ represents CR ¹¹ or N, Z ² represents CR ¹² or N, Z ³ represents CR ¹³ or N, Z ⁴ represents CR ¹⁴ or N, and Z ⁶ represents CR ¹⁶ or N, Z ⁷ represents CR ¹⁷ or N, Z ⁸ represents CR ¹⁸ or N, and Z ⁹ represents CR ¹⁹ or N. R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ , and R ¹⁸ and R ¹⁹ may be combined with each other to form a cyclic structure.

For Z ¹ to Z ⁴ and R ¹¹ to R ¹⁴ in General Formula (3), reference may be made to the corresponding explanation of General Formula (2). Z ⁶ to Z ⁹ and R ¹⁶ to R ¹⁹ in general formula (3) correspond in that order to Z ¹ to Z ⁴ and R ¹¹ to R ¹⁴ in general formula (2), and these details can be found in the general You can refer to the explanations of Z ¹ to Z ⁴ and R ¹¹ to R ¹⁴ in equation (2).

In one aspect of the present invention, the number of N among Z ¹ to Z ⁴ and Z ⁶ to Z ⁹ is preferably 0 to 2, and is preferably 0 or 1. In one aspect of the present invention, among Z ¹ to Z ⁴ and Z ⁶ to Z ⁹ , the number of N is 1. In a preferred embodiment of the present invention, among Z ¹ to Z ⁴ and Z ⁶ to Z ⁹ , the number of N is 0. When 0, it represents a substituted or unsubstituted carbazol-9-yl group. The carbazol-9-yl group may be unsubstituted, may be substituted with a substituent selected from substituent group A, may be substituted with a substituent selected from substituent group B, or may be substituted with a substituent selected from substituent group C. It may be substituted with a substituent selected from substituent group D, or may be substituted with a substituent selected from substituent group E. In a preferred embodiment of the present invention, the donor group bonded to the 5-membered ring is a carbazol-9-yl group substituted with a group containing at least one substituted or unsubstituted aryl group, for example, a group containing at least one substituted or unsubstituted aryl group. It is a carbazol-9-yl group substituted with a substituted aryl group. In one aspect of the present invention, at least one of the 2nd and 7th positions is a substituted or unsubstituted aryl group. In one aspect of the present invention, at least one of the 3rd and 6th positions is a substituted or unsubstituted aryl group. The aryl group referred to herein may be unsubstituted, may be substituted with a substituent selected from substituent group A, may be substituted with a substituent selected from substituent group B, or may be substituted with a substituent selected from substituent group C, It may be substituted with a substituent selected from substituent group D, or may be substituted with a substituent selected from substituent group E.

The donor group bonded to the 5-membered ring is a substituted or unsubstituted indole-1-yl group, and the ring is fused to the indole ring constituting the indole-1-yl group, thereby forming a condensed ring with a ring number of 4 or more. It's okay. Hereafter, in this specification, a group that satisfies this condition is referred to as a “ring-condensed indol-1-yl group.”

The ring-condensed indol-1-yl group may be polycyclic with one ring condensed to the benzene ring or pyrrole ring constituting the indole-1-yl group, or may be polycyclic or monocyclic with two or more rings. For example, when two are condensed, it is preferable that one is condensed with a benzene ring and one is condensed with a pyrrole ring. The two condensed rings may be the same or different. By condensing the ring to the indole ring, a condensed ring having a ring number of 4 or more, 5 or more, or 6 or more may be formed, and it is preferable to form a condensed ring with a ring number of 5 or more. For example, a compound forming a condensed ring with a ring number of 4, a compound forming a condensed ring with a ring number of 5, a compound forming a condensed ring with a ring number of 6, a compound forming a condensed ring with a ring number of 8, A compound may be employed.

The ring may be condensed only at the 2nd and 3rd positions (b), 4th and 5th positions (e), 5th and 6th positions (f), and 6th and 7th positions (g) of the indole ring. It may be condensed only, or may be condensed at both the 4th and 5th positions (e) and the 6th and 7th positions (g). In addition, it may be condensed with any one of the 4th and 5th positions (e), the 5th and 6th positions (f), and the 6th and 7th positions (g), and the 2nd and 3rd positions (b) (see the formula below, * is a bond indicates location).

[Formula 6]

The ring directly condensed to the benzene ring or pyrrole ring constituting the indole-1-yl group (if the condensed ring is polycyclic, refers to only the directly condensed ring among the rings constituting the polycycle) is an aromatic hydrocarbon ring or an aromatic polycyclic ring. It may be any of small, aliphatic hydrocarbon rings, and aliphatic heterocycles. Preferred is the case where one or more rings selected from the group consisting of a benzene ring and an aromatic heterocycle are directly condensed.

The heterocycle referred to here is a ring containing a hetero atom. The heteroatom is preferably selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom, and is more preferably selected from an oxygen atom, a sulfur atom, and a nitrogen atom. In one preferred embodiment, the heteroatom is an oxygen atom. In another preferred embodiment, the heteroatom is a sulfur atom. In another preferred embodiment, the heteroatom is a nitrogen atom. The number of heteroatoms contained as ring skeleton constituent atoms of the heterocycle is 1 or more, preferably 1 to 3, and more preferably 1 or 2. In a preferred embodiment, the number of heteroatoms is 1. When the number of heteroatoms is two or more, they are preferably heteroatoms of the same type, but may be composed of heteroatoms of different types. For example, two or more heteroatoms may all be nitrogen atoms. Ring skeleton constituent atoms other than heteroatoms are carbon atoms. The number of atoms in the ring skeleton constituting the heterocycle directly condensed to the benzene ring constituting the indole-1-yl group is preferably 4 to 8, more preferably 5 to 7, and even more preferably 5 or 6. desirable. In a preferred embodiment, the number of atoms constituting the ring skeleton constituting the heterocycle is 5. It is preferable that two or more conjugated double bonds exist in the heterocycle, and it is preferable that the conjugated system of the indole ring is expanded by condensing the heterocycle (that is, it is preferable that it has aromaticity). Preferred examples of heterocycles include furan rings, thiophene rings, and pyrrole rings.

Another ring may be condensed to the ring directly condensed to the benzene ring or pyrrole ring constituting the indole-1-yl group. Moreover, the ring to be condensed may be a single ring or a condensed ring. Examples of the condensed ring include an aromatic hydrocarbon ring, an aromatic heterocycle, an aliphatic hydrocarbon ring, and an aliphatic heterocycle.

In a preferred embodiment of the present invention, at least one heterocycle is directly condensed with the benzene ring or pyrrole ring constituting the indol-1-yl group. In a preferred aspect of the present invention, the condensed ring constituting the ring-condensed indol-1-yl group contains two or more heterocycles. For example, a case containing two heterocycles or a case containing three heterocycles can be exemplified.

Examples of aromatic hydrocarbon rings in this 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 aliphatic hydrocarbon rings include cyclopentane rings, cyclohexane rings, and cycloheptane rings. Examples of aliphatic heterocycles include piperidine ring, pyrrolidine ring, and imidazoline ring. Specific examples of condensed rings 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 pills and cinnoline pills can be mentioned.

In a preferred embodiment of the present invention, the ring-condensed indol-1-yl group is a benzofuran-condensed indol-1-yl group, a benzothiophene-condensed indol-1-yl group, an indole-condensed indol-1-yl group, or a siladenene-condensed indole. -1-This is a diary. In a more preferred aspect of the present invention, the indol-1-yl group is a benzofuran-condensed indol-1-yl group, a benzothiophene-condensed indol-1-yl group, or an indole-condensed indol-1-yl group.

In the present invention, a substituted or unsubstituted benzofluor[2,3-e]indol-1-yl group can be employed as the benzofuran condensed indol-1-yl group. Additionally, a substituted or unsubstituted benzofluo[3,2-e]indole-1-yl group can also be employed. Additionally, a substituted or unsubstituted benzofluo[2,3-f]indole-1-yl group can also be employed. Additionally, a substituted or unsubstituted benzofluo[3,2-f]indole-1-yl group can also be employed. Additionally, a substituted or unsubstituted benzofluo[2,3-g]indole-1-yl group can also be employed. Additionally, a substituted or unsubstituted benzofluo[3,2-g]indole-1-yl group can also be employed. In the condensed rings constituting these groups, the rings may be further condensed or may not be condensed.

In the present invention, a substituted or unsubstituted benzofluo[2,3-a]carbazol-9-yl group can be employed as the benzofuran condensed indol-1-yl group. Additionally, a substituted or unsubstituted benzofluo[3,2-a]carbazol-9-yl group can also be employed. Additionally, a substituted or unsubstituted benzofluo[2,3-b]carbazol-9-yl group can also be employed. Additionally, a substituted or unsubstituted benzofluo[3,2-b]carbazol-9-yl group can also be employed. Additionally, a substituted or unsubstituted benzofluo[2,3-c]carbazol-9-yl group can also be employed. Additionally, a substituted or unsubstituted benzofluo[3,2-c]carbazol-9-yl group can also be employed. In the condensed rings constituting these groups, the rings may be further condensed or may not be condensed.

Preferred benzofuran condensed indol-1-yl groups include groups having any of the structures below, and the hydrogen atom in the structures below may or may not be substituted. For example, it is preferably substituted by an aryl group such as a phenyl group, or the 3rd position of the carbazole ring is substituted. In addition, in the benzene ring in the structure below, the ring may be further condensed, or the ring may not be condensed. Dashed lines indicate binding sites.

[Formula 7]

A carbazole-9-yl group in which two benzofuran rings are condensed at the 2nd and 3rd positions can also be used. Specifically, it is a group having one of the structures below, and the hydrogen atom in the structure below may or may not be substituted. In addition, in the benzene ring in the structure below, the ring may be further condensed, or the ring may not be condensed.

[Formula 8]

In the present invention, a substituted or unsubstituted benzothieno[2,3-e]indol-1-yl group can be employed as the benzothiophene condensed indol-1-yl group. Additionally, a substituted or unsubstituted benzothieno[3,2-e]indole-1-yl group can also be employed. Additionally, a substituted or unsubstituted benzothieno[2,3-f]indole-1-yl group can also be employed. Additionally, a substituted or unsubstituted benzothieno[3,2-f]indole-1-yl group can also be employed. Additionally, a substituted or unsubstituted benzothieno[2,3-g]indole-1-yl group can also be employed. Additionally, a substituted or unsubstituted benzothieno[3,2-g]indole-1-yl group can also be employed. In the condensed rings constituting these groups, the rings may be further condensed or may not be condensed.

In the present invention, a substituted or unsubstituted benzothieno[2,3-a]carbazol-9-yl group can be employed as the benzothiophene condensed indol-1-yl group. Additionally, a substituted or unsubstituted benzothieno[3,2-a]carbazol-9-yl group can also be employed. Additionally, a substituted or unsubstituted benzothieno[2,3-b]carbazol-9-yl group can also be employed. Additionally, a substituted or unsubstituted benzothieno[3,2-b]carbazol-9-yl group can also be employed. Additionally, a substituted or unsubstituted benzothieno[2,3-c]carbazol-9-yl group may be employed. Additionally, a substituted or unsubstituted benzothieno[3,2-c]carbazol-9-yl group can also be employed. In the condensed rings constituting these groups, the rings may be further condensed or may not be condensed.

Preferred benzothiophene condensed indol-1-yl groups include groups having any of the structures below, and the hydrogen atom in the structures below may or may not be substituted. For example, it is preferably substituted by an aryl group such as a phenyl group, or the 3rd position of the carbazole ring is substituted. In addition, in the benzene ring in the structure below, the ring may be further condensed, or the ring may not be condensed.

[Formula 9]

A carbazole-9-yl group in which two benzothiophene rings are condensed at the 2nd and 3rd positions can also be used. Specifically, it is a group having one of the structures below, and the hydrogen atom in the structure below may or may not be substituted. In addition, in the benzene ring in the structure below, the ring may be further condensed, or the ring may not be condensed.

[Formula 10]

In the present invention, a substituted or unsubstituted indolo[2,3-e]indol-1-yl group can be employed as the indole condensed indole-1-yl group. Additionally, substituted or unsubstituted indolo[3,2-e]indole-1-yl group can also be employed. Additionally, substituted or unsubstituted indolo[2,3-f]indole-1-yl group can also be employed. Additionally, substituted or unsubstituted indolo[3,2-f]indole-1-yl group can also be employed. Additionally, substituted or unsubstituted indolo[2,3-g]indole-1-yl group can also be employed. Additionally, substituted or unsubstituted indolo[3,2-g]indole-1-yl group can also be employed. In the condensed rings constituting these groups, the rings may be further condensed or may not be condensed.

In the present invention, a substituted or unsubstituted indolo[2,3-a]carbazol-9-yl group can be employed as the indole condensed indole-1-yl group. Additionally, a substituted or unsubstituted indolo[3,2-a]carbazole-9-yl group can also be employed. Additionally, a substituted or unsubstituted indolo[2,3-b]carbazole-9-yl group can also be employed. Additionally, a substituted or unsubstituted indolo[3,2-b]carbazole-9-yl group can also be employed. Additionally, a substituted or unsubstituted indolo[2,3-c]carbazole-9-yl group can also be employed. Additionally, a substituted or unsubstituted indolo[3,2-c]carbazole-9-yl group can also be employed. In the condensed rings constituting these groups, the rings may be further condensed or may not be condensed.

Preferred indole condensation indole-1-yl groups include groups having any of the following structures, and the hydrogen atom in the following structures may be substituted or may be unsubstituted. For example, it is preferably substituted by an aryl group such as a phenyl group, or the 3rd position of the carbazole ring is substituted. In addition, in the benzene ring in the structure below, the ring may be further condensed, or the ring may not be condensed.

[Formula 11]

In a preferred embodiment of the present invention, the benzofuran condensed indol-1-yl group, the benzothiophene condensed indol-1-yl group, the indole condensed indol-1-yl group, and the siladenene condensed indol-1-yl group are substituted or unsubstituted. It is substituted with a substituted aryl group. Preferably, it is substituted with a substituted or unsubstituted phenyl group. As the substituent for the aryl group or phenyl group herein, it is possible to select a group selected from any one of substituent groups A to E, and can preferably be selected from substituent group E. Moreover, it is also preferable that the aryl group or phenyl group referred to here is unsubstituted. In a preferred embodiment of the present invention, the ring-condensed indol-1-yl group is a benzofuran-condensed indol-1-yl group substituted with a substituted or unsubstituted aryl group.

Below, specific examples of the donor group bonded to a 5-membered ring that can be adopted in General Formula (1) are shown. However, the donor group bonded to a 5-membered ring that can be employed in the present invention is not limited to the following specific examples. Additionally, in the following specific examples, Ph represents a phenyl group, D represents a deuterium atom, and * represents a bonding position. Additionally, methyl groups are omitted. For this reason, for example, D2 represents 3-methylcarbazol-9-yl group.

[Formula 12-1]

[Formula 12-2]

[Formula 12-3]

[Formula 12-4]

[Formula 12-5]

[Formula 12-6]

[Formula 12-7]

[Formula 12-8]

[Formula 12-9]

[Formula 12-10]

[Formula 12-11]

[Formula 12-12]

[Formula 12-13]

[Formula 12-14]

[Formula 12-15]

[Formula 12-16]

[Formula 12-17]

Among R ¹ to R ¹⁰ in General Formula (1), when they are neither a cyano group nor a donor group bonded to a 5-membered ring (hereinafter referred to as "remaining R ¹ to R ¹⁰ "), they are hydrogen atoms or deuterium. It is a substituent that is neither an atom nor a cyano group nor a donor group bonded to a 5-membered ring (hereinafter referred to as the “remaining substituents”).

The remaining R ¹ to R ¹⁰ may all be hydrogen atoms or deuterium atoms, for example, all may be hydrogen atoms, or may all be deuterium atoms. Among the remaining R ¹ to R ¹⁰ , the number of remaining substituents is preferably 0 to 6, for example, may be within the range of 0 to 4, may be within the range of 0 to 3, or may be within the range of 0 to 2. do.

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 substituents: It may be selected from group E. In one aspect of the present invention, the other substituent is a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. In a preferred embodiment of the present invention, the other substituent is a substituted or unsubstituted aryl group, for example, a phenyl group which may be substituted with an alkyl group or an aryl group.

The “aryl group” and “heteroaryl group” may be a single ring or a condensed ring in which two or more rings are condensed. In the case of a condensed ring, the number of condensed rings is preferably 2 to 6, and can be selected from, for example, 2 to 4. Specific examples of rings 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 phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 2-pyridyl group, 3-pyridyl group, 4- A pyridyl group can be mentioned. The substituents of the aryl group and the heteroaryl group may be selected from substituent group A below, may be selected from substituent group B below, may be selected from substituent group C below, or may be selected from substituent group D below. may be selected from the substituent group E below.

In general formula (1), R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , and R ¹⁰ and R ¹ may be bonded to each other to form a cyclic structure. For the description and specific examples of the cyclic structure mentioned here, reference can be made to the description and specific examples of the condensed ring in the description of “ring condensation” above.

In one aspect of the invention, at least one of R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁹ and R ¹⁰ One set is combined with each other to form a ring structure. In one aspect of the present invention, at least one set of R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , and R ⁷ and R ⁸ are combined with each other It forms a circular structure. In one aspect of the present invention, R ⁹ and R ¹⁰ are bonded to each other to form a cyclic structure. In one aspect of the present invention, R ⁴ and R ⁵ , R ⁸ and R ⁹ , and R ¹⁰ and R ¹ are not combined with each other to form a cyclic structure. In one aspect of the present invention, R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , and R ¹⁰ and R ¹ are not bonded to each other to form a cyclic structure. In one aspect of the present invention, R ³ and R ⁴ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ are not bonded to each other to form a cyclic structure. In one aspect of the invention, R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , R ¹⁰ and R ¹ are all combined with each other to form a cyclic structure. not forming In one aspect of the invention, R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ , R ⁹ , R ¹⁰ and R ¹ are not combined with each other to form a cyclic structure. In one aspect of the invention, R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , and R ¹⁰ and R ¹ are not combined with each other to form a ring structure.

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

In one aspect of the present invention, the compound represented by general formula (1) has a symmetric structure. For example, it may have an axisymmetric structure. When having an axisymmetric structure, R ¹ and R ⁸ in 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 aspect of the present invention, the compound represented by general formula (1) has an asymmetric structure.

As used herein, “substituent group A” refers to a hydroxyl group, a halogen atom (e.g. a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (e.g. carbon atoms 1 to 40), an alkoxy group. (e.g., carbon number 1 to 40), alkylthio group (e.g., carbon number 1 to 40), aryl group (e.g., carbon number 6 to 30), aryloxy group (e.g., carbon number 6 to 30), aryl thi group group (e.g., 6 to 30 carbon atoms), heteroaryl group (e.g., 5 to 30 ring atoms), heteroaryloxy group (e.g., 5 to 30 ring atoms), heteroarylthio group (e.g., number of ring skeleton atoms 5 to 30), acyl group (e.g., 1 to 40 carbon atoms), alkenyl group (e.g., 1 to 40 carbon atoms), alkynyl group (e.g., 1 to 40 carbon atoms) , alkoxycarbonyl group (e.g., carbon number 1 to 40), aryloxycarbonyl group (e.g., carbon number 1 to 40), heteroaryloxycarbonyl group (e.g., carbon number 1 to 40), silyl group (e.g., carbon number It means one group or a combination of two or more groups selected from the group consisting of trialkylsilyl groups of 1 to 40) and nitro groups.

In this specification, “substituent group B” refers to 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), or an aryloxy group ( For example, 6 to 30 carbon atoms), heteroaryl group (for example, 5 to 30 ring atoms), heteroaryloxy group (for example, 5 to 30 ring atoms), diarylamino group (for example, 5 to 30 ring atoms), For example, it means one group selected from the group consisting of 0 to 20 carbon atoms, or a combination of two or more groups.

In this specification, “substituent group C” refers to an alkyl group (for example, 1 to 20 carbon atoms), an aryl group (for example, 6 to 22 carbon atoms), or a heteroaryl group (for example, 5 to 20 carbon atoms in the ring skeleton). , means one group selected from the group consisting of diarylamino groups (for example, having 12 to 20 carbon atoms), or a group of two or more groups combined.

In this specification, “substituent group D” refers to an alkyl group (e.g., 1 to 20 carbon atoms), an aryl group (e.g., 6 to 22 carbon atoms), and a heteroaryl group (e.g., 5 to 20 ring skeleton atoms). It means one group or a combination of two or more groups selected from the group consisting of.

As used herein, “substituent group E” refers to one group selected from the group consisting of an alkyl group (e.g., having 1 to 20 carbon atoms) and an aryl group (e.g., having 6 to 22 carbon atoms), or a combination of two or more groups. it means.

In this specification, the substituent when described as "substituent" or "substituted or unsubstituted" may be selected from, for example, substituent group A, substituent group B, or substituent group C. , may be selected from substituent group D, and may be selected from substituent group E.

Below, specific examples of compounds represented by general formula (1) are given. However, the compound represented by General Formula (1) that can be used in the present invention should not be interpreted limitedly by these specific examples.

In Table 1, the structures of compounds 1 to 30 are individually shown by specifying R ¹ to R ¹⁰ in the general formula (1) for each compound. Table 2 shows the structures of compounds 1 to 1008962 by collectively indicating R ¹ to R ¹⁰ of a plurality of compounds in each column. For example, in compounds 1 to 447 in Table 2, R ¹ , R ³ to R ⁸ are fixed to H (hydrogen atom), and R ⁹ and R ¹⁰ are fixed to CN (cyano group). And those where R ² is D1 to D447 are designated as compounds 1 to 447 in that order. In compounds 448 to 894, R ¹ , R ² , R ⁴ to R ⁸ are fixed to H (hydrogen atom), and R ⁹ and R ¹⁰ are fixed to CN (cyano group). And, those where R ³ is D1 to D447 are designated as compounds 448 to 894 in that order. Similarly, compounds 895 to 1788 and compounds 806025 to 806918 are also specified. In compounds 1789 to 201597, R ¹ , R ³ to R ⁶ , and R ⁸ are fixed to H (hydrogen atom), and R ⁹ and R ¹⁰ are fixed to CN (cyano group). And, those where R ² is D1 and R ⁷ are D1 to D447 are designated as compounds 1789 to 2235 in that order, and those where R ² is D2 and R ⁷ are D1 to D447 are designated as compounds 2236 to 2681 in that order; Number the compounds in the order that R ² is D3 and R ⁷ are D1 to D447 as compounds 2682 to 3128, and finally, compound numbers in that order where R ² is D447 and R ⁷ are D1 to D447. It is from 201151 to 201597. In the same manner, compounds 201598 to 806024 and compounds 806919 to 1006727 are also specified. In compounds 1006728 to 1007174, R ² , R ³ and R ⁴ are the same, and they are D1 to D447 in that order. Similarly, compounds 1007175 to 1008962 are also specified. Here, in compounds 1007175~1007621, R ² , R ³ , and R ⁷ are the same, in compounds 1007622~1008068, R ² , R ³ , and R ⁶ are the same, and in compounds 1008069~1008515, R ² , R ³ , and R ⁶ and R ⁷ are the same, and in compounds 1008516 to 1008962, R ¹ and R ³ and R ⁶ and R ⁸ are the same.

In Tables 1 and 2, compounds 1 to 1008962 have individually specified structures and are specifically disclosed in this specification. In addition, compounds 1 to 30 are specified in both Tables 1 and 2.

[Table 1]

[Table 2]

Compounds 1 to 1008962 in which all hydrogen atoms present in the molecule are replaced with deuterium atoms are disclosed as Compounds 1(D) to 1008962(D). In addition, when rotational isomers exist among the compounds represented by General Formula (1), the mixture of rotational isomers and each separated rotational isomer are also disclosed in this specification.

In the present invention, the compounds listed in each column of Table 2 can be selected as a group. For example, a total of 18 groups can be individually selected by selecting compounds 1 to 447 as one group and compounds 448 to 894 as another group.

The molecular weight of the compound represented by General Formula (1) is preferably 1500 or less, and more preferably 1200 or less, for example, when it is intended to form and use an organic layer containing the compound represented by General Formula (1) by vapor deposition. It is preferable, it is more preferable that it is 1000 or less, and it is even more preferable that it is 900 or less. The lower limit of molecular weight is the molecular weight of the minimum compound represented by General Formula (1).

The compound represented by General Formula (1) may be formed into a film by a coating method regardless of molecular weight. Using the coating method, it is possible to form a film even if it is a compound with a relatively large molecular weight. The compound represented by General Formula (1) has the advantage of being easily soluble in organic solvents. For this reason, the compound represented by General Formula (1) is easy to apply a coating method and is easy to purify to increase purity.

It is also conceivable to apply the present invention 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, it is conceivable to use a polymer obtained by pre-existing a polymerizable group in the structure represented by General Formula (1) and polymerizing the polymerizable group as a light-emitting material. For example, prepare a monomer containing a polymerizable functional group at any site in the general formula (1), polymerize it alone or copolymerize it with another monomer to obtain a polymer having a repeating unit, and then polymerize the monomer. It is conceivable to use it as a light-emitting material. Alternatively, it is also conceivable to obtain dimers or trimers by coupling compounds having the structure represented by General Formula (1), and to use them as a light-emitting material.

Examples of polymers having a repeating unit containing a structure represented by General Formula (1) include polymers containing a structure represented by either of the following two general formulas.

[Formula 13]

In the above general formula, Q represents a group containing the 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 preferably has a structure represented by -X ¹¹ -L ¹¹ -. Here, X ¹¹ represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom. L ¹¹ represents a linking group, and is preferably a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group, and is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenylene group. It is more preferable.

In the above general formula, R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ each independently represent a substituent. Preferably, it is a substituted or unsubstituted alkyl group with 1 to 6 carbon atoms, a substituted or unsubstituted alkoxy group with 1 to 6 carbon atoms, or a halogen atom, and more preferably, it is an unsubstituted alkyl group with 1 to 3 carbon atoms, or a halogen atom. It is an unsubstituted alkoxy group, a fluorine atom, or a chlorine atom, and more preferably an unsubstituted alkyl group with 1 to 3 carbon atoms, or an unsubstituted alkoxy group with 1 to 3 carbon atoms.

The linking group represented by L ¹ and L ² can be bonded to any site in the general formula (1) constituting Q. Two or more linking groups may be connected to one Q to form a cross-linked structure or network structure.

As a specific structural example of a repeating unit, a structure represented by the following formula can be given.

[Formula 14]

A polymer having a repeating unit containing these formulas is obtained by introducing a hydroxy group into any portion of the general formula (1), reacting it with the following compound as a linker to introduce a polymerizable group, and polymerizing the polymerizable group. It can be synthesized.

[Formula 15]

The polymer containing the structure represented by the general formula (1) in the molecule may be a polymer composed only of repeating units having the structure represented by the general formula (1), or may be a polymer containing repeating units having a structure other than that. In addition, the repeating unit having a structure represented by General Formula (1) contained in the polymer may be a single type or two or more types. Examples of repeating units that do not have the structure represented by General Formula (1) include those derived from monomers used in normal copolymerization. For example, repeating units derived from monomers having ethylenically unsaturated bonds such as ethylene and styrene can be mentioned.

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

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

In one embodiment of the present disclosure, the compound represented by the general formula (1), when excited by thermal or electronic means, appears in the UV region, blue, green, yellow, orange, and red regions of the visible spectrum (e.g., from about 420 nm to It can emit light in the (about 500 nm, about 500 nm to about 600 nm, or about 600 nm to about 700 nm) or near-infrared region.

In one embodiment of the present disclosure, the compound represented by general formula (1) emits light in the red or orange region of the visible spectrum (e.g., about 620 nm to about 780 nm, about 650 nm) when excited by thermal or electronic means. It can be released.

In one embodiment of the present disclosure, the compound represented by general formula (1), when excited by thermal or electronic means, is in the orange or yellow region of the visible spectrum (e.g., about 570 nm to about 620 nm, about 590 nm, about 570 nm). It can shine in.

In one embodiment of the present disclosure, the compound represented by general formula (1), when excited by thermal or electronic means, can emit light in the green region of the visible spectrum (e.g., about 490 nm to about 575 nm, about 510 nm). there is.

In one embodiment of the present disclosure, the compound represented by general formula (1) can emit light in the blue region of the visible spectrum (e.g., about 400 nm to about 490 nm, about 475 nm) when excited by thermal or electronic means. there is.

In one embodiment of the present disclosure, the compound represented by General Formula (1) can emit light in the ultraviolet spectrum region (for example, 280 to 400 nm) when excited by thermal or electronic means.

In one embodiment of the present disclosure, the compound represented by General Formula (1) can emit light in the infrared spectrum region (for example, 780 nm to 2 μm) when excited by thermal or electronic means.

In a preferred embodiment of the present disclosure, the compound represented by general formula (1) emits light in a region of 520 nm or more when excited by thermal or electronic means. In a preferred embodiment of the present invention, light is emitted especially in the green region, 520 nm to 560 nm. Additionally, in another preferred embodiment of the present invention, light of 560 nm to 640 nm is emitted.

In one embodiment of the present disclosure, an organic semiconductor device can be manufactured using a compound represented by General Formula (1). The organic semiconductor element referred to here may be an organic optical element in which light interposes, or may be an organic element in which light does not interpose. The organic light element may be an organic light-emitting element that emits light, may be an organic light-receiving element that receives light, or may be an element that generates energy transfer by light within the element. In one embodiment of the present disclosure, an organic optical device such as an organic electroluminescence device or a solid-state imaging device (for example, a CMOS image sensor) can be manufactured using the compound represented by General Formula (1). In one embodiment of the present disclosure, a CMOS (complementary metal oxide semiconductor) or the like can be manufactured using a compound represented by General Formula (1).

The electronic properties of a small molecule chemical library can be calculated using known ab initio quantum chemical calculations. For example, the Hartree-Fock equation (TD- By analyzing DFT/B3LYP/6-31G*), molecular fragments (parts) having HOMO above a certain threshold and LUMO below a certain threshold can be screened.

As a result, for example, when there is a HOMO energy (for example, ionization potential) of -6.5 eV or more, the donor moiety (“D”) can be selected. Also, for example, when there is a LUMO energy (e.g., electron affinity) of -0.5 eV or less, the acceptor portion ("A") can be selected. The bridge moiety (“B”) is a strong conjugation system that can, for example, strictly constrain the acceptor and donor moieties into specific conformations, thereby preventing overlap between the π conjugation systems of the donor and acceptor moieties. .

In one embodiment, the compound library is screened using one or more of the following characteristics.

1. Light emission near a specific wavelength

2. Calculated triplet state above a certain energy level

3. ΔE _ST value below a certain value

4. Quantum yield above a certain value

5. HOMO level

6. LUMO level

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

In some embodiments, the compound represented by general formula (1) is more than 25%, for example, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%. , represents a quantum yield of about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95% or more.

[Method for synthesizing compounds represented by General Formula (1)]

Compounds represented by General Formula (1) include novel compounds.

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

[Composition using a compound represented by General Formula (1)]

In one embodiment, one compound is combined with a compound represented by general formula (1), disperses the same compound, covalently bonds with the same compound, coats the same compound, supports the same compound, or associates with the same compound. When used with the above materials (eg, small molecules, polymers, metals, metal complexes, etc.), a solid film or layer is formed. For example, a film can be formed by combining the compound represented by General Formula (1) with an electroactive material. In some cases, the compound represented by General Formula (1) may be combined with a hole transport polymer. In some cases, the compound represented by General Formula (1) may be combined with an electron transport polymer. In some cases, the compound represented by General Formula (1) may be combined with a hole transport polymer and an electron transport polymer. In some cases, the compound represented by General Formula (1) may be combined with a copolymer having both a hole transport part and an electron transport part. According to the above embodiment, electrons and/or holes formed in a solid film or layer can be made to interact with the compound represented by General Formula (1).

[Formation of film]

In one embodiment, a film containing the compound represented by General Formula (1) can be formed in a wet process. In the wet process, a solution containing a composition containing the compound of the present invention is applied to a surface to form a film after removal of the solvent. Wet processes include, but are not limited to, spin coating, slit coating, inkjet (spray), gravure printing, offset printing, and flexo printing. 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 (for example, an alkyl group) that increases solubility in organic solvents can be introduced into the compound contained in the composition.

In one embodiment, a film containing the compound of the present invention can be formed in a dry process. In some embodiments, a vacuum deposition method may be employed as a dry process, but is not limited thereto. When employing a vacuum deposition method, the compounds constituting the film may be co-deposited from individual deposition sources, or may be co-deposited from a single deposition source in which the compounds are mixed. When using a single deposition source, a mixed powder obtained by mixing the powders of the compounds may be used, a compression molded body obtained by compressing the mixed powder may be used, or a mixture obtained by heating and melting each compound and cooling may be used. In one embodiment, co-deposition is performed under conditions where the deposition rate (weight loss rate) of a plurality of compounds contained in a single deposition source matches or approximately matches, so that the composition ratio of the plurality of compounds contained in the deposition source corresponds to the composition ratio. A film of any composition ratio can be formed. By mixing a plurality of compounds in the same composition ratio as that of the film to be formed as a deposition source, a film having a desired composition ratio can be easily formed. In one embodiment, the temperature at which each compound to be co-deposited achieves the same weight loss rate can be specified, and that temperature can be adopted as the temperature at the time of co-deposition.

[Examples of use of compounds represented by General Formula (1)]

Compounds represented by General Formula (1) are useful as materials for organic light-emitting devices. In particular, it is preferably used for organic light emitting diodes and the like.

Organic light emitting diode:

One aspect of the present invention relates to the use of a compound represented by the general formula (1) of the present invention as a light-emitting material for an organic light-emitting device. In one embodiment, the compound represented by General Formula (1) of the present invention can be effectively used as a light-emitting material in the light-emitting layer of an organic light-emitting device. In one embodiment, the compound represented by General Formula (1) includes 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 relates to the use of a compound represented by general formula (1) as a delayed phosphor. In one embodiment of the present invention, the compound represented by General Formula (1) can be used as a host material and can be used together with one or more light-emitting materials, and the light-emitting material may be a fluorescent material, a phosphorescent material, or TADF. . In one embodiment, the compound represented by General Formula (1) can also be used as a hole transport material. In one embodiment, the compound represented by General Formula (1) can be used as an electron transport material. In one embodiment, the present invention relates to a method of generating delayed fluorescence from a compound represented by general formula (1). In one embodiment, an organic light-emitting device containing a compound as a light-emitting material emits delayed fluorescence and exhibits high light emission efficiency.

In one embodiment, the light-emitting layer contains a compound represented by General Formula (1), and the compound represented by General Formula (1) is oriented parallel to the substrate. In some embodiments, the substrate is a film forming surface. In some embodiments, the orientation of the compound represented by general formula (1) with respect to the film forming surface affects or determines the propagation direction of light emitted by the aligning compound. In one embodiment, the light extraction efficiency from the light emitting layer is improved by aligning the propagation direction of light emitted by the compound represented by General Formula (1).

One aspect of the present invention relates to an organic light emitting device. In some embodiments, the organic light emitting device includes a light emitting layer. In one embodiment, the light-emitting layer contains a compound represented by General Formula (1) as a light-emitting material. In one embodiment, the organic light-emitting device is an organic light luminescence device (organic PL device). In one embodiment, the organic light-emitting device is an organic electroluminescence device (organic EL device). In one embodiment, the compound represented by General Formula (1) assists light emission of other light-emitting materials included in the light-emitting layer (as a so-called assist dopant). In one embodiment, the compound represented by General Formula (1) contained in the light-emitting layer is at its lowest singlet excitation energy level, and the lowest singlet excitation energy level of the host material contained in the light-emitting layer is different from the light emitting layer contained in the light-emitting layer. The material's lowest excitation is contained between the singlet energy levels.

In one embodiment, the organic light luminescence element includes at least one light-emitting layer. In one embodiment, the organic electroluminescence element includes at least an anode, a cathode, and an organic layer between the anode and the cathode. In one embodiment, the organic layer includes at least a light emitting layer. In one embodiment, the organic layer includes only the light-emitting layer. In one embodiment, the organic layer includes one or more organic layers in addition to the light emitting layer. Examples of the organic layer include a hole transport layer, a hole injection layer, an electron barrier layer, a hole barrier layer, an electron injection layer, an electron transport layer, and an exciton barrier layer. In one embodiment, the hole transport layer may be a hole injection transport layer with a hole injection function, and the electron transport layer may be an electron injection transport layer with an electron injection function. An example of an organic electroluminescence device is shown in Figure 1.

Emissive layer:

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

In some embodiments, only light-emitting materials are used as the light-emitting layer. In one embodiment, the light-emitting layer includes a light-emitting material and a host material. In one embodiment, the light-emitting material is one or more compounds represented by General Formula (1). In one embodiment, in order to improve the light emission efficiency of the organic electroluminescence device and the organic light luminescence device, singlet excitons and triplet excitons generated in the light-emitting material are confined within the light-emitting material. In one embodiment, a host material is used in the light-emitting layer in addition to the light-emitting material. In some embodiments, the host material is an organic compound. In one embodiment, the organic compound has a singlet excitation energy and a triplet excitation energy, at least one of which is higher than that of the light-emitting material of the present invention. In one embodiment, the singlet exciton and triplet exciton generated in the light-emitting material of the present invention are confined in the molecules of the light-emitting material of the present invention. In one embodiment, singlet and triplet excitons are sufficiently restrained to improve light emission efficiency. In some embodiments, although high light emission efficiency is still obtained, singlet excitons and triplet excitons are not sufficiently confined, that is, the host material capable of achieving high light emission efficiency is not particularly limited and is not limited to the present invention. It can be used in inventions. In one embodiment, light emission occurs in the light-emitting material in the light-emitting layer of the device of the present invention. In some embodiments, the synchronized light includes both fluorescence and delayed fluorescence. In one embodiment, the synchronized light includes synchronized light from the host material. In one embodiment, the synchronized light consists of synchronized light from a host material. In one embodiment, the synchronized light includes synchronized light from the compound represented by General Formula (1) and synchronized light from the host material. In some embodiments, TADF molecules and host materials are used. In one embodiment, TADF is an assist dopant and has a lower singlet excitation energy than the host material in the light-emitting layer and a higher singlet excitation energy than the light-emitting material in the light-emitting layer.

When using the compound represented by General Formula (1) as an assist dopant, it is possible to employ various compounds as a light-emitting material (preferably a fluorescent material). Such luminescent materials include anthracene derivatives, tetracene derivatives, naphthacene derivatives, pyrene derivatives, perylene derivatives, chrysene derivatives, rubrene derivatives, coumarin derivatives, pyran derivatives, stilbene derivatives, fluorene derivatives, and anthryl derivatives. , pyromethene derivatives, terphenyl derivatives, terphenylene derivatives, fluoranthene derivatives, amine derivatives, quinacridone derivatives, oxadiazole derivatives, malononitrile derivatives, carbazole derivatives, zulolidine derivatives, thiazole derivatives , it is possible to use derivatives containing metals (Al, Zn), etc. These example skeletons may have substituents or may not have substituents. Additionally, these example skeletons may be combined.

Below, light emitting materials that can be used in combination with an assist dopant having a structure represented by General Formula (1) are exemplified.

[Formula 16-1]

[Formula 16-2]

[Formula 16-3]

In addition, the compounds described in paragraphs 0220 to 0239 of WO2015/022974 can also be particularly preferably employed as a light-emitting material used with an assist dopant having a structure represented by General Formula (1).

In one embodiment, when a host material is used, the amount of the compound of the present invention as a light-emitting material contained in the light-emitting layer is 0.1% by weight or more. In one embodiment, when a host material is used, the amount of the compound of the present invention as a light-emitting material contained in the light-emitting layer is 1% by weight or more. In one embodiment, when a host material is used, the amount of the compound of the present invention as a light-emitting material contained in the light-emitting layer is 50% by weight or less. In one embodiment, when a host material is used, the amount of the compound of the present invention as a light-emitting material contained in the light-emitting layer is 20% by weight or less. In one embodiment, when a host material is used, the amount of the compound of the present invention as a light-emitting material contained in the light-emitting layer is 10% by weight or less.

In one embodiment, the host material of the light-emitting layer is an organic compound having a hole transport function and an electron transport function. In one embodiment, the host material of the light emitting layer is an organic compound that prevents the wavelength of radiated light from increasing. In one embodiment, the host material of the light-emitting layer is an organic compound with a high glass transition temperature.

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

[Formula 17-1]

[Formula 17-2]

In one embodiment, the light-emitting layer includes two or more types of TADF molecules with different structures. For example, the light-emitting layer can be made of three types of materials with higher singlet excitation energy levels in that order: the host material, the first TADF molecule, and the second TADF molecule. At this time, the difference ΔE _ST between the lowest singlet excitation energy level and the lowest triplet excitation energy level of 77K for both the first TADF molecule and the second TADF molecule is preferably 0.3 eV or less, more preferably 0.25 eV or less, and 0.2 It is more preferably eV or less, more preferably 0.15 eV or less, more preferably 0.1 eV or less, even more preferably 0.07 eV or less, even more preferably 0.05 eV or less, even more preferably 0.03 eV or less, It is particularly preferable that it is 0.01 eV or less. The concentration of the first TADF molecules in the light emitting layer is preferably greater than the concentration of the second TADF molecules. Additionally, the concentration of the host material in the light-emitting layer is preferably greater than the concentration of the second TADF molecule. The concentration of the first TADF molecules in the light emitting layer may be larger, smaller, or the same as the concentration of the host material. In one embodiment, the composition in the light emitting layer may be 10 to 70% by weight of the host material, 10 to 80% by weight of the first TADF molecule, and 0.1 to 30% by weight of the second TADF molecule. In one embodiment, the composition in the light-emitting layer may be 20 to 45% by weight of the host material, 50 to 75% by weight of the first TADF molecule, and 5 to 20% by weight of the second TADF molecule. In one embodiment, the luminescence quantum yield ϕPL1(A) due to optical excitation of the co-deposited film of the first TADF molecule and the host material (concentration of the first TADF molecule in this co-deposited film = A% by weight) and the second TADF The luminescence quantum yield ϕPL2(A) due to optical excitation of the co-deposited film of the molecule and the host material (concentration of the second TADF molecule in this co-deposited film = A% by weight) is determined by the relational expression ϕPL1(A) > ϕPL2(A) satisfies. In one embodiment, the luminescence quantum yield ϕPL2(B) due to light excitation of the co-deposited film of the second TADF molecule and the host material (concentration of the second TADF molecule in this co-deposited film = B% by weight), and the second TADF The luminescence quantum yield ϕPL2(100) due to optical excitation of a single molecule film satisfies the relational expression ϕPL2(B)>ϕPL2(100). In some embodiments, the light-emitting layer may include three types of TADF molecules with different structures. The compound of the present invention may be any of a plurality of TADF compounds included in the light-emitting layer.

In one embodiment, the light-emitting layer can be made of a material selected from the group consisting of a host material, an assist dopant, and a light-emitting material. In some embodiments, the light-emitting layer does not include metallic elements. In one embodiment, the light-emitting layer may be made of a material composed only of atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms, oxygen atoms, and sulfur atoms. Alternatively, the light-emitting layer may be made of a material composed only of atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms, and oxygen atoms. Alternatively, the light-emitting layer may be made of a material composed only of atoms selected from the group consisting of carbon atoms, hydrogen atoms, nitrogen atoms, and oxygen atoms.

When the light-emitting layer contains a TADF material other than the compound of the present invention, the TADF material may be a known delayed fluorescent material. As preferred delayed fluorescent materials, paragraphs 0008 to 0048 and 0095 to 0133 of WO2013/154064, paragraphs 0007 to 0047 and 0073 to 0085 of WO2013/011954, paragraphs 0007 to 0033 and 0059 to 0066 of WO2013/011955, Paragraph of No. 2013/081088 0008-0071 and 0118-0133, paragraphs 0009-0046 and 0093-0134 of Japanese Patent Publication No. 2013-256490, paragraphs 0008-0020 and 0038-0040 of Japanese Patent Publication No. 2013-116975, WO2013/133359 Paragraph 0007~0032 and 0079 to 0084, paragraphs 0008 to 0054 and 0101 to 0121 of WO2013/161437, paragraphs 0007 to 0041 and 0060 to 0069 of Japanese Patent Application Publication No. 2014-9352, and paragraphs 0008 to 0048 and 0 of Japanese Patent Application Publication No. 2014-9224. 067~ 0076, the paragraph of the short paragraph 0013 ~ 0025, the short paragraph 0013 ~ 0026 of the Japanese Patent Patent Publication No. 2017-119664, the paragraph of the Japanese Patent Patent No. 2017-222623 0010 to 0050, paragraphs 0012 to 0043 of Japanese Patent Application Laid-Open No. 2018-100411, and paragraphs 0016 to 0044 of WO2018/047853, compounds included in the general formula, particularly exemplary compounds, and include those capable of emitting delayed fluorescence. . In addition, herein, Japanese Patent Publication No. 2013-253121, WO2013/133359, WO2014/034535, WO2014/115743, WO2014/122895, WO2014/126200, WO2014/136758, WO2014/1 No. 33121, WO2014 /No. 136860, WO2014/196585, WO2014/189122, WO2014/168101, WO2015/008580, WO2014/203840, WO2015/002213, WO2015/016200, No. 9725, WO2015/072470, WO2015 /108049, WO2015/080182, WO2015/072537, WO2015/080183, Japanese Patent Publication No. 2015-129240, WO2015/129714, WO2015/129715, WO2015/133501, No. 15/136880, WO2015/ These are light-emitting materials described in No. 137244, WO2015/137202, WO2015/137136, WO2015/146541, and WO2015/159541, and those capable of emitting delayed fluorescence can be preferably employed. In addition, the above-mentioned publication described in this paragraph is incorporated herein as part of this specification.

Below, each member of the organic electroluminescence element and each layer other than the light-emitting layer are explained.

write:

In some embodiments, the organic electroluminescence device of the present invention is supported by a substrate, and the substrate is not particularly limited, and includes materials commonly used in organic electroluminescence devices, such as glass, transparent plastic, Any material formed by quartz or silicon may be used.

anode:

In some embodiments, the anode of the organic electroluminescence device is made of a metal, alloy, conductive compound, or a combination thereof. In some embodiments, the metal, alloy or conductive compound has a high work function (4 eV or greater). In some embodiments, the metal is Au. In some embodiments, the conductive transparent material is selected from CuI, indium-tin oxide (ITO), SnO ₂ and ZnO. In some embodiments, an amorphous material capable of forming a transparent conductive film, such as IDIXO (In ₂ O ₃ -ZnO), is used. In some embodiments, the anode is a thin film. In some embodiments, the thin film is fabricated by vapor deposition or sputtering. In some embodiments, the film is patterned by photolithographic methods. In some embodiments, when the pattern does not need to be high precision (for example, about 100 μm or more), the pattern may be formed using a mask of a shape suitable for deposition or sputtering as an electrode material. In some embodiments, when a coating material such as an organic conductive compound can be applied, a wet film forming method such as a printing method or a coating method is used. In some embodiments, when synchronized light passes through the anode, the anode has a transmission of greater than 10% and the anode has a sheet resistance of less than a few hundred ohms per unit area. In some embodiments, the thickness of the anode is between 10 and 1,000 nm. In some embodiments, the thickness of the anode is 10-200 nm. In some embodiments, the thickness of the anode varies depending on the material used.

cathode:

In some embodiments, the cathode is made of an electrode material such as a metal with a low work function (4 eV or less) (referred to as an electron injection metal), an alloy, a conductive compound, or a combination thereof. In some embodiments, the electrode material is sodium, sodium-potassium alloy, magnesium, lithium, magnesium-copper mixture, magnesium-silver mixture, magnesium-aluminum mixture, magnesium-indium mixture, aluminum-aluminum oxide (Al ₂ O ₃ ) is selected from mixtures, indium, lithium-aluminum mixtures and rare earth elements. In some embodiments, a mixture of an electron injecting metal and a second metal that is a stable metal with a higher work function than the electron injecting metal is used. In some embodiments, the mixture is selected from a magnesium-silver mixture, a magnesium-aluminum mixture, a magnesium-indium mixture, an aluminum-aluminum oxide (Al ₂ O ₃ ) mixture, a lithium-aluminum mixture, and aluminum. In some embodiments, the mixture improves electron injection properties and resistance to oxidation. In some embodiments, the cathode is manufactured by forming the electrode material into a thin film by vapor deposition or sputtering. In some embodiments, the cathode has a sheet resistance of less than a few hundred ohms per unit area. In some embodiments, the thickness of the cathode is between 10 nm and 5 μm. In some embodiments, the thickness of the cathode is 50-200 nm. In some embodiments, either the anode or cathode of the organic electroluminescence device is transparent or translucent to transmit synchronized light. In some embodiments, transparent or translucent electroluminescence elements enhance light emission brightness.

In some embodiments, the cathode is formed of the conductive transparent material described above with respect to the anode, thereby forming a transparent or translucent cathode. In some embodiments, the device includes an anode and a cathode, but both are transparent or translucent.

Injection layer:

The injection layer is a layer between the electrode and the organic layer. In some embodiments, the injection layer reduces the driving voltage, thereby enhancing the optical radiation brightness. 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 transport layer, and between the cathode and the light-emitting layer or the electron transport layer. In some embodiments, an injection layer is present. In some embodiments, no injection layer is present.

Below, examples of preferred compounds that can be used as hole injection materials are given.

[Formula 18]

Next, examples of preferred compounds that can be used as electron injection materials are given.

[Formula 19]

Barrier layer:

The barrier layer is a layer that can prevent charges (electrons or holes) and/or excitons present in the light-emitting layer from diffusing to the outside of the light-emitting layer. In some embodiments, the electron barrier layer exists between the light-emitting layer and the hole transport layer and prevents electrons from passing through the light-emitting layer and reaching the hole transport layer. In some embodiments, the hole barrier layer exists between the light-emitting layer and the electron transport layer and prevents holes from passing through the light-emitting layer and reaching the electron transport layer. In some embodiments, the barrier layer prevents excitons from diffusing outside the light-emitting layer. In some embodiments, the electron barrier layer and the hole barrier layer constitute an exciton barrier layer. The term “electron barrier layer” or “exciton barrier layer” used in this specification includes a layer that has both the functions of an electron barrier layer and an exciton barrier layer.

Hole barrier layer:

The hole barrier layer functions as an electron transport layer. In some embodiments, during transport of electrons, the hole barrier layer prevents holes from reaching the electron transport layer. In some embodiments, the hole barrier layer increases the probability of recombination of electrons and holes in the light emitting layer. The material used for the hole barrier layer may be the same material as described above for the electron transport layer.

Below, examples of preferred compounds that can be used in the hole barrier layer are given.

[Formula 20]

Electronic barrier layer:

The electron barrier layer transports holes. In some embodiments, during transport of holes, the electron barrier layer prevents electrons from reaching the hole transport layer. In some embodiments, the electron barrier layer increases the probability of recombination of electrons and holes in the light emitting layer. The material used for the electron barrier layer may be the same material as described above for the hole transport layer.

Specific examples of preferred compounds that can be used as electronic barrier materials are given below.

[Formula 21]

Exciton barrier layer:

The exciton barrier layer prevents excitons generated through recombination of holes and electrons in the light-emitting layer from diffusing to the electron transport layer. In some embodiments, the exciton barrier layer enables effective confinement of excitons in the light-emitting layer. In some embodiments, the light emission efficiency of the device is improved. In some embodiments, the exciton barrier layer is adjacent to the light emitting layer on either the anode side or the cathode side and on both sides. In some embodiments, when the exciton barrier layer is present on the anode side, the layer may be present between the hole transport layer and the light-emitting layer and adjacent to the light-emitting layer. In some embodiments, when the exciton barrier layer is present on the cathode side, the layer may be present between the light-emitting layer and the cathode and adjacent to the light-emitting layer. In some embodiments, the hole injection layer, the electron barrier layer, or the same layer exists between the anode and the exciton barrier layer adjacent to the light emitting layer on the anode side. In some embodiments, the hole injection layer, the electron barrier layer, the hole barrier layer, or the same layer exists between the cathode and the exciton barrier layer adjacent to the light emitting layer on the cathode side. In some embodiments, the exciton barrier layer includes singlet excitation energy and triplet excitation energy, at least one of which is higher than the singlet excitation energy and triplet excitation energy, respectively, of the luminescent material.

Hole transport layer:

The hole transport layer contains 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 hole injection or transport properties and electron barrier properties. In some embodiments, the hole transport material is an organic material. In some embodiments, the hole transport material is an inorganic material. Examples of known hole transport materials that can be used in the present invention include, but are not limited to, triazole derivatives, oxadiazole derivatives, imidazole derivatives, carbazole derivatives, indolocarbazole derivatives, polyarylalkane derivatives, and pyrazoline derivatives. , pyrazolone derivatives, phenylenediamine derivatives, allylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers. and conductive polymer oligomers (particularly thiophene oligomers), or combinations thereof. In some embodiments, the hole transport material is selected from porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds. In some embodiments, the hole transport material is an aromatic tertiary amine compound. Specific examples of preferred compounds that can be used as hole transport materials are given below.

[Formula 22]

Electron transport layer:

The electron transport layer contains an electron transport material. In some embodiments, the electron transport layer is a single layer. In some embodiments, the electron transport layer has multiple layers.

In some embodiments, the electron transport material only needs to have the function of transporting electrons injected from the cathode to the light emitting layer. In some embodiments, the electron transport material also functions as a hole barrier material. Examples of the electron transport layer that can be used in the present invention include, but are not limited to, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimide, fluoreneylidenemethane derivatives, and anthraquinodimethane. , anthrone derivatives, oxadiazole derivatives, azole derivatives, azine derivatives or combinations thereof, or polymers thereof. In some embodiments, the electron transport material is a thiadiazole derivative or quinoxaline derivative. In some embodiments, the electron transport material is a polymeric material. Specific examples of preferred compounds that can be used as electron transport materials are given below.

[Formula 23]

Additionally, examples of compounds preferred as materials that can be added to each organic layer are given. For example, adding it as a stabilizing material is considered.

[Formula 24]

Although preferred materials that can be used in organic electroluminescence devices have been specifically exemplified, the materials that can be used in the present invention are not limited to the following exemplary compounds. Moreover, even if a compound is exemplified as a material with a specific function, it is also possible to divert it as a material with other functions.

device:

In some embodiments, a light emitting layer is included in the device. For example, devices include, but are not limited to, OLED valves, OLED lamps, displays for televisions, monitors for computers, mobile phones, and tablets.

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

In some embodiments, the compositions described herein can be incorporated into various photosensitive or photoactivated devices, such as OLEDs or optoelectronic devices. In some embodiments, the constructs may be useful in facilitating charge transfer or energy transfer within a device, and/or as a hole transport material. Examples of the device include organic light-emitting diodes (OLEDs), organic integrated circuits (OICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), and organic light-emitting diodes (OLEDs). solar cells (O-SC), organic optical detection devices, organic photoreceptors, organic field-quench devices (O-FQDs), light-emitting fuel cells (LECs) or organic laser diodes (O-lasers). I can hear it.

Valve or lamp:

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

In some embodiments, the device includes OLEDs with different colors. In some embodiments, the device includes an array comprising a combination of OLEDs. In some embodiments, the combination of OLEDs is a combination of three colors (e.g., RGB). In some embodiments, the combination of OLEDs is a combination of colors that are neither red, green, nor blue (e.g., orange and yellow-green). In some embodiments, the combination of OLEDs is a combination of two, four, or more colors.

In some embodiments, the device may:

a circuit board having a first side having a mounting surface and a second side opposite thereto, and defining at least one opening;

At least one OLED on the mounting surface, wherein the at least one OLED has a light-emitting structure including at least one organic layer including an anode, a cathode, and a light-emitting layer between the anode and the cathode. With OLED,

A housing for a circuit board,

An OLED light having at least one connector disposed at an end of the housing, wherein the housing and the connector define a package suitable for mounting into a lighting fixture.

In some embodiments, the OLED light has multiple OLEDs mounted on a circuit board so that light radiates in multiple directions. In some embodiments, some of the light emitted in the first direction is polarized and radiated in the second direction. In some embodiments, a reflector is used to polarize light emitted in the first direction.

Display or screen:

In some embodiments, the light emitting layer of the present invention can be used in screens or displays. In some embodiments, the compounds of the present invention are deposited onto a substrate using processes such as, but not limited to, vacuum evaporation, deposition, vapor deposition, or chemical vapor deposition (CVD). In some embodiments, the substrate is a photo plate structure useful in two-sided etching to provide pixels of unique aspect ratios. The screen (also called a mask) is used in the manufacturing process of OLED displays. The design of the corresponding artwork pattern makes it possible to place very steep and narrow tie bars between pixels in the vertical direction and large, wide rectangular openings in the horizontal direction. This allows for the fine patterning of pixels required for high-resolution displays while optimizing chemical vapor deposition on the TFT backplane.

By internal patterning of pixels, it becomes possible to construct three-dimensional pixel openings of various aspect ratios in the horizontal and vertical directions. Additionally, the use of imaged "stripes" or halftone circles in pixel areas undercuts these specific patterns and protects them from etching in certain areas until they are removed from the substrate. Then, all pixel areas are processed at the same etch rate, but their depth varies by the halftone pattern. By varying the size and spacing of the halftone pattern, different etchings with varying degrees of protection within a pixel are possible, allowing for the localized deep etching needed to form steep vertical squares.

A preferred material for the deposition mask is invar. Invar is a metal alloy cold rolled into a long thin sheet at a steel mill. Invar cannot be electrodeposited onto a spin mandrel as a nickel mask. An appropriate and low-cost method for forming an opening region in a deposition mask is a method by wet chemical etching.

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 lithography (eg, photolithography and e-beam lithography). In some embodiments, the screen or display pattern is fabricated using wet chemical etching. In a further embodiment, the screen or display pattern is processed using plasma etching.

Method of manufacturing the device:

OLED displays are generally manufactured by forming a large mother panel and then cutting the mother panel into cell panel units. Typically, for each cell panel on the mother panel, a thin film transistor (TFT) having an active layer and source/drain electrodes is formed on a base material, and a planarization film is applied to the TFT to form a pixel electrode, a light emitting layer, a counter electrode, and The encapsulation layer is formed sequentially over time and is formed by cutting from the mother panel.

In another aspect of the present invention, a method for manufacturing an organic light emitting diode (OLED) display is provided, the method comprising:

A process of forming a barrier layer on the base substrate of the mother panel,

A process of forming a plurality of display units on a cell panel basis on the barrier layer;

A process of forming an encapsulation layer on each display unit of the cell panel;

It includes a process of applying an organic film to the interface between the cell panels.

In some embodiments, the barrier layer is an inorganic film formed, for example, of SiNx, and the ends of the barrier layer are covered with an organic film formed of polyimide or acrylic. In some embodiments, the organic film assists in smoothly cutting the mother panel into cell panel units.

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 have a thin film transistor (TFT) layer, a planarization film formed on the TFT layer, and a light emitting unit formed on the planarization film, and the organic film applied to the interface portion may be the planarization film. It is formed of the same material as the material of and is formed simultaneously with the formation of the flattening film. In some embodiments, the light emitting unit is connected to the TFT layer by a passivation layer, a planarizing film therebetween, and an encapsulation layer that covers and protects the light emitting unit. In some embodiments of the above manufacturing methods, the organic film is connected to neither the display unit nor the encapsulation layer.

Each of the organic film and the flattening film may contain either polyimide or acrylic. In some embodiments, the barrier layer may be an inorganic film. In some embodiments, the base substrate may be formed of polyimide. The method also includes the steps of mounting a carrier substrate formed of a glass material on another surface of the base substrate before forming a barrier layer on one surface of the base substrate formed of polyimide, and prior to cutting along the interface portion, A step of separating the carrier substrate from the base substrate may be included. In some embodiments, the OLED display is a flexible display.

In some embodiments, the passivation layer is an organic film disposed on the TFT layer to cover the TFT layer. In some embodiments, the planarizing film is an organic film formed on a passivation layer. In some embodiments, the planarizing film is formed of polyimide or acrylic, just like the organic film formed at the end of the barrier layer. In some embodiments, when manufacturing an OLED display, the planarization film and the organic film are formed simultaneously. In some embodiments, the organic film may be formed at an end of the barrier layer, such that a portion of the organic film is in direct contact with the base substrate and the remaining portion of the organic film surrounds the end of the barrier layer. , in contact with the barrier layer.

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

In some embodiments, when a voltage is applied to the pixel electrode through the TFT layer, an appropriate voltage is formed between the pixel electrode and the counter electrode, thereby causing the organic light emitting layer to emit light, thereby forming an image. Hereinafter, the 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 penetration of external moisture may be formed as a thin film-like encapsulation structure in which organic films and inorganic films are alternately laminated. In some embodiments, the encapsulation layer has a thin film-like encapsulation structure in which a plurality of thin films are stacked. In some embodiments, the organic film applied to the interface portion is arranged at intervals from each of the plurality of display units. In some embodiments, the organic film is formed such that a portion of the organic film is directly in contact with the base substrate and the remaining portion of the organic film is in contact with the barrier layer while surrounding an end of the barrier layer.

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

In some embodiments, the barrier layer is formed on the surface of the base substrate opposite the carrier substrate. In one embodiment, the barrier layer is patterned according to the size of each cell panel. For example, a base substrate is formed on all surfaces of the mother panel, while a barrier layer is formed according to the size of each cell panel, thereby forming a groove at the interface between the barrier layers of the cell panels. Each cell panel can be cut along the groove.

In some embodiments, the above manufacturing method further includes 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 is formed in the base substrate. does not penetrate into In some embodiments, the TFT layer of each cell panel is formed, and a passivation layer, which is an inorganic film, and a planarizing film, which is an organic film, are disposed on the TFT layer and cover the TFT layer. At the same time that a flattening film made of, for example, polyimide or acrylic is formed, the groove of the interface portion is covered with an organic film, for example, made of polyimide or acrylic. This prevents cracks from occurring by allowing the organic film to absorb the impact generated when each cell panel is cut along the groove at the interface portion. That is, when all barrier layers are completely exposed without organic films, the impact generated when each cell panel is cut along the groove at the interface portion is transmitted to the barrier layer, thereby increasing the risk of cracks occurring. However, in one embodiment, the grooves of the interface portion between the barrier layers are covered with an organic film, and in order to absorb the shock that would be transmitted to the barrier layer without the organic film, each cell panel is gently cut to form a crack in the barrier layer. You can prevent this from happening. In one embodiment, the organic film and the planarization film covering the groove of the interface portion are arranged at intervals from each other. For example, when the organic film and the planarizing film are connected to each other as one layer, there is a risk of external moisture entering the display unit through the remaining portion of the organic film and the planarizing film. The films are spaced apart from each other such that the organic films are spaced apart from the display unit.

In some embodiments, the 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. Accordingly, after the mother panel is completely manufactured, the carrier substrate supporting the base substrate is separated from the base substrate. In some embodiments, when a laser beam is irradiated to 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 mother panel is cut in cell panel units. In some embodiments, the mother panel is cut along the interface between cell panels using a cutter. In some embodiments, the groove of the interface portion along which the mother panel is cut is covered with an organic film, so that the organic film absorbs shock during cutting. In some embodiments, cracking can be prevented in the barrier layer during cutting.

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 a base substrate, a display unit formed on the barrier layer, an encapsulation layer formed on the display unit, and an organic film applied to an end of the barrier layer.

Example

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 procedures, etc. shown below can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as limited by the specific examples shown below. In addition, evaluation of luminescence characteristics was performed using a source meter (2400 series, manufactured by Keithley), a semiconductor parameter analyzer (E5273A, manufactured by Agilent Technologies), an optical power meter measurement device (1930C, manufactured by Newport), and an optical spectrometer (Ocean Optics). This was carried out using a spectroradiometer (SR-3 manufactured by Topcon) and a streak camera (C4334 type manufactured by Hamamatsu Photonics Co., Ltd.). In addition, the energy of HOMO and LUMO was measured by photoelectron spectroscopy (AC-3, manufactured by Riken Geki, etc.) in air.

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

(Synthesis Example 1)

[Formula 25]

intermediate a

Under a nitrogen stream, a dimethylformamide solution (10 mL) of 2-fluoro-9,10-phenanthrenequinone (3.85 g, 17.0 mmol) and potassium cyanide (0.055 g, 0.85 mmol) was stirred for 30 minutes, and then stirred for 30 minutes. Methylsilyl cyanide (6.4 mL, 51.0 mmol) was added, and the mixture was stirred at room temperature for 3 hours. After that, dry acetonitrile (60 mL) and phosphorus tribromide (2.4 mL, 25.5 mmol) were added, the temperature was raised to 50°C, and the mixture was stirred overnight. This mixture was returned to room temperature, aqueous ammonia was added, quenched, extracted with dichloromethane, and dried with anhydrous magnesium sulfate. This was concentrated under reduced pressure, and the resulting mixture was purified by silica gel column chromatography to obtain intermediate a (2.10 g, 8.6 mmol, yield 51%).

^1H NMR (400MHz, CDCl ₃ )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 spectral analysis: theoretical value 246.06, observed value 247.98.

Compound 15

Under a nitrogen stream, intermediate a (0.5 g) was added to a dimethylformamide solution (40 mL) of 5H-benzofluo[3,2-c]carbazole (1.01 g, 4.0 mmol) and potassium carbonate (0.69 g, 5.0 mmol). , 2.0 mmol) was added and stirred at 150°C overnight. This mixture was returned to room temperature, water was added, 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, 0.86 mmol, yield 43%).

^1H NMR(400MHz, CDCl ₃ )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 spectral analysis: theoretical 483.14, observed 484.13.

Compound 185

Under a nitrogen stream, a dimethylformamide solution of 7H-bisbenzoflu[3,2-c:2',3'-g]carbazole (0.83 g, 2.4 mmol) and potassium carbonate (0.55 g, 4.0 mmol) ( 50 mL), intermediate a (0.5 g, 2.0 mmol) was added, and the mixture was stirred at 150°C for 5 hours. This mixture was returned to room temperature, water was added, 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, 1.3 mmol, 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 spectral analysis: theoretical value 573.15, observed value 574.26

(Synthesis Example 2)

[Formula 26]

intermediate b

Under a nitrogen stream, a dimethylformamide solution (5 mL) of 3-fluoro-9,10-phenanthrenequinone (2.19 g, 9.7 mmol) and potassium cyanide (0.031 g, 0.48 mmol) was stirred for 30 minutes, and then stirred for 30 minutes. Methylsilyl cyanide (3.6 mL, 29.1 mmol) was added, and the mixture was stirred at room temperature for 3 hours. After that, dry acetonitrile (30 mL) and phosphorus tribromide (1.4 mL, 14.5 mmol) were added, the temperature was raised to 50°C, and the mixture was stirred overnight. This mixture was returned to room temperature, aqueous ammonia was added, quenched, extracted with dichloromethane, and dried with anhydrous magnesium sulfate. This was concentrated under reduced pressure, and the resulting mixture was purified by silica gel column chromatography to obtain intermediate b (0.88 g, 3.6 mmol, yield 37%).

ASAP mass spectral analysis: theoretical value 246.06, observed value 247.76.

Compound 632

Under a nitrogen stream, a dimethylformamide solution of 7H-bisbenzoflu[3,2-c:2',3'-g]carbazole (1.0 g, 2.8 mmol) and potassium carbonate (0.67 g, 4.8 mmol) ( 50 mL), intermediate b (0.6 g, 2.4 mmol) was added, and stirred at 150°C for 5 hours. This mixture was returned to room temperature, water was added, 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, 1.3 mmol, 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 spectral analysis: theoretical value 573.15, observed value 574.24

Compound 894

Under nitrogen flow, 10,15-dihydro-15-phenyl-benzofluo[3,2-a]indolo[3,2-c]carbazole (0.55 g, 1.32 mmol) and potassium carbonate (0.31 g, 2.2 mmol) mmol), intermediate b (0.28 g, 1.1 mmol) was added to the dimethylformamide solution (50 mL), and the mixture was stirred at 150°C for 6 hours. This mixture was returned to room temperature, water was added, 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, 0.41 mmol, 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 spectral analysis: theoretical value 648.20, observed value 649.64

(Synthesis Example 3)

[Formula 27]

intermediate c

Under a nitrogen stream, a dimethylformamide solution (12 mL) of 2,7-fluoro-9,10-phenanthrenequinone (3.1 g, 12.7 mmol) and potassium cyanide (0.04 g, 0.63 mmol) was stirred for 30 minutes. , trimethylsilyl cyanide (4.77 mL, 38.1 mmol) was added, and stirred at room temperature for 3 hours. After that, dry acetonitrile (72 mL) and phosphorus tribromide (1.5 mL, 15.2 mmol) were added, the temperature was raised to 50°C, and the mixture was stirred overnight. This mixture was returned to room temperature, aqueous ammonia was added, quenched, extracted with dichloromethane, and dried over anhydrous magnesium sulfate. This was concentrated under reduced pressure, and the resulting mixture was purified by silica gel column chromatography to obtain intermediate c (0.71 g, 2.68 mmol, yield 21%).

^1H NMR (400MHz, CDCl ₃ )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 spectral analysis: theoretical value 246.05, observed value 264.02.

Compound 21949

Under a nitrogen stream, intermediate c was added to a nitrobenzene solution (16 mL) of 12H-[1]benzothieno[2,3-a]carbazole (1.0 g, 3.78 mmol) and potassium carbonate (1.04 g, 7.55 mmol). (0.4g, 1.51mmol) was added and stirred at 195°C overnight. This mixture was returned to room temperature, hexane was added, and the precipitated solid was filtered and washed with hexane. The obtained solid was purified by silica gel column chromatography to obtain compound 21949 (0.12 g, 0.16 mmol, 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 spectral analysis: theoretical value 770.16, observed value 771.42.

Compound 34941

Nitrobenzene solution (40 mL) 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) under nitrogen flow. Intermediate c (1.0 g, 3.7 mmol) was added and stirred at 195°C for 1 hour. This mixture was returned to room temperature, hexane was added, and the precipitated solid was filtered and washed with hexane. The obtained solid was purified by silica gel column chromatography to obtain compound 34941 (0.77 g, 0.86 mmol, yield 23%).

¹ H 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 spectral analysis: theoretical value 888.30, observed value 890.40.

Compound 35837

Nitrobenzene solution (3 mL) 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) under nitrogen stream. Intermediate c (0.072 g, 0.27 mmol) was added and stirred at 195°C for 1 hour. This mixture was returned to room temperature, hexane was added, and the precipitated solid was filtered and washed with hexane. The obtained solid was purified by silica gel column chromatography to obtain compound 35837 (0.11 g, 0.12 mmol, yield 45%).

¹ H 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 spectral analysis: theoretical value 888.30, observed value 889.56.

Compound 8061

Under a nitrogen stream, intermediate c (0.1 g) was added to a dimethylformamide solution (10 mL) of 5H-benzofluo[3,2-c]carbazole (0.285 g, 1.2 mmol) and potassium carbonate (0.15 g, 1.2 mmol). , 0.37 mmol) was added and stirred at 150°C for 2 hours. This mixture was returned to room temperature, water was added, 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, 0.19 mmol, 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 spectral analysis: theoretical value 738.21, observed value 739.25

(Synthesis Example 4)

[Formula 28]

intermediate d

Under a nitrogen stream, 2-fluoro-5-formylbenzonitrile (4.3g, 19.0mmol), copper powder (2.9g, 47.5mmol), and copper(I) 2-thiophenecarboxylic acid (0.9g, 4.75mmol) Dimethyl sulfoxide solution (100 mL) was stirred at 50°C overnight. Afterwards, the mixture was returned to room temperature, water was added, quenched, extracted with ethyl acetate, and dried over anhydrous magnesium sulfate. This was concentrated under reduced pressure, and the resulting mixture was purified by silica gel column chromatography to obtain intermediate d (2.36 g, 7.7 mmol, yield 82%).

^1H NMR (400MHz, CDCl ₃ )δ9.76(s, 2H), 8.26(d, J=6.4Hz, 2H), 7.16(d, J=8.8Hz, 2H).

ASAP mass spectral analysis: theoretical value 296.04, observed value 297.18.

intermediate e

Under a nitrogen stream, a toluene solution (70 mL) of intermediate d (2.3 g, 7.7 mmol) and p-toluenesulfonylhydrazide (2.9 g, 15.8 mmol) was stirred at 60°C for 30 minutes, and toluene (150 mL) was added. Returned to room temperature. Afterwards, 4ÅMS (2.3g), lithium tert-butoxide (1.8g, 23.1mmol), rhodium(II) acetate (dimer) (0.05g, 0.11mmol), and toluene (180mL) were added to this reaction, and incubated at 90°C. Stirred for 2 hours. Afterwards, this mixture was returned to room temperature, and a short column using silica gel (ethyl acetate) was performed to obtain a crude product. This was purified by silica gel column chromatography to obtain intermediate e (1.84 g, 6.97 mmol, yield 91%).

^1H NMR (400MHz, CDCl ₃ )δ8.30-8.27(m, 4H), 7.81(s, 2H).

ASAP mass spectral analysis: theoretical value 264.05, observed value 265.02.

Compound 434559

Under a nitrogen stream, a dimethylformamide solution (50 mL) 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) ), intermediate e (0.5 g, 1.9 mmol) was added, and stirred at 150°C for 1 hour. This mixture was returned to room temperature, water was added, 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, 1.76 mmol, yield 92%).

¹ H NMR (400 MHz, 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 spectral analysis: theoretical value 888.30, observed value 889.75

(Synthesis Example 5)

[Formula 29]

intermediate f

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

^1H NMR (400MHz, CDCl ₃ )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 spectral analysis: theoretical value 246.21, observed value 246.94.

intermediate g

4,5-difluoro-[1,1'-biphenyl]-2,2'dicarboxialdehyde f (9.30 g, 38.0 mmol) and copper(I) chloride (0.375 g, 3.8 mmol). Methyl sulfoxide (200 mL) was added. A 70% tert-butylhydroperoxide solution (26 mL, 189 mmol) was added dropwise to this solution and stirred at room temperature for 10 minutes. After completion of the reaction, the mixture was cooled to room temperature, water was added, and filtration and extraction were performed. The obtained mixture was purified by silica gel column chromatography and then recrystallized to obtain g (6.1 g, yield 66%) of 2,3-difluoro-9,10-phenanthrenequinone.

^1H NMR (400MHz, CDCl ₃ )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 spectral analysis: theoretical value 244.20, observed value 244.99.

intermediate h

Under a nitrogen stream, a dimethylformamide solution (30 mL) of 2,3-difluoro-9,10-phenanthrenequinone g (3.0 g, 12.29 mmol) and potassium cyanide (0.080 g, 1.23 mmol) was reacted for 30 minutes. After stirring, trimethylsilyl cyanide (4.6 mL, 36.9 mmol) was added, and the mixture was stirred at room temperature for 3 hours. After that, dry acetonitrile (200 mL) and phosphorus tribromide (3.5 mL, 36.9 mmol) were added, the temperature was raised to 70°C, and the mixture was stirred overnight. This mixture was returned to room temperature, aqueous ammonia was added, quenched, extracted with dichloromethane, and dried with anhydrous magnesium sulfate. This was concentrated under reduced pressure, and the resulting mixture was purified by silica gel column chromatography to obtain intermediate h (1.64 g, 6.2 mmol, yield 50%).

^1H NMR (400MHz, CDCl ₃ )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 spectral analysis: theoretical value 264.23, observed value 265.10.

Compound 806951

Under a nitrogen stream, intermediate h was added to a dimethylformamide solution (100 mL) of 5H-2-phenylbenzofluo[3,2-c]carbazole (2.52 g, 7.57 mmol) and potassium carbonate (1.25 g, 9.08 mmol). (0.800 g, 3.03 mmol) was added and stirred at 140°C for 4 hours. This mixture was returned to room temperature, water was added, 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, 1.92 mmol, yield 64%).

^1H NMR(400MHz, CDCl ₃ )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, 3.2 Hz, 1H), 7.69-7.52(m, 8H), 7.46-7.22(m, 15H).

ASAP mass spectral analysis: theoretical value 891.00, observed value 891.59

Compound 806993

Under a nitrogen stream, a dimethylformamide solution (100 mL) 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) ), intermediate h (0.780 g, 2.95 mmol) was added, and stirred at 150°C for 9 hours. This mixture was returned to room temperature, water was added, 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, 0.675 mmol, yield 22.9%).

^1H NMR (400MHz, CDCl ₃ )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 spectral analysis: theoretical value 889.03, observed value 889.68

(Synthesis Example 5)

[Formula 30]

intermediate i

Under nitrogen flow, 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 -Dichloromethane in a mixture of 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). A mixed solution of (500 mL)/trifluoroacetic acid (500 mL) was added, the temperature was raised to 90°C, and the reaction was allowed to occur overnight. After completion of the reaction, it was cooled to room temperature, and filtration and extraction were performed. The obtained mixture was purified by silica gel column chromatography to obtain intermediate i (13.0 g, yield 34.8%).

^1H NMR (400MHz, CDCl ₃ )δ10.25(s, 1H), 7.64(t, J=8.8Hz, 1H)

ASAP mass spectral analysis: theoretical value 237.94, observed value 239.07.

intermediate j

Under nitrogen stream, 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), carbonic acid To the mixture of potassium (15.0 g, 109 mmol), a mixed solution of toluene (540 mL)/ethanol (360 mL)/water (180 mL) was added, the temperature was raised to 90°C, and the reaction was allowed to occur overnight. After completion of the reaction, the mixture was cooled to room temperature, water was added, 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, CDCl ₃ )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 spectral analysis: theoretical value 264.04, observed value 265.06.

intermediate k

Dimethyl sulfoxide (150 mL) was added to a mixture of intermediate j (3.94 g, 14.9 mmol) and copper(I) chloride (0.295 g, 2.98 mmol). A 70% tert-butylhydroperoxide solution (6.13 mL, 44.7 mmol) was added dropwise to this solution, and the mixture was stirred at room temperature for 16 hours. After completion of the reaction, water was added and filtration and extraction were performed. The obtained mixture was purified by silica gel column chromatography and then recrystallized to obtain intermediate k (0.97 g, yield 25%).

^1H NMR (400MHz, CDCl ₃ )δ8.39(d, J=8.2Hz, 1H), 8.26(d, J=7.8Hz, 1H), 7.91(t, 8.2Hz, 1H), 7.78(t, 7.8 Hz, 1H), 7.56(t, J=7.6Hz, 1H)

ASAP mass spectral analysis: theoretical value 262.02, observed value 263.01.

intermediate m

Under a nitrogen stream, a dimethylformamide solution (7 mL) of intermediate k (1.55 g, 5.91 mmol) and potassium cyanide (0.038 g, 0.59 mmol) was stirred for 30 minutes, and trimethylsilyl cyanide (2.22 mL, 17.7 mmol) was added. ) was added and stirred at room temperature for 3 hours. After that, dry acetonitrile (42 mL) and phosphorus tribromide (1.68 mL, 17.7 mmol) were added, the temperature was raised to 80°C, and the mixture was stirred overnight. This mixture was returned to room temperature, aqueous ammonia was added, quenched, extracted with dichloromethane, and dried with anhydrous magnesium sulfate. This was concentrated under reduced pressure, and the resulting mixture was purified by silica gel column chromatography to obtain intermediate m (0.18 g, 0.64 mmol, yield 10%).

^1H NMR (400MHz, CDCl ₃ )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 spectral analysis: theoretical value 282.04, observed value 283.11.

Compound 1006742

Under a nitrogen stream, intermediate m (0.13 g, 0.46 mmol) was added and stirred at 190°C for 16 hours. This mixture was returned to room temperature, water was added, 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, 0.060 mmol, yield 13%).

^1H NMR (400MHz, CDCl ₃ )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 spectral analysis: theoretical value 993.27, observed value 994.65

(Example 1) Production and evaluation of thin films

By vacuum deposition on a quartz substrate, Compound 15 and mCBP were deposited from different deposition sources under vacuum conditions of less than 1×10 ^-3 Pa, and a thin film with a concentration of Compound 15 of 20% by weight was formed with a thickness of 100 nm.

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

The maximum emission wavelength (λmax) and photoluminescence quantum yield (PLQY) when 300 nm excitation light was irradiated on each formed thin film were measured. In addition, the energy of HOMO and LUMO were measured. The results are shown in Table 3.

[Table 3]

(Example 2) Fabrication and evaluation of organic electroluminescence device

Each thin film was laminated by vacuum deposition at a vacuum degree of 5.0 x 10 ^-5 Pa on a glass substrate on which an anode made of indium tin oxide (ITO) with a film thickness of 50 nm was formed. First, HAT-CN was formed on ITO to a thickness of 10 nm, and NPD was formed on it to a thickness of 30 nm. Next, Tris-PCz was formed to a thickness of 10 nm, and EBL1 was formed to a thickness of 5 nm. Next, EBL1 and Compound 15 were co-deposited from different deposition sources to form a layer with a thickness of 40 nm, which was used as a light-emitting layer. The concentration of compound 15 in the light emitting layer was 40% by mass. Next, SF3-TRZ was formed to a thickness of 10 nm, and then Liq and SF3-TRZ were co-deposited from different deposition sources to form a layer with a thickness of 30 nm. The concentrations of Liq and SF3-TRZ in this layer were 30 mass% and 70 mass%, respectively. Additionally, Liq was formed to a thickness of 2 nm, and then aluminum (Al) was deposited to a thickness of 100 nm to form a cathode, thereby forming an organic electroluminescence device.

Instead of compound 15, 185, 632, 806951, 806993, and 8061 were used, respectively, to produce an organic electroluminescence device using the same procedure.

When each fabricated organic electroluminescence device is continuously energized and emits light at a driving voltage of 2 mA/cm ² , maximum external quantum efficiency (EQE), and 5.5 mA/cm ² , the luminescence intensity decreases to 95% of the initial value. The time (LT95) required to complete each test was measured. The results are shown in Table 4. LT95 is expressed as a relative value when compound 632 is set to 1.

[Table 4]

An organic electroluminescence device using compound 8061 also showed a high EQE of 9.7%.

The compound represented by General Formula (1) has a high photoluminescence quantum yield and is excellent as a light-emitting material. Additionally, an organic electroluminescence device using a compound represented by General Formula (1) has high luminous efficiency, low driving voltage, and long lifespan.

[Formula 31]

1 listing
2 anode
3 hole injection layer
4 hole transport layer
5 emitting layer
6 electron transport layer
7 cathode

Claims (26)

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

[In General Formula (1), R ¹ to R ¹⁰ each independently represent a hydrogen atom, a deuterium atom, or a substituent. However, 1 or 2 of R ¹ to R ¹⁰ represents a cyano group, and 1 to 4 of R ¹ to R ¹⁰ represents a donor group bonded to a 5-membered ring.
R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , R ¹⁰ and R ¹ may be combined with each other to form a cyclic structure.] In claim 1,
A compound in which the donor group bonded to the 5-membered ring is a substituted or unsubstituted ring-condensed indol-1-yl group. In claim 1,
A compound wherein the donor group bonded to the 5-membered ring is a substituted or unsubstituted ring-condensed carbazol-9-yl group. In claim 1,
A compound wherein the donor group bonded to the 5-membered ring is a ring-condensed carbazol-9-yl group substituted with a substituent. In claim 1,
A compound wherein the donor group bonded to the 5-membered ring is a ring-condensed carbazol-9-yl group substituted with an aryl group or heteroaryl group. In claim 1,
A compound wherein the donor group bonded to the 5-membered ring is a ring-condensed carbazol-9-yl group substituted with an aryl group. In claim 3,
The ring-condensed carbazol-9-yl group is a carbazol-9-yl group in which a ring is condensed with one or more atoms selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom as ring skeleton constituent atoms. In claim 3,
A compound in which the ring-condensed carbazol-9-yl group is a ring-condensed carbazol-9-yl group containing at least one atom selected from the group consisting of an oxygen atom and a sulfur atom as a ring skeleton constituent atom. In claim 3,
A compound in which two of R ¹ to R ¹⁰ are cyano groups, and two of R ¹ to R ¹⁰ are substituted or unsubstituted ring-condensed carbazol-9-yl groups. In claim 3,
A compound in which two of R ¹ to R ¹⁰ are the same substituted or unsubstituted ring-condensed carbazol-9-yl group. In claim 3,
A compound in which two of R ¹ to R ¹⁰ are cyano groups and one of R ¹ to R ¹⁰ is a substituted or unsubstituted ring-condensed carbazol-9-yl group. In claim 1,
A compound wherein R ⁹ and R ¹⁰ are cyano groups. In claim 1,
A compound wherein R ² and R ⁷ are cyano groups. In claim 1,
A compound having an axisymmetric structure. A light-emitting material comprising the compound according to any one of claims 1 to 14. A delayed phosphor comprising the compound according to any one of claims 1 to 14. A membrane comprising the compound according to any one of claims 1 to 14. An organic semiconductor device comprising the compound according to any one of claims 1 to 14. An organic light-emitting device comprising the compound according to any one of claims 1 to 14. In claim 19,
An organic light-emitting device, wherein the device has a layer containing the compound, and the layer also includes a host material. In claim 20,
An organic light-emitting device, wherein the layer containing the compound also contains a delayed fluorescent material in addition to the compound and the host material, and the lowest singlet excitation energy of the delayed fluorescent material is lower than that of the host material and higher than that of the compound. In claim 20,
An organic light-emitting device, wherein the device has a layer containing the compound, and the layer also includes a light-emitting material having a structure different from that of the compound. In claim 20,
An organic light-emitting device in which the amount of light emitted from the compound is greatest among the materials included in the device. In claim 22,
An organic light-emitting device in which the amount of light emitted from the light-emitting material is greater than the amount of light emitted from the compound. The method of any one of claims 19 to 24,
An organic electroluminescence device, an organic light-emitting device. The method of any one of claims 19 to 24,
An organic light-emitting device that emits delayed fluorescence.