JPWO2015137244A1 - Luminescent materials, organic light emitting devices and compounds - Google Patents

Abstract

The compound represented by the general formula (1) is useful as a light emitting material. R1 and R2 each independently represents a substituted or unsubstituted aryl group, and at least one of R1 and R2 is an aryl group substituted with an N, N-diarylamino group.

Description

  The present invention relates to a compound useful as a light emitting material and an organic light emitting device using the compound.

  Researches for increasing the light emission efficiency of organic light emitting devices such as organic electroluminescence devices (organic EL devices) are being actively conducted. In particular, various efforts have been made to increase the light emission efficiency by newly developing and combining electron transport materials, hole transport materials, light emitting materials, and the like constituting the organic electroluminescence element. On the other hand, the results of studies on synthesis methods and optical properties of compounds having a bisthiadiazoloquinoxaline skeleton have been reported. There are also reports mentioning that they can be used as materials for electroluminescent devices.

  Non-Patent Document 1 describes a method for synthesizing a compound having a bisthiadiazoloquinoxaline skeleton. However, Non-Patent Document 1 does not describe at all that a compound having a bisthiadiazoloquinoxaline skeleton is useful as a light-emitting material of an organic electroluminescence device.

  Non-Patent Document 2 describes the results of studying spectroscopic characteristics and electrochemical characteristics of a compound having a bisthiadiazoloquinoxaline skeleton, and this compound is useful as a carrier transfer material for organic electroluminescence devices. It also mentions that there is. However, Non-Patent Document 2 does not describe at all the usefulness of a compound having a bisthiadiazoloquinoxaline skeleton as a luminescent material. In addition, the compounds specifically exemplified in the same document have an alkyl group or a substituted phenyl group in a structure in which a phenyl group is substituted on the pyrazine ring of the bisthiadiazoloquinoxaline skeleton or a structure in which the phenyl group is condensed. There is no description of compounds that are substituted and substituted with a substituent other than an alkyl group or a substituted phenyl group on a phenyl group substituted with a bisthiadiazoloquinoxaline skeleton or a condensed ring of a phenyl group.

J. Heterocyclic Chem. 1975, 12, 829-833 Chem. Lett. 2011, 40, 1252-1253

On the other hand, when the present inventors began various studies on a compound group having a bisthiadiazoloquinoxaline skeleton, among a large number of compounds having a bisthiadiazoloquinoxaline skeleton, It has been found for the first time that a compound group having a structure may be useful as a light emitting material. In particular, the present inventors have found that a compound group in which a diarylaminoaryl group is substituted on a pyrazine ring of a bisthiadiazoloquinoxaline skeleton has a remarkable possibility.
As described above, Non-Patent Document 1 describes a method for synthesizing a compound having a bisthiadiazoloquinoxaline skeleton, but it describes that the compound can be used as a material for an organic electroluminescence device. Not. On the other hand, Non-Patent Document 2 describes that a compound having a bisthiadiazoloquinoxaline skeleton is useful as a carrier transfer material for an organic electroluminescence device. However, no investigation has been made as to whether or not the compound described in Non-Patent Document 2 can function as a light-emitting material. Since the light-emitting material is different in required properties and functions from the carrier transfer material, the usefulness of the compound described in Non-Patent Document 2 as the light-emitting material is unknown. Further, Non-Patent Document 2 does not describe a compound in which a diarylaminoaryl group is substituted on the pyrazine ring of a bisthiadiazoloquinoxaline skeleton, and its usefulness as a light-emitting material cannot be predicted.

  Under such circumstances, the present inventors have further investigated the usefulness of a compound having a bisthiadiazoloquinoxaline skeleton as a light-emitting material, and conducted research aiming to find a compound having excellent light-emitting properties. Piled up. And the general formula of the compound useful as a luminescent material was derived, and the earnest examination was advanced for the purpose of generalizing the structure of the organic light emitting element with high luminous efficiency.

  As a result of intensive studies, the present inventors have confirmed that a compound in which a specific substituent is substituted on the pyrazine ring of a bisthiadiazoloquinoxaline skeleton has excellent properties as a light-emitting material. In addition, it has been found that such a group of compounds is useful as a delayed fluorescent material, and it has been clarified that an organic light-emitting device having high emission efficiency can be provided at low cost. Based on these findings, the present inventors have provided the following present invention as means for solving the above problems.

［一般式（１）において、Ｒ¹およびＲ²は各々独立に置換もしくは無置換のアリール基を表し、Ｒ¹およびＲ²の少なくとも一方は、Ｎ，Ｎ−ジアリールアミノ基が置換したアリール基である。］
［２］ 一般式（１）のＲ¹およびＲ²の少なくとも一方が、下記一般式（２）で表わされる基であることを特徴とする［１］に記載の発光材料。

［一般式（２）において、＊は一般式（１）におけるピラジン環への結合部位を表す。Ａｒ¹〜Ａｒ³は各々独立に炭素数４〜１０の置換もしくは無置換の炭素環芳香族基または炭素数４〜１０の置換もしくは無置換の複素環芳香族基を表す。］
［３］ 一般式（２）のＡｒ¹が、無置換のフェニレン基、無置換のナフチレン基または無置換のビフェニレン基であることを特徴とする［２］に記載の発光材料。
［４］ 一般式（２）のＡｒ¹が、無置換のフェニレン基であることを特徴とする［２］または［３］に記載の発光材料。
［５］ 一般式（２）のＡｒ²およびＡｒ³が、各々独立に置換もしくは無置換のフェニル基または置換もしくは無置換のナフチル基であることを特徴とする［２］〜［４］のいずれか１項に記載の発光材料。
［６］ 一般式（２）のＡｒ²およびＡｒ³が、各々独立に置換もしくは無置換のフェニル基であることを特徴とする［２］〜［５］のいずれか１項に記載の発光材料。
［７］ 一般式（２）のＡｒ₂およびＡｒ₃が、単結合または連結基を介して互いに結合していることを特徴とする［２］〜［６］のいずれか１項に記載の発光材料。
［８］ 一般式（１）で表される化合物が、下記一般式（３）で表される化合物であることを特徴とする［１］に記載の発光材料。

［一般式（３）において、Ｒ³およびＲ⁴は各々独立に水素原子または置換基を表し、Ｒ³およびＲ⁴の少なくとも一方は、下記一般式（４）で表される基である。］

［一般式（４）において、＊は一般式（３）におけるベンゼン環への結合部位を表す。Ｘは置換もしくは無置換のメチレン基、置換もしくは無置換のエチレン基、置換もしくは無置換のビニレン基、置換もしくは無置換のイミノ基、酸素原子または硫黄原子を表す。］
［９］ 一般式（４）のＸが、酸素原子であることを特徴とする［８］に記載の発光材料。
［１０］ 前記一般式（１）で表される化合物からなる遅延蛍光体。
［１１］ ［１］〜［９］のいずれか１項に記載の発光材料を含むことを特徴とする有機発光素子。
［１２］ 遅延蛍光を放射することを特徴とする［１１］に記載の有機発光素子。
［１３］ 有機エレクトロルミネッセンス素子であることを特徴とする［１１］または［１２］に記載の有機発光素子。
［１４］ 下記一般式（３）で表される化合物。

［一般式（３）において、Ｒ³およびＲ⁴は各々独立に水素原子または置換基を表し、Ｒ³およびＲ⁴の少なくとも一方は、下記一般式（４）で表される基である。］

［一般式（４）において、＊は一般式（３）におけるベンゼン環への結合部位を表す。Ｘは置換もしくは無置換のメチレン基、置換もしくは無置換のエチレン基、置換もしくは無置換のビニレン基、置換もしくは無置換のイミノ基、酸素原子または硫黄原子を表す。］[1] A light emitting material comprising a compound represented by the following general formula (1).

[In General Formula (1), R ¹ and R ² each independently represent a substituted or unsubstituted aryl group, and at least one of R ¹ and R ² is an aryl group substituted with an N, N-diarylamino group. is there. ]
[2] The luminescent material as described in [1], wherein at least one of R ¹ and R ^{2 in} the general formula (1) is a group represented by the following general formula (2).

[In General Formula (2), * represents the bonding site to the pyrazine ring in General Formula (1). Ar ^{1 to} Ar ³ each independently represents a substituted or unsubstituted carbocyclic aromatic group having 4 to 10 carbon atoms or a substituted or unsubstituted heterocyclic aromatic group having 4 to 10 carbon atoms. ]
[3] The luminescent material according to [2], wherein Ar ^{1 in the} general formula (2) is an unsubstituted phenylene group, an unsubstituted naphthylene group, or an unsubstituted biphenylene group.
[4] The luminescent material according to [2] or [3], wherein Ar ^{1 in the} general formula (2) is an unsubstituted phenylene group.
[5] Any one of [2] to [4], wherein Ar ² and Ar ^{3 in} the general formula (2) are each independently a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group. The light emitting material according to claim 1.
[6] The light-emitting material according to any one of [2] to [5], wherein Ar ² and Ar ^{3 in} the general formula (2) are each independently a substituted or unsubstituted phenyl group. .
[7] The luminescence according to any one of [2] to [6], wherein Ar ₂ and Ar _{3 in} the general formula (2) are bonded to each other through a single bond or a linking group. material.
[8] The light-emitting material according to [1], wherein the compound represented by the general formula (1) is a compound represented by the following general formula (3).

[In General Formula (3), R ³ and R ⁴ each independently represent a hydrogen atom or a substituent, and at least one of R ³ and R ⁴ is a group represented by the following General Formula (4). ]

[In General Formula (4), * represents the bonding site to the benzene ring in General Formula (3). X represents a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted vinylene group, a substituted or unsubstituted imino group, an oxygen atom or a sulfur atom. ]
[9] The luminescent material according to [8], wherein X in the general formula (4) is an oxygen atom.
[10] A delayed phosphor comprising the compound represented by the general formula (1).
[11] An organic light emitting device comprising the light emitting material according to any one of [1] to [9].
[12] The organic light-emitting device according to [11], which emits delayed fluorescence.
[13] The organic light-emitting device according to [11] or [12], which is an organic electroluminescence device.
[14] A compound represented by the following general formula (3).

[In General Formula (3), R ³ and R ⁴ each independently represent a hydrogen atom or a substituent, and at least one of R ³ and R ⁴ is a group represented by the following General Formula (4). ]

[In General Formula (4), * represents the bonding site to the benzene ring in General Formula (3). X represents a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted vinylene group, a substituted or unsubstituted imino group, an oxygen atom or a sulfur atom. ]

  The compound of the present invention is useful as a light emitting material. The compounds of the present invention include those that emit delayed fluorescence. An organic light emitting device using the compound of the present invention as a light emitting material can realize high luminous efficiency.

It is a schematic sectional drawing which shows the layer structural example of an organic electroluminescent element. 2 is an emission absorption spectrum of a toluene solution of exemplary compound (1) of Example 1. It is an emission absorption spectrum of the thin film type organic photoluminescence element of Exemplified Compound (1) of Example 1 and CBP. It is a transient attenuation | damping curve of the thin film type organic photoluminescent element of the exemplary compound (1) of Example 1, and CBP. 2 is an emission absorption spectrum of a toluene solution of Example Compound (2) of Example 2. It is a light emission absorption spectrum of the example compound (2) of Example 2 and a thin film type organic photoluminescence device of mCBP. 2 is a transient decay curve of a toluene solution of Example Compound (2) in Example 2. It is a transient attenuation | damping curve of the thin film type organic photoluminescent element of the exemplary compound (2) of Example 2, and mCBP. 2 is an emission spectrum of an organic electroluminescent element of the exemplary compound (2) of Example 3. It is a graph which shows the voltage-current density-luminance characteristic of the organic electroluminescent element of the exemplary compound (2) of Example 3. It is a graph which shows the current density-external quantum efficiency characteristic of the organic electroluminescent element of the exemplary compound (2) of Example 3. It is a graph which shows the current density-power efficiency characteristic of the organic electroluminescent element of the exemplary compound (2) of Example 3. It is a graph which shows the current density-current efficiency characteristic of the organic electroluminescent element of the exemplary compound (2) of Example 3.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments and specific examples of the present invention, but the present invention is not limited to such embodiments and specific examples. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value. In addition, the isotope species of the hydrogen atom present in the molecule of the compound used in the present invention is not particularly limited. For example, all the hydrogen atoms in the molecule may be ¹ H, or a part or all of them are ² H. (Deuterium D) may be used.

一般式（１）において、Ｒ¹およびＲ²は各々独立に置換もしくは無置換のアリール基を表し、Ｒ¹およびＲ²の少なくとも一方は、Ｎ，Ｎ−ジアリールアミノ基が置換したアリール基である。Ｎ，Ｎ−ジアリールアミノ基が置換したアリール基は、Ｒ¹およびＲ²のうちの一方であってもよいし、Ｒ¹およびＲ²の両方であってもよいが、Ｒ¹およびＲ²の両方であることが好ましい。Ｒ¹およびＲ²の両方がＮ，Ｎ−ジアリールアミノ基が置換したアリール基であるとき、それらのＮ，Ｎ−ジアリールアミノ基は互いに同一であっても異なっていてもよいが、同一であることが好ましい。[Compound represented by general formula (1)]
The luminescent material of the present invention is characterized by comprising a compound represented by the following general formula (1).

In the general formula (1), R ¹ and R ² each independently represent a substituted or unsubstituted aryl group, and at least one of R ¹ and R ² is an aryl group substituted with an N, N-diarylamino group . N, N-aryl group diarylamino group is substituted, may be one of R ¹ and R ^2, may be both of R ¹ and R ^2, R ¹ and R ² Both are preferred. When both R ¹ and R ² are aryl groups substituted by N, N-diarylamino groups, these N, N-diarylamino groups may be the same or different from each other, but are the same It is preferable.

The aryl group substituted by the N, N-diarylamino group is preferably a group represented by the following general formula (2).

In the general formula (2), * represents a binding site to the pyrazine ring in the general formula (1). Ar ^{1 to} Ar ³ each independently represents a substituted or unsubstituted carbocyclic aromatic group having 4 to 10 carbon atoms or a substituted or unsubstituted heterocyclic aromatic group having 4 to 10 carbon atoms. The aromatic groups represented by Ar ^{1 to} Ar ³ may be the same or different from each other, but Ar ² and Ar ³ are preferably the same. When a plurality of groups represented by the general formula (2) are present in the compound represented by the general formula (1), the plurality of Ar ^{1 to} Ar ³ may be the same as or different from each other.
Preferably Ar ¹ of Ar ¹ to Ar ³ is an unsubstituted carbocyclic aromatic group, an unsubstituted phenylene group, more preferably an unsubstituted naphthylene group or unsubstituted biphenylene group, unsubstituted The phenylene group is more preferable.
Ar ² and Ar ³ are preferably each independently a substituted or unsubstituted carbocyclic aromatic group, more preferably a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group. More preferably, it is a substituted phenyl group. Ar ² and Ar ³ may be bonded by a single bond or may be linked via a linking group. Examples of the linking group include a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted vinylene group, a substituted or unsubstituted imino group, an oxygen atom or a sulfur atom. Among these, when the ethylene group and the vinylene group are substituted with a plurality of substituents, two adjacent substituents may be bonded to each other to form a cyclic structure. Regarding the explanation and preferred examples of the cyclic structure formed by bonding two adjacent substituents to each other, for the cyclic structure formed by bonding two substituents to each other when X is an ethylene group or vinylene group Reference can be made to the description and preferred examples.

When ^one of R ¹ and R ² is an aryl group substituted with an N, N-diarylamino group, the substituted or unsubstituted aryl group that the other can take is a substituted or unsubstituted carbocyclic aromatic group Or a substituted or unsubstituted heterocyclic aromatic group, preferably a substituted or unsubstituted carbocyclic aromatic group, preferably a substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl It is more preferably a group or a substituted or unsubstituted biphenyl group, and further preferably a substituted or unsubstituted phenyl group.

Preferable examples of the compound represented by the general formula (1) include a compound represented by the following general formula (3).

In the general formula (3), R ³ and R ⁴ each independently represent a hydrogen atom or a substituent, and at least one of R ³ and R ⁴ is a group represented by the following general formula (4). Groups represented by the following general formula (4) may be one of R ³ and R ^4, may it be both R ³ and R ^4, both of R ³ and R ⁴ It is preferable that When both R ³ and R ⁴ are groups represented by the following general formula (4), the two groups represented by the following general formula (4) may be the same or different from each other. Are preferably the same.

  In the general formula (4), * represents a bonding site to the benzene ring in the general formula (3). X represents a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted vinylene group, a substituted or unsubstituted imino group, an oxygen atom or a sulfur atom, and a methylene group substituted with a methyl group Or it is preferably an oxygen atom, and more preferably an oxygen atom.

Substituents that can be substituted on R ¹ and R ² , substituents that R ³ and R ⁴ can take, substituents that can be substituted on Ar ^{1 to} Ar ^3, and substituents that can be substituted on X include, for example, hydroxy groups, halogen atoms , A cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkyl-substituted amino group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms An aryl group having 6 to 40 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, and a carbon number 1-10 alkylsulfonyl group, C1-C10 haloalkyl group, amide group, C2-C10 alkylamide group, C3-C20 trialkylsilyl group, C4-C20 trialkylsilyl A Kill group, trialkylsilyl alkenyl group having 5 to 20 carbon atoms and an trialkylsilyl alkynyl group and a nitro group having 5 to 20 carbon atoms. Among these specific examples, those that can be substituted with a substituent may be further substituted. More preferred substituents are a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, carbon A substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms and a dialkyl-substituted amino group having 1 to 20 carbon atoms. More preferable substituents are a fluorine atom, a chlorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, and a substituted group having 6 to 15 carbon atoms. Or it is an unsubstituted aryl group, a C3-C12 substituted or unsubstituted heteroaryl group.

  When X is an ethylene group or vinylene group substituted with a plurality of substituents, two adjacent substituents of the ethylene group or vinylene group may be bonded to each other to form a cyclic structure. The cyclic structure may be an aromatic ring or an alicyclic ring, may contain a hetero atom, and the cyclic structure may be a condensed ring of two or more rings. The hetero atom here is preferably selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. Examples of cyclic structures formed include benzene ring, naphthalene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, imidazoline ring, oxazole ring, isoxazole ring, thiazole And a ring, an isothiazole ring, a cyclohexadiene ring, a cyclohexene ring, a cyclopentaene ring, a cycloheptatriene ring, a cycloheptadiene ring, and a cycloheptaene ring.

  Below, the specific example of a compound represented by General formula (1) is illustrated. However, the compound represented by the general formula (1) that can be used in the present invention should not be limitedly interpreted by these specific examples.

The molecular weight of the compound represented by the general formula (1) is, for example, 1500 or less when the organic layer containing the compound represented by the general formula (1) is intended to be formed by vapor deposition. Preferably, it is preferably 1200 or less, and more preferably 1000 or less. The lower limit of the molecular weight is the molecular weight of the minimum compound represented by the general formula (1).
The compound represented by the general formula (1) may be formed by a coating method regardless of the molecular weight. If a coating method is used, a film can be formed even with a compound having a relatively large molecular weight.

By applying the present invention, it is also conceivable 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 previously polymerizing a polymerizable group in the structure represented by the general formula (1) and polymerizing the polymerizable group as a light emitting material. Specifically, by preparing a monomer containing a polymerizable functional group in either R ¹ or R ² of the general formula (1) and polymerizing this alone or copolymerizing with other monomers, It is conceivable to obtain a polymer having a repeating unit and use the polymer as a light emitting material. Alternatively, it is also conceivable that dimers and trimers are obtained by reacting compounds having a structure represented by the general formula (1) and used as a luminescent material.

As an example of a polymer having a repeating unit including a structure represented by the general formula (1), a polymer including a structure represented by the following general formula (5) or (6) can be given.

In the general formula (5) or (6), Q represents a group including the structure represented by the general formula (1), and L ¹ and L ² represent a linking group. Carbon number of a coupling group becomes like this. Preferably it is 0-20, More preferably, it is 1-15, More preferably, it is 2-10. And preferably has a structure represented by - linking group -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, preferably a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group, and a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted group A phenylene group is more preferable.
In the general formula (5) or (6), R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ each independently represent a substituent. Preferably, it is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, or a halogen atom, more preferably an unsubstituted alkyl group having 1 to 3 carbon atoms. An unsubstituted alkoxy group having 1 to 3 carbon atoms, a fluorine atom, and a chlorine atom, and more preferably an unsubstituted alkyl group having 1 to 3 carbon atoms and an unsubstituted alkoxy group having 1 to 3 carbon atoms.
The linking group represented by L ¹ and L ² is any ^one of R ¹ and R ^{2 in} the structure of the general formula (1) constituting Q, any one of Ar ^{1 to} Ar ^{3 in} the general formula (2), It can be bonded to either R ³ or R ^{4 in} the structure of the formula (3), or X in the structure of the general formula (4). Two or more linking groups may be linked to one Q to form a crosslinked structure or a network structure.

Specific examples of the structure of the repeating unit include structures represented by the following formulas (7) to (10).

In the polymer having a repeating unit containing these formulas (7) to (10), a hydroxy group is introduced into either R ¹ or R ^{2 in} the structure of the general formula (1), and this is used as a linker as follows. It can be synthesized by reacting a compound to introduce a polymerizable group and polymerizing the polymerizable group.

  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 other structures may be used. It may be a polymer containing repeating units. The repeating unit having a structure represented by the general formula (1) contained in the polymer may be a single type or two or more types. Examples of the repeating unit not having the structure represented by the general formula (1) include those derived from monomers used in ordinary copolymerization. Examples thereof include a repeating unit derived from a monomer having an ethylenically unsaturated bond such as ethylene and styrene.

一般式（３）において、Ｒ³およびＲ⁴は各々独立に水素原子または置換基を表し、Ｒ³およびＲ⁴の少なくとも一方は、下記一般式（４）で表される基である。

一般式（４）において、＊は一般式（３）におけるベンゼン環への結合部位を表す。Ｘは置換もしくは無置換のメチレン基、置換もしくは無置換のエチレン基、置換もしくは無置換のビニレン基、置換もしくは無置換のイミノ基、酸素原子または硫黄原子を表す。
一般式（３）におけるＲ³、Ｒ⁴および一般式（４）におけるＸの説明と好ましい範囲については、上記の一般式（１）で表される化合物の好ましい例として例示した一般（３）で表される化合物の説明を参照することができる。[Compound represented by formula (3)]
Of the compounds represented by the general formula (1), the compound represented by the following general formula (3) is a novel compound.

In the general formula (3), R ³ and R ⁴ each independently represent a hydrogen atom or a substituent, and at least one of R ³ and R ⁴ is a group represented by the following general formula (4).

In the general formula (4), * represents a bonding site to the benzene ring in the general formula (3). X represents a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted vinylene group, a substituted or unsubstituted imino group, an oxygen atom or a sulfur atom.
Regarding R ³ , R ⁴ in the general formula (3) and X in the general formula (4) and preferred ranges thereof, the general formula (3) illustrated as a preferred example of the compound represented by the general formula (1) above. Reference may be made to the description of the compounds represented.

[Synthesis Method of Compound Represented by General Formula (3)]
The compound represented by the general formula (3) can be synthesized by combining known reactions. For example, a compound in which R ³ and R ⁴ in general formula (3) are groups represented by general formula (4) starts from compound A (4,5-Diamino-bisbenzo [1,2,5] thiadiazole) It can be synthesized as a raw material by the following reaction.

A compound in which R ³ in the general formula (3) is a group represented by the general formula (4) and R ⁴ is a hydrogen atom is a compound A (4,5-Diamino-bisbenzo [1,2,5 ] thiadiazole) and the compound obtained by the following reaction I can be synthesized by the following reaction II using the starting material as a starting material.

For the explanation of X in the above reaction formula, the corresponding description in the general formula (3) can be referred to. Z represents a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom, a bromine atom, and an iodine atom are preferable. Ar represents a phenyl group.
The above reaction is an application of a known reaction, and known reaction conditions can be appropriately selected and used. Compound A as a starting material can be synthesized by the method described in AP Komin, M. Carmack, J. Heterocyclic Chem. 1975, 12, 829-833. The details of the above reaction can be referred to the synthesis examples described below. The compound represented by the general formula (3) can also be synthesized by combining other known synthesis reactions.

[Organic light emitting device]
The compound represented by the general formula (1) of the present invention is useful as a light emitting material of an organic light emitting device. For this reason, the compound represented by General formula (1) of this invention can be effectively used as a luminescent material for the light emitting layer of an organic light emitting element. The compound represented by the general formula (1) includes a delayed fluorescent material (delayed phosphor) that emits delayed fluorescence. That is, the present invention relates to a delayed phosphor having a structure represented by the general formula (1), an invention using a compound represented by the general formula (1) as a delayed phosphor, and a general formula (1). An invention of a method for emitting delayed fluorescence using the represented compound is also provided. An organic light emitting device using such a compound as a light emitting material emits delayed fluorescence and has a feature of high luminous efficiency. The principle will be described below by taking an organic electroluminescence element as an example.

  In an organic electroluminescence element, carriers are injected into a light emitting material from both positive and negative electrodes to generate an excited light emitting material and emit light. In general, in the case of a carrier injection type organic electroluminescence element, 25% of the generated excitons are excited to the excited singlet state, and the remaining 75% are excited to the excited triplet state. Therefore, the use efficiency of energy is higher when phosphorescence, which is light emission from an excited triplet state, is used. However, since the excited triplet state has a long lifetime, energy saturation occurs due to saturation of the excited state and interaction with excitons in the excited triplet state, and in general, the quantum yield of phosphorescence is often not high. On the other hand, the delayed fluorescent material transitions to the excited triplet state due to intersystem crossing, etc., and then crosses back to the excited singlet state due to triplet-triplet annihilation or absorption of thermal energy, and emits fluorescence. To do. In the organic electroluminescence device, it is considered that a thermally activated delayed fluorescent material by absorption of thermal energy is particularly useful. When a delayed fluorescent material is used for the organic electroluminescence element, excitons in the excited singlet state emit fluorescence as usual. On the other hand, excitons in the excited triplet state absorb heat generated by the device and cross between the excited singlets to emit fluorescence. At this time, since the light is emitted from the excited singlet, the light is emitted at the same wavelength as the fluorescence, but the light lifetime (luminescence lifetime) generated by the reverse intersystem crossing from the excited triplet state to the excited singlet state is normal. Since the fluorescence becomes longer than the fluorescence and phosphorescence, it is observed as fluorescence delayed from these. This can be defined as delayed fluorescence. If such a heat-activated exciton transfer mechanism is used, the ratio of the compound in an excited singlet state, which normally generated only 25%, is increased to 25% or more by absorbing thermal energy after carrier injection. It can be raised. If a compound that emits strong fluorescence and delayed fluorescence even at a low temperature of less than 100 ° C is used, the heat of the device will sufficiently cause intersystem crossing from the excited triplet state to the excited singlet state and emit delayed fluorescence. Efficiency can be improved dramatically.

By using the compound represented by the general formula (1) of the present invention as a light-emitting material of a light-emitting layer, excellent organic light-emitting devices such as an organic photoluminescence device (organic PL device) and an organic electroluminescence device (organic EL device) Can be provided. At this time, the compound represented by the general formula (1) of the present invention may have a function of assisting light emission of another light emitting material included in the light emitting layer as a so-called assist dopant. That is, the compound represented by the general formula (1) of the present invention contained in the light emitting layer includes the lowest excitation singlet energy level of the host material contained in the light emitting layer and the lowest excitation of other light emitting materials contained in the light emitting layer. It may have the lowest excited singlet energy level between singlet energy levels.
The organic photoluminescence element has a structure in which at least a light emitting layer is formed on a substrate. The organic electroluminescence element has a structure in which an organic layer is formed at least between an anode, a cathode, and an anode and a cathode. The organic layer includes at least a light emitting layer, and may consist of only the light emitting layer, or may have one or more organic layers in addition to the light emitting layer. Examples of such other organic layers include a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, and an exciton blocking layer. The hole transport layer may be a hole injection / transport layer having a hole injection function, and the electron transport layer may be an electron injection / transport layer having an electron injection function. A specific example of the structure of an organic electroluminescence element is shown in FIG. In FIG. 1, 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, 5 is a light emitting layer, 6 is an electron transport layer, and 7 is a cathode.
Below, each member and each layer of an organic electroluminescent element are demonstrated. In addition, description of a board | substrate and a light emitting layer corresponds also to the board | substrate and light emitting layer of an organic photo-luminescence element.

(substrate)
The organic electroluminescence device of the present invention is preferably supported on a substrate. The substrate is not particularly limited and may be any substrate conventionally used for organic electroluminescence elements. For example, a substrate made of glass, transparent plastic, quartz, silicon, or the like can be used.

(anode)
As the anode in the organic electroluminescence element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used. For the anode, a thin film may be formed by vapor deposition or sputtering of these electrode materials, and a pattern of a desired shape may be formed by photolithography, or when pattern accuracy is not so high (about 100 μm or more) ), A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material. Or when using the material which can be apply | coated like an organic electroconductivity compound, wet film-forming methods, such as a printing system and a coating system, can also be used. When light emission is extracted from the anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.

(cathode)
On the other hand, as the cathode, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include 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 ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the point of durability against electron injection and oxidation, a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture, Suitable are a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, a lithium / aluminum mixture, aluminum and the like. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm. In order to transmit the emitted light, if either one of the anode or the cathode of the organic electroluminescence element is transparent or translucent, the emission luminance is advantageously improved.
In addition, by using the conductive transparent material mentioned in the description of the anode as a cathode, a transparent or semi-transparent cathode can be produced. By applying this, an element in which both the anode and the cathode are transparent is used. Can be produced.

(Light emitting layer)
The light emitting layer is a layer that emits light after excitons are generated by recombination of holes and electrons injected from each of the anode and the cathode, and the light emitting material may be used alone for the light emitting layer. , Preferably including a luminescent material and a host material. As a luminescent material, the 1 type (s) or 2 or more types chosen from the compound group of this invention represented by General formula (1) can be used. In order for the organic electroluminescent device and the organic photoluminescent device of the present invention to exhibit high luminous efficiency, it is important to confine singlet excitons and triplet excitons generated in the light emitting material in the light emitting material. Therefore, it is preferable to use a host material in addition to the light emitting material in the light emitting layer. As the host material, an organic compound having at least one of excited singlet energy and excited triplet energy higher than that of the light emitting material of the present invention can be used. As a result, singlet excitons and triplet excitons generated in the light emitting material of the present invention can be confined in the molecules of the light emitting material of the present invention, and the light emission efficiency can be sufficiently extracted. However, even if singlet excitons and triplet excitons cannot be sufficiently confined, there are cases where high luminous efficiency can be obtained, so that host materials that can achieve high luminous efficiency are particularly limited. And can be used in the present invention. In the organic light emitting device or organic electroluminescent device of the present invention, light emission is generated from the light emitting material of the present invention contained in the light emitting layer. This emission includes both fluorescence and delayed fluorescence. However, light emission from the host material may be partly or partly emitted.
When the host material is used, the amount of the compound of the present invention, which is a light emitting material, is preferably 0.1% by weight or more, more preferably 1% by weight or more, and 50% or more. It is preferably no greater than wt%, more preferably no greater than 20 wt%, and even more preferably no greater than 10 wt%.
The host material in the light-emitting layer is preferably an organic compound that has a hole transporting ability and an electron transporting ability, prevents the emission of longer wavelengths, and has a high glass transition temperature.

(Injection layer)
The injection layer is a layer provided between the electrode and the organic layer for lowering the driving voltage and improving the luminance of light emission. There are a hole injection layer and an electron injection layer, and between the anode and the light emitting layer or the hole transport layer. Further, it may be present between the cathode and the light emitting layer or the electron transport layer. The injection layer can be provided as necessary.

(Blocking layer)
The blocking layer is a layer that can prevent diffusion of charges (electrons or holes) and / or excitons existing in the light emitting layer to the outside of the light emitting layer. The electron blocking layer can be disposed between the light emitting layer and the hole transport layer and blocks electrons from passing through the light emitting layer toward the hole transport layer. Similarly, a hole blocking layer can be disposed between the light emitting layer and the electron transporting layer to prevent holes from passing through the light emitting layer toward the electron transporting layer. The blocking layer can also be used to block excitons from diffusing outside the light emitting layer. That is, each of the electron blocking layer and the hole blocking layer can also function as an exciton blocking layer. The term “electron blocking layer” or “exciton blocking layer” as used herein is used in the sense of including a layer having the functions of an electron blocking layer and an exciton blocking layer in one layer.

(Hole blocking layer)
The hole blocking layer has a function of an electron transport layer in a broad sense. The hole blocking layer has a role of blocking holes from reaching the electron transport layer while transporting electrons, thereby improving the recombination probability of electrons and holes in the light emitting layer. As the material for the hole blocking layer, the material for the electron transport layer described later can be used as necessary.

(Electron blocking layer)
The electron blocking layer has a function of transporting holes in a broad sense. The electron blocking layer has a role to block electrons from reaching the hole transport layer while transporting holes, thereby improving the probability of recombination of electrons and holes in the light emitting layer. .

(Exciton blocking layer)
The exciton blocking layer is a layer for preventing excitons generated by recombination of holes and electrons in the light emitting layer from diffusing into the charge transport layer. It becomes possible to efficiently confine in the light emitting layer, and the light emission efficiency of the device can be improved. The exciton blocking layer can be inserted on either the anode side or the cathode side adjacent to the light emitting layer, or both can be inserted simultaneously. That is, when the exciton blocking layer is provided on the anode side, the layer can be inserted adjacent to the light emitting layer between the hole transport layer and the light emitting layer, and when inserted on the cathode side, the light emitting layer and the cathode Between the luminescent layer and the light-emitting layer. Further, a hole injection layer, an electron blocking layer, or the like can be provided between the anode and the exciton blocking layer adjacent to the anode side of the light emitting layer, and the excitation adjacent to the cathode and the cathode side of the light emitting layer can be provided. Between the child blocking layer, an electron injection layer, an electron transport layer, a hole blocking layer, and the like can be provided. When the blocking layer is disposed, at least one of the excited singlet energy and the excited triplet energy of the material used as the blocking layer is preferably higher than the excited singlet energy and the excited triplet energy of the light emitting material.

(Hole transport layer)
The hole transport layer is made of a hole transport material having a function of transporting holes, and the hole transport layer can be provided as a single layer or a plurality of layers.
The hole transport material has any one of hole injection or transport and electron barrier properties, and may be either organic or inorganic. Known hole transport materials that can be used include, for example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, carbazole derivatives, indolocarbazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, Examples include 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. An aromatic tertiary amine compound and an styrylamine compound are preferably used, and an aromatic tertiary amine compound is more preferably used.

(Electron transport layer)
The electron transport layer is made of a material having a function of transporting electrons, and the electron transport layer can be provided as a single layer or a plurality of layers.
The electron transport material (which may also serve as a hole blocking material) may have a function of transmitting electrons injected from the cathode to the light emitting layer. Examples of the electron transport layer that can be used include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide oxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like. Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

  When producing an organic electroluminescent element, you may use not only the compound represented by General formula (1) for a light emitting layer but layers other than a light emitting layer. In that case, the compound represented by General formula (1) used for a light emitting layer and the compound represented by General formula (1) used for layers other than a light emitting layer may be same or different. For example, the compound represented by the general formula (1) may be used for the injection layer, blocking layer, hole blocking layer, electron blocking layer, exciton blocking layer, hole transporting layer, electron transporting layer, and the like. . The method for forming these layers is not particularly limited, and the layer may be formed by either a dry process or a wet process.

Below, the preferable material which can be used for an organic electroluminescent element is illustrated concretely. However, the material that can be used in the present invention is not limited to the following exemplary compounds. Moreover, even if it is a compound illustrated as a material which has a specific function, it can also be diverted as a material which has another function. In addition, R and R _{1 to} R ₇ in the structural formulas of the following exemplary compounds each independently represent a hydrogen atom or a substituent. n represents an integer of 3 to 5.

  First, preferred compounds that can also be used as a host material for the light emitting layer are listed.

  Next, examples of preferable compounds that can be used as the hole injection material will be given.

  Next, examples of preferred compounds that can be used as a hole transport material are listed.

  Next, examples of preferable compounds that can be used as an electron blocking material are given.

  Next, preferred compound examples that can be used as a hole blocking material are listed.

  Next, examples of preferable compounds that can be used as an electron transporting material will be given.

  Next, examples of preferable compounds that can be used as the electron injection material are given.

  Furthermore, preferable compound examples are given as materials that can be added. For example, adding as a stabilizing material can be considered.

The organic electroluminescence device produced by the above-described method emits light by applying an electric field between the anode and the cathode of the obtained device. At this time, if the light is emitted by excited singlet energy, light having a wavelength corresponding to the energy level is confirmed as fluorescence emission and delayed fluorescence emission. In addition, in the case of light emission by excited triplet energy, a wavelength corresponding to the energy level is confirmed as phosphorescence. Since normal fluorescence has a shorter fluorescence lifetime than delayed fluorescence, the emission lifetime can be distinguished from fluorescence and delayed fluorescence.
On the other hand, with respect to phosphorescence, in ordinary organic compounds such as the compounds of the present invention, the excited triplet energy is unstable and is converted into heat and the like, and the lifetime is short and it is immediately deactivated. In order to measure the excited triplet energy of a normal organic compound, it can be measured by observing light emission under extremely low temperature conditions.

  The organic electroluminescence element of the present invention can be applied to any of a single element, an element having a structure arranged in an array, and a structure in which an anode and a cathode are arranged in an XY matrix. According to the present invention, an organic light emitting device with greatly improved light emission efficiency can be obtained by containing the compound represented by the general formula (1) in the light emitting layer. The organic light emitting device such as the organic electroluminescence device of the present invention can be further applied to various uses. For example, it is possible to produce an organic electroluminescence display device using the organic electroluminescence element of the present invention. For details, see “Organic EL Display” (Ohm Co., Ltd.) written by Shizushi Tokito, Chiba Adachi and Hideyuki Murata. ) Can be referred to. In particular, the organic electroluminescence device of the present invention can be applied to organic electroluminescence illumination and backlights that are in great demand.

  The features of the present invention will be described more specifically with reference to synthesis examples and examples. The following materials, processing details, processing procedures, and the like can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below. Note that the evaluation of the light emission characteristics is as follows: source meter (manufactured by Keithley: 2400 series), semiconductor parameter analyzer (manufactured by Agilent Technologies: E5273A), optical power meter measuring device (manufactured by Newport: 1930C), optical spectrometer (Ocean Optics Co., Ltd .: USB2000), spectroradiometer (Topcon Co., Ltd .: SR-3), and streak camera (Hamamatsu Photonics Co., Ltd. model C4334) were used.

The difference between the singlet energy of each material (E _S1) and triplet energy (E _T1) (ΔE _ST) calculates the triplet energy singlet energy (E _S1) in the following manner, Delta] E _ST = It was determined by E _S1 -E _T1.
(1) Singlet energy E _S1
A sample having a thickness of 100 nm was prepared on a Si substrate by co-evaporating the measurement target compound and mCBP so that the measurement target compound had a concentration of 6% by weight. The fluorescence spectrum of this sample was measured at room temperature (300K). By integrating the luminescence from immediately after the excitation light incidence to 100 nanoseconds after the incidence, a fluorescence spectrum having a luminescence intensity on the vertical axis and a wavelength on the horizontal axis was obtained. In the fluorescence spectrum, the vertical axis represents light emission and the horizontal axis represents wavelength. A tangent line was drawn with respect to the short-wave rise of the emission spectrum, and the wavelength value λedge [nm] at the intersection of the tangent line and the horizontal axis was obtained. A value obtained by converting this wavelength value into an energy value by the following conversion formula was defined as E _S1 .
Conversion formula: E _S1 [eV] = 1239.85 / λedge
For the measurement of the emission spectrum, a nitrogen laser (Lasertechnik Berlin, MNL200) was used as an excitation light source, and a streak camera (Hamamatsu Photonics, C4334) was used as a detector.
(2) Triplet energy E _T1
The same sample as the singlet energy E _S1 was cooled to 5 [K], the sample for phosphorescence measurement was irradiated with excitation light (337 nm), and the phosphorescence intensity was measured using a streak camera. By integrating the luminescence from 1 millisecond after the excitation light incidence to 10 milliseconds after the incidence, a phosphorescence spectrum having the luminescence intensity on the vertical axis and the wavelength on the horizontal axis was obtained. A tangent line was drawn with respect to the rising edge of the phosphorescence spectrum on the short wavelength side, and a wavelength value λ edge [nm] at the intersection of the tangent line and the horizontal axis was obtained. A value obtained by converting this wavelength value into an energy value by the following conversion formula was defined as _ET1 .
Conversion formula: E _T1 [eV] = 1239.85 / λedge
The tangent to the short wavelength rising edge of the phosphorescence spectrum was drawn as follows. When moving on the spectrum curve from the short wavelength side of the phosphorescence spectrum to the maximum value on the shortest wavelength side among the maximum values of the spectrum, tangents at each point on the curve are considered toward the long wavelength side. The slope of this tangent line increases as the curve rises (that is, as the vertical axis increases). The tangent drawn at the point where the value of the slope takes the maximum value was taken as the tangent to the rising edge of the phosphorescence spectrum on the short wavelength side.
In addition, the maximum point having a peak intensity of 10% or less of the maximum peak intensity of the spectrum is not included in the above-mentioned maximum value on the shortest wavelength side, and has the maximum slope value closest to the maximum value on the shortest wavelength side. The tangent drawn at the point where the value was taken was taken as the tangent to the rising edge of the phosphorescence spectrum on the short wavelength side.

化合物Ａ（4,5-Diamino-bisbenzo [1,2,5]thiadiazole）は、既知の方法（A. P. Komin, M.Carmack, J. Heterocyclic Chem. 1975, 12, 829-833）で合成した。
化合物Ａ（１．００ｇ，４．４６ｍｍｏｌ）と4-4'-Dibromobenzil（２．１３ｇ，５．７９ｍｍｏｌ，１．３ｅｑ）とＣＨ₃ＣＯ₂Ｈ（１２０ｍＬ）を窒素置換した５００ｍＬ三つ口フラスコに加え、６０時間加熱還流を行った。反応終了後、反応液から溶媒を減圧除去し、得られた固体をカラムクロマトグラフィーにより精製した。カラムクロマトグラフィーによる精製は、塩化メチレン：ヘキサン＝１：２の混合溶媒を展開溶媒に用いて4-4'-Dibromobenzilを十分に溶出させた後、塩化メチレンのみを展開溶媒に用いて化合物Ｂを溶出させることで行った。以上の工程により、化合物Ｂを収量６６３ｍｇ、収率２６％で得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，４００ＭＨｚ）δ７．５９（ｄ，Ｊ＝８．５３Ｈｚ，４Ｈ），７．５６（ｄ，Ｊ＝８．５３Ｈｚ，４Ｈ）．[Synthesis Example 1] Synthesis of Exemplary Compound (1) (1) Synthesis Step of Compound B

Compound A (4,5-Diamino-bisbenzo [1,2,5] thiadiazole) was synthesized by a known method (AP Komin, M. Carmack, J. Heterocyclic Chem. 1975, 12, 829-833).
In a 500 mL three-necked flask in which Compound A (1.00 g, 4.46 mmol), 4-4′-Dibromobenzil (2.13 g, 5.79 mmol, 1.3 eq) and CH ₃ CO ₂ H (120 mL) were replaced with nitrogen were added. In addition, the mixture was refluxed for 60 hours. After completion of the reaction, the solvent was removed from the reaction solution under reduced pressure, and the resulting solid was purified by column chromatography. For purification by column chromatography, 4-4'-Dibromobenzil is sufficiently eluted using a mixed solvent of methylene chloride: hexane = 1: 2 as a developing solvent, and then compound B is prepared using only methylene chloride as a developing solvent. Elution was performed. Through the above steps, Compound B was obtained in a yield of 663 mg and a yield of 26%.
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.59 (d, J = 8.53 Hz, 4H), 7.56 (d, J = 8.53 Hz, 4H).

Ｐｄ₂（ｄｂａ）₃（Tris(dibenzylidenacetone)dipalladium(o)）（５００ｍｇ，０．５４ｍｍｏｌ，０．１０ｅｑ）を窒素置換した１Ｌ三つ口フラスコに加えた。一方、化合物Ｂ（３．００ｇ，５．３９ｍｍｏｌ）、Diphenylamine（４．５５ｇ，２６．９ｍｍｏｌ，５．０ｅｑ）、Ｎａ（ＯｔＢｕ）（Sodium tert-butoxide）（７．７６ｇ，８０．８ｍｍｏｌ，１５ｅｑ）およびトルエン３５０ｍＬを別の容器に加えて均一な溶液に調製し、この溶液を１Ｌ三つ口フラスコの中に加えた。この混合物に、Ｐ（ｔ−Ｂｕ）₃(Tri-tert-butylphosphine)のトルエン溶液（１．０ｍｏｌ／Ｌ）を０．５４ｍＬ（０．５４ｍｍｏｌ，０．１０ｅｑ）加えた後、４０℃に昇温して２時間加熱撹拌を行った。反応終了後、反応溶液を１Ｌ分液ロートに移し、水２５０ｍＬと塩化メチレン３００ｍＬを加えて撹拌した後、有機層を回収した。水層を塩化メチレン２００ｍＬで７回洗浄した後、洗浄液と有機層をひとつに合わせて硫酸マグネシウムで脱水し、減圧濃縮した。得られた固体をカラムクロマトグラフィーで精製した。カラムクロマトグラフィーによる精製は、塩化メチレン：ヘキサン＝１：４の混合溶媒を展開溶媒に用いて過剰のDiphenylamineを十分に溶出させた後、塩化メチレンのみを展開溶媒に用いて例示化合物（１）を溶出させることで行った。溶出した粗例示化合物（１）を、沸騰させたテトラヒドロフランとエタノールの混合溶媒に溶かした後、室温まで冷却することにより例示化合物（１）を析出させた。以上の工程により、例示化合物（１）を収量１．６６ｇ、収率４２％で得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，４００ＭＨｚ）δ７．６５（ｄ，Ｊ＝８．２８Ｈｚ，４Ｈ），７．３０（ｔ，Ｊ＝７．８０Ｈｚ，８Ｈ），７．１５（ｄ，Ｊ＝７．８０Ｈｚ，８Ｈ），７．１０（ｔ，Ｊ＝７．５３Ｈｚ，４Ｈ），７．０５（ｄ，Ｊ＝８．２８Ｈｚ，４Ｈ）．
ＵＶ吸収（塩化メチレン）：４４１ｎｍ（ε＝１．９×１０⁴）
ＵＶ蛍光（塩化メチレン）：５７８ｎｍ(2) Synthesis process of exemplary compound (1)

Pd ₂ (dba) ₃ (Tris (dibenzylidenacetone) dipalladium (o)) (500 mg, 0.54 mmol, 0.10 eq) was added to a nitrogen-substituted 1 L three-necked flask. On the other hand, Compound B (3.00 g, 5.39 mmol), Diphenylamine (4.55 g, 26.9 mmol, 5.0 eq), Na (OtBu) (Sodium tert-butoxide) (7.76 g, 80.8 mmol, 15 eq) And 350 mL of toluene was added to another container to prepare a homogeneous solution, and this solution was added into a 1 L three-necked flask. To this mixture was added 0.54 mL (0.54 mmol, 0.10 eq) of a toluene solution (1.0 mol / L) of P (t-Bu) ₃ (Tri-tert-butylphosphine), and the temperature was raised to 40 ° C. The mixture was then heated and stirred for 2 hours. After completion of the reaction, the reaction solution was transferred to a 1 L separatory funnel, 250 mL of water and 300 mL of methylene chloride were added and stirred, and then the organic layer was recovered. The aqueous layer was washed 7 times with 200 mL of methylene chloride, and then the washing solution and the organic layer were combined, dried over magnesium sulfate, and concentrated under reduced pressure. The obtained solid was purified by column chromatography. For purification by column chromatography, excess diphenylamine was sufficiently eluted using a mixed solvent of methylene chloride: hexane = 1: 4 as a developing solvent, and then the exemplified compound (1) was prepared using only methylene chloride as the developing solvent. Elution was performed. The eluted crude exemplary compound (1) was dissolved in a mixed solvent of boiling tetrahydrofuran and ethanol, and then cooled to room temperature to precipitate the exemplary compound (1). Through the above steps, the exemplary compound (1) was obtained in a yield of 1.66 g and a yield of 42%.
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.65 (d, J = 8.28 Hz, 4H), 7.30 (t, J = 7.80 Hz, 8H), 7.15 (d, J = 7. 80 Hz, 8H), 7.10 (t, J = 7.53 Hz, 4H), 7.05 (d, J = 8.28 Hz, 4H).
UV absorption (methylene chloride): 441 nm (ε = 1.9 × 10 ⁴ )
UV fluorescence (methylene chloride): 578 nm

Ｐｄ₂（ｄｂａ）₃（４４９ｍｇ，０．４９ｍｍｏｌ，０．１０ｅｑ）を窒素置換した１Ｌ三つ口フラスコに加えた。一方、化合物Ｂ（２．７２ｇ，４．８９ｍｍｏｌ）、Phenoxazine（１．９７ｇ，１０．８ｍｍｏｌ，２．２ｅｑ）、Ｎａ（ＯｔＢｕ）（１．１２ｇ，１１．７ｍｍｏｌ，２．４ｅｑ）、トルエン３００ｍＬを別の容器に加えて均一な溶液に調製し、この溶液を１Ｌ三つ口フラスコの中に加えた。この混合物に、Ｐ（ｔ−Ｂｕ）₃のトルエン溶液（１．０ｍｏｌ／Ｌ）を０．９８ｍＬ（０．９８ｍｍｏｌ，０．２０ｅｑ）加えた後、９０℃に昇温して１８時間加熱撹拌を行った。反応終了後、反応溶液を１Ｌ分液ロートに移し、水３００ｍＬと塩化メチレン３００ｍＬを加えて撹拌した後、有機層を回収した。水層を塩化メチレン２００ｍＬで４回洗浄した後、洗浄液と有機層をひとつにあわせて硫酸ナトリウムで脱水し、減圧濃縮した。得られた固体をカラムクロマトグラフィーで精製した。カラムクロマトグラフィによる精製は、酢酸エチル：ヘキサン＝１：２の混合溶媒を展開溶媒に用いて過剰のPhenoxazineを十分に溶出させた後、塩化メチレンのみを展開溶媒に用いて例示化合物（２）を溶出させることで行った。以上の工程により、例示化合物（２）を収量１．６１ｇ、収率４３％で得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，４００ＭＨｚ）δ７．９６（ｄ，Ｊ＝８．５３Ｈｚ，４Ｈ），７．４６（ｄ，Ｊ＝８．５３Ｈｚ，４Ｈ），６．７１（ｄｄ，Ｊ＝７．８０Ｈｚ，Ｊ＝１．４６Ｈｚ，４Ｈ），６．６６（ｔｄ，Ｊ＝７．８０Ｈｚ，Ｊ＝１．２２Ｈｚ，４Ｈ），６．５６（ｔｄ，Ｊ＝７．８０Ｈｚ，Ｊ＝１．４６Ｈｚ，４Ｈ），５．９８（ｄｄ，Ｊ＝７．８０Ｈｚ，Ｊ＝１．２２Ｈｚ，４Ｈ）．
ＵＶ吸収（トルエン）：４３０ｎｍ（ε＝５．６×１０³）
ＵＶ蛍光（トルエン）：５７３ｎｍ(Synthesis Example 2) Synthesis of Exemplary Compound (2)

Pd ₂ (dba) ₃ (449 mg, 0.49 mmol, 0.10 eq) was added to a 1 L three-necked flask purged with nitrogen. On the other hand, Compound B (2.72 g, 4.89 mmol), Phenoxazine (1.97 g, 10.8 mmol, 2.2 eq), Na (OtBu) (1.12 g, 11.7 mmol, 2.4 eq), 300 mL of toluene. It was added to another container to prepare a homogeneous solution, and this solution was added into a 1 L three-necked flask. To this mixture was added 0.98 mL (0.98 mmol, 0.20 eq) of a toluene solution (1.0 mol / L) of P (t-Bu) ₃ , and then the mixture was heated to 90 ° C. and heated and stirred for 18 hours. went. After completion of the reaction, the reaction solution was transferred to a 1 L separatory funnel, 300 mL of water and 300 mL of methylene chloride were added and stirred, and then the organic layer was recovered. The aqueous layer was washed 4 times with 200 mL of methylene chloride, and then the washing solution and the organic layer were combined, dried over sodium sulfate, and concentrated under reduced pressure. The obtained solid was purified by column chromatography. For purification by column chromatography, excess Phenoxazine was sufficiently eluted using a mixed solvent of ethyl acetate: hexane = 1: 2 as a developing solvent, and then the exemplified compound (2) was eluted using only methylene chloride as the developing solvent. It was done by letting. Through the above steps, the exemplary compound (2) was obtained in a yield of 1.61 g and a yield of 43%.
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.96 (d, J = 8.53 Hz, 4H), 7.46 (d, J = 8.53 Hz, 4H), 6.71 (dd, J = 7. 80 Hz, J = 1.46 Hz, 4H), 6.66 (td, J = 7.80 Hz, J = 1.22 Hz, 4H), 6.56 (td, J = 7.80 Hz, J = 1.46 Hz, 4H), 5.98 (dd, J = 7.80 Hz, J = 1.22 Hz, 4H).
UV absorption (toluene): 430 nm (ε = 5.6 × 10 ³ )
UV fluorescence (toluene): 573 nm

(Example 1) Preparation and evaluation of organic photoluminescence device using exemplary compound (1) A toluene solution (concentration 10 ^-4 mol / L) of exemplary compound (1) was prepared in a glove box under an Ar atmosphere.
In addition, the exemplified compound (1) and CBP were deposited from different vapor deposition sources on a quartz substrate by a vacuum vapor deposition method under a vacuum degree of 3 × 10 ⁻⁴ Pa or less. A thin film having a thickness of 0.0% by weight was formed to a thickness of 100 nm to obtain an organic photoluminescence element.
About the sample using these exemplary compounds (1), the emission spectrum and absorption spectrum by 330 nm excitation light were measured. The emission absorption spectrum of the toluene solution of the exemplified compound (1) is shown in FIG. 2, and the emission absorption spectrum of the organic photoluminescence device having the thin film of the exemplified compound (1) and CBP is shown in FIG. The emission wavelength λmax of the toluene solution of the exemplary compound (1) was 515 nm, and the photoluminescence quantum efficiency was 12.9% without bubbling and 19.5% with nitrogen bubbling. The emission wavelength λmax of the organic photoluminescence device having the thin film of Example Compound (1) and CBP was 521 nm, and the photoluminescence quantum efficiency was 20.5% under the atmosphere and 38.1% under the nitrogen stream.
FIG. 4 shows the results of measuring the transient attenuation curve of the organic photoluminescence device having the thin film of the exemplary compound (1) and CBP. This transient decay curve shows the result of measuring the luminescence lifetime obtained by measuring the process in which the emission intensity is deactivated by applying excitation light to the compound. In the case of normal single component light emission (fluorescence or phosphorescence), the light emission intensity decays in a single exponential manner. This means that if the vertical axis of the graph is semi-log, it will decay linearly. In the transient attenuation curve of this example, such a linear component (fluorescence) is observed at the initial stage of observation, but a component deviating from linearity appears after several microseconds. This is light emission of the delay component, and the signal added to the initial component becomes a loose curve with a tail on the long time side. Thus, by measuring the light emission lifetime, it was confirmed that the exemplary compound (1) is a light emitter containing a delay component in addition to the fluorescent component.
According to the molecular orbital calculation of the example compound (1) (using Gaussian09, PBE0 / 6-31 (d) and TD-PBE0 / 6-31 (d) conditions) The energy difference ΔE _st value between (S ₁ ) and the excited triplet state (T ₁ ) was 0.437 eV, and the frequency factor f value for the S ₀ → S ₁ transition was 0.09. The ΔE _st value was used as a measure of the probability of thermal activation, and it was considered that the smaller the value, the more likely the thermal activation delayed fluorescence occurs. The f value is the ease of the transition from S ₀ (ground state) to S ₁ (excited singlet state). In this calculation, the f value is used as a measure of the ease of light emission (fluorescence intensity). It was considered that the larger this value, the stronger the fluorescence.

(Example 2) Preparation and evaluation of organic photoluminescence device using exemplary compound (2) Except for using exemplary compound (2) instead of exemplary compound (1), exemplary compound ( A toluene solution of 2) was prepared. In addition, organic photoluminescence having a thin film of exemplary compound (2) and mCBP was used in the same manner as in Example 1 except that exemplary compound (2) was used instead of exemplary compound (1) and mCBP was used instead of CBP. An element was produced.
FIG. 5 shows the results of measuring the emission spectrum and the absorption spectrum of the exemplary compound (2) with a 430 nm excitation light, and the organic photoluminescence device having the thin film of the exemplary compound (2) and mCBP with a 342 nm excitation light. The results of measuring the emission spectrum and absorption spectrum are shown in FIG. The emission wavelength λmax of the toluene solution of the exemplary compound (2) was 634 nm, and the photoluminescence quantum efficiency was 6.1% without bubbling and 12.5% with nitrogen bubbling. In addition, the emission wavelength λmax of the organic photoluminescence device having a thin film of Example Compound (2) and mCBP was 585 nm, and the photoluminescence quantum efficiency was 56.0% under the atmosphere and 62.8% under the nitrogen stream. .
Moreover, the result of having measured the transient decay curve by 405 nm excitation light about the toluene solution of exemplary compound (2) is shown in FIG. 7, About 340 nm excitation light about the organic photoluminescent element which has the thin film of exemplary compound (2) and mCBP A transient decay curve is shown in FIG. 7 and 8, in each sample, the transient decay curve is shifted backward in the presence of nitrogen than in the atmosphere. This is presumably because the reverse intersystem crossing from the excited triplet state to the excited singlet state is inhibited in the atmosphere, while this reverse intersystem crossing occurs in the presence of nitrogen. From this, it was confirmed that the organic photoluminescence device having the toluene solution of Exemplified Compound (2) and the thin film of Exemplified Compound 2 and mCBP emits delayed fluorescence. In addition, according to the molecular orbital calculation (see Example 1) of the exemplary compound (2), the energy difference ΔE _st value between the excited singlet state and the excited triplet state is 0.0567 eV, and the f value is 0.0339. Met. The ΔE _st value was smaller than the exemplified compound (1), which was expected to be advantageous for thermally activated delayed fluorescence, but the f value was smaller than the exemplified compound (1), so the results were interesting. Was held. In fact, since the compound (2) exhibited strong delayed fluorescence, it was found that a small ΔE _st value is important for expressing strong thermally activated delayed fluorescence.

(Example 3) Production and evaluation of organic electroluminescence device using exemplary compound (2) Each thin film was vacuum-deposited on a glass substrate on which an anode made of indium tin oxide (ITO) having a thickness of 100 nm was formed. In this way, the layers were stacked at a vacuum degree of 3 × 10 ⁻⁴ Pa. First, α-NPD was formed to a thickness of 35 nm on ITO. Next, Exemplified Compound (2) and mCBP were co-evaporated from different vapor deposition sources to form a layer having a thickness of 15 nm as a light emitting layer. At this time, the concentration of the exemplary compound (2) was 6.0% by weight. Next, TPBi is formed to a thickness of 65 nm, further lithium fluoride (LiF) is vacuum-deposited to 0.8 nm, and then aluminum (Al) is evaporated to a thickness of 100 nm to form a cathode. A luminescence element was obtained.
FIG. 9 shows an emission spectrum of the manufactured organic electroluminescence device measured at 1 mA / cm ² , 10 mA / cm ² , and 100 mA / cm ² , and FIG. 10 shows voltage-current density characteristics. FIG. 11 shows the current density-external quantum efficiency characteristics, FIG. 12 shows the current density-power efficiency characteristics, and FIG. 13 shows the current density-current efficiency characteristics. The organic electroluminescence device using the exemplified compound (2) as the light emitting material had an external quantum efficiency of 9.14% at 0.07 mA / cm ² and was able to obtain high light emission efficiency. Assuming that an ideal organic electroluminescence device balanced using a fluorescent material having a light emission quantum efficiency of 100% is prototyped, if the light extraction efficiency is 20 to 30%, the external quantum efficiency of fluorescent light emission is 5 -7.5%. This value is generally regarded as a theoretical limit value of the external quantum efficiency of an organic electroluminescence device using a fluorescent material. The organic electroluminescence device of the present invention using the exemplified compound (2) is extremely excellent in that high external quantum efficiency exceeding the theoretical limit value is realized. The organic electroluminescence device of the present embodiment is a power efficiency 10.0lm / W at 0.003mA / cm ^2, current efficiency at 0.008mA / cm ² is 10.1cd / A, higher power Efficiency and high current efficiency could be obtained.

  The compound of the present invention is useful as a light emitting material. For this reason, the compound of this invention is effectively used as a luminescent material for organic light emitting elements, such as an organic electroluminescent element. Since the compounds of the present invention include those that emit delayed fluorescence, it is also possible to provide an organic light-emitting device with high luminous efficiency. For this reason, this invention has high industrial applicability.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Anode 3 Hole injection layer 4 Hole transport layer 5 Light emitting layer 6 Electron transport layer 7 Cathode

Claims (14)

A luminescent material comprising a compound represented by the following general formula (1).

[In General Formula (1), R ¹ and R ² each independently represent a substituted or unsubstituted aryl group, and at least one of R ¹ and R ² is an aryl group substituted with an N, N-diarylamino group. is there. ] ^2. The luminescent material according to claim 1, wherein at least one of R ¹ and R ^{2 in} the general formula (1) is a group represented by the following general formula (2).

[In General Formula (2), * represents the bonding site to the pyrazine ring in General Formula (1). Ar ^{1 to} Ar ³ each independently represents a substituted or unsubstituted carbocyclic aromatic group having 4 to 10 carbon atoms or a substituted or unsubstituted heterocyclic aromatic group having 4 to 10 carbon atoms. ] The light emitting material according to claim 2, wherein Ar ^{1 in the} general formula (2) is an unsubstituted phenylene group, an unsubstituted naphthylene group, or an unsubstituted biphenylene group. The luminescent material according to claim 2 or 3, wherein Ar ^{1 in the} general formula (2) is an unsubstituted phenylene group. The Ar ² and Ar ^{3 in} the general formula (2) are each independently a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, according to any one of claims 2 to 4. Luminescent material. The luminescent material according to claim 2, wherein Ar ² and Ar ^{3 in} the general formula (2) are each independently a substituted or unsubstituted phenyl group. The luminescent material according to claim 2, wherein Ar ₂ and Ar _{3 in} the general formula (2) are bonded to each other via a single bond or a linking group. The light emitting material according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (3).

[In General Formula (3), R ³ and R ⁴ each independently represent a hydrogen atom or a substituent, and at least one of R ³ and R ⁴ is a group represented by the following General Formula (4). ]

[In General Formula (4), * represents the bonding site to the benzene ring in General Formula (3). X represents a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted vinylene group, a substituted or unsubstituted imino group, an oxygen atom or a sulfur atom. ]   The luminescent material according to claim 8, wherein X in the general formula (4) is a methylene group substituted with a methyl group or an oxygen atom. A delayed phosphor comprising a compound represented by the following general formula (1).

[In General Formula (1), R ¹ and R ² each independently represent a substituted or unsubstituted aryl group, and at least one of R ¹ and R ² is an aryl group substituted with an N, N-diarylamino group. is there. ]   An organic light emitting device comprising the light emitting material according to claim 1.   The organic light emitting device according to claim 11, which emits delayed fluorescence.   The organic light-emitting device according to claim 11, wherein the organic light-emitting device is an organic electroluminescence device. A compound represented by the following general formula (3).

[In General Formula (3), R ³ and R ⁴ each independently represent a hydrogen atom or a substituent, and at least one of R ³ and R ⁴ is a group represented by the following General Formula (4). ]

[In General Formula (4), * represents the bonding site to the benzene ring in General Formula (3). X represents a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted vinylene group, a substituted or unsubstituted imino group, an oxygen atom or a sulfur atom. ]

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