JP2016084284A - Compound, light-emitting material, and organic light-emitting element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound useful as a light-emitting material.SOLUTION: The compound is represented by the formula (D)n-A. [D represents a group represented by formula (2); A represents a n-valent group including a structure of formula (3); and n represents an integer from 1 to 8]. [Zrepresents O, S, C=O, or a single bond; Rto Reach represent a hydrogen atom or a substituent; Y represents O, S or N-Ar; and Arrepresents an aryl group.]SELECTED DRAWING: None

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. Among them, studies on organic electroluminescence devices using compounds containing an oxadiazole ring or a triazole ring have been found, and several proposals have been made so far.

For example, Patent Document 1 describes that a compound containing an oxadiazole ring represented by the following general formula has high electron transport properties and can improve the characteristics of a light-emitting element. In the following general formula, Ar ¹ is an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be substituted with an aryl group having 6 to 10 carbon atoms forming a ring, Ar ² is an aryl group having 6 to 10 carbon atoms or a heteroaryl group having 4 to 9 carbon atoms forming a ring, and R ¹ and R ² are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is prescribed. However, no compound is described in which the ring to which Ar ² is bonded has a structure other than an anthracene ring in the following general formula.

Patent Document 2 describes that a compound containing a triazole ring represented by the following general formula has high carrier transportability and can improve the light emission efficiency of the light emitting element. In the following general formula, Ar ¹ and Ar ² are an aryl group or a heteroaryl group, Ar ³ is an arylene group or a heteroarylene group, and R ¹¹ and R ¹² are a hydrogen atom, an alkyl group, an alkoxy group, or an aryl group. It is stipulated that However, a compound in which the ring bonded to Ar ³ in the following general formula is other than a carbazole ring is not described. Further, there is no description about a compound in which a carbazole ring bonded to Ar ³ is further substituted with a diarylamino group.

Patent Document 3 describes that a compound containing a triazole ring represented by the following general formula has high carrier transportability and can improve the light emission efficiency of the light emitting element. In the following general formula, A is an oxygen atom or a sulfur atom, Ar ¹ and Ar ² are aryl groups having 6 to 13 carbon atoms, Ar ⁴ is an arylene group having 6 to 13 carbon atoms, and R ¹ to R ⁷ is defined as a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 13 carbon atoms. However, a compound having a structure other than the ring containing the following A in the ring bonded to Ar ⁴ in the following general formula is not described.

JP 2010-254675 A JP 2008-308490 A JP 2012-6912 A

Thus, about the compound containing an oxadiazole ring and a triazole ring, examination is made | formed until now and some proposals regarding the application to an organic electroluminescent element are also made | formed. However, for compounds containing in the molecule both the structure represented by the following general formula (2) including [1] oxadiazole ring or triazole ring, and [2] phenoxazine ring, phenothiazine ring, etc. Has not been considered. In addition, few compounds having both of these two types of rings in the molecule are known. For this reason, it is extremely difficult to accurately predict what kind of property the compound having both of these rings will exhibit. In particular, as to the usefulness as a luminescent material, it is difficult to find a document that can serve as a basis for prediction, as is clear from the fact that the use as a luminescent material is not described in the cited documents 1 to 3.
In view of these problems of the prior art, the present inventors have synthesized a compound containing both an oxadiazole ring and a phenoxazine ring in the molecule and evaluated the usefulness as a light emitting material. We proceeded with examination. In addition, a general formula of a compound useful as a light-emitting material has been derived, and extensive studies have been conducted with the aim of generalizing the structure of an organic light-emitting device having high luminous efficiency.

  As a result of diligent studies to achieve the above object, the present inventors have included [1] oxadiazole ring, thiodiazole ring or triazole ring, and [2] phenoxazine ring, phenothiazine ring, etc. The present inventors have succeeded in synthesizing compounds containing both structures represented by the general formula (2), and have revealed for the first time that these compounds are useful as light emitting materials. In addition, it has been found that some of these compounds are useful as delayed fluorescent materials, and it has been clarified that an organic light-emitting device with high luminous 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（２）において、Ｚ¹はＯ、Ｓ、Ｃ＝Ｏ、Ｃ（Ｒ²¹）（Ｒ²²）、Ｓｉ（Ｒ²³）（Ｒ²⁴）または単結合を表し、Ｒ²¹〜Ｒ²⁴は各々独立に炭素数１〜８のアルキル基を表す。Ｒ¹〜Ｒ⁸は各々独立に水素原子または置換基を表す。Ｒ¹とＲ²、Ｒ²とＲ³、Ｒ³とＲ⁴、Ｒ⁵とＲ⁶、Ｒ⁶とＲ⁷、Ｒ⁷とＲ⁸は、それぞれ互いに結合して環状構造を形成していてもよい。ただし、Ｚ¹が単結合であるとき、Ｒ¹〜Ｒ⁸の少なくとも１つは置換もしくは無置換のジアリールアミノ基を表す。］

［一般式（３）において、ＹはＯ、ＳまたはＮ−Ａｒ³を表し、Ａｒ³は置換もしくは無置換のアリール基を表す。］ [1] A compound represented by the following general formula (1).
General formula (1)
(D) n-A
[In General Formula (1), D represents a group represented by the following General Formula (2), and A represents an n-valent group including a structure represented by the following General Formula (3). n represents an integer of 1 to 8. ]

[In the general formula (2), Z ¹ represents O, S, C═O, C (R ²¹ ) (R ²² ), Si (R ²³ ) (R ²⁴ ) or a single bond, and R ^{21 to} R ²⁴ represent Each independently represents an alkyl group having 1 to 8 carbon atoms. R ^{1 to} R ⁸ each independently represents a hydrogen atom or a substituent. 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 may be bonded to each other to form a cyclic structure. Good. However, when Z ¹ is a single bond, at least one of R ^{1 to} R ⁸ represents a substituted or unsubstituted diarylamino group. ]

[In General Formula (3), Y represents O, S or N—Ar ³ , and Ar ³ represents a substituted or unsubstituted aryl group. ]

［一般式（４）において、ＹはＯ、ＳまたはＮ−Ａｒ³を表し、Ａｒ¹およびＡｒ²は各々独立に置換もしくは無置換の芳香族基を表す。］
［３］ 一般式（１）のｎが１〜４のいずれかの整数であることを特徴とする［１］または［２］に記載の化合物。 [2] The compound according to [1], wherein A in the general formula (1) has a structure represented by the following general formula (4).

[In General Formula (4), Y represents O, S or N—Ar ³ , and Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aromatic group. ]
[3] The compound according to [1] or [2], wherein n in the general formula (1) is an integer of 1 to 4.

［一般式（５）において、Ｚ¹およびＺ²は各々独立にＯ、Ｓ、Ｃ＝Ｏ、Ｃ（Ｒ²¹）（Ｒ²²）、Ｓｉ（Ｒ²³）（Ｒ²⁴）または単結合を表し、Ｒ²¹〜Ｒ²⁴は各々独立に炭素数１〜８のアルキル基を表す。Ａｒ¹およびＡｒ²は各々独立に置換もしくは無置換の芳香族基を表す。ＹはＯ、ＳまたはＮ−Ａｒ³を表し、Ａｒ³は置換もしくは無置換のアリール基を表す。Ｒ¹〜Ｒ⁸およびＲ¹¹〜Ｒ¹⁸は各々独立に水素原子または置換基を表す。Ｒ¹とＲ²、Ｒ²とＲ³、Ｒ³とＲ⁴、Ｒ⁵とＲ⁶、Ｒ⁶とＲ⁷、Ｒ⁷とＲ⁸、Ｒ¹¹とＲ¹²、Ｒ¹²とＲ¹³、Ｒ¹³とＲ¹⁴、Ｒ¹⁵とＲ¹⁶、Ｒ¹⁶とＲ¹⁷、Ｒ¹⁷とＲ¹⁸は、それぞれ互いに結合して環状構造を形成していてもよい。ただし、Ｚ¹が単結合であるとき、Ｒ¹〜Ｒ⁸の少なくとも１つは置換もしくは無置換のジアリールアミノ基を表し、Ｚ²が単結合であるとき、Ｒ¹¹〜Ｒ¹⁸の少なくとも１つは置換もしくは無置換のジアリールアミノ基を表す。ｎ１およびｎ２は、各々独立に０〜８のいずれかの整数を表し、ｎ１とｎ２の和は１〜８である。］
［５］ 一般式（５）のＺ¹およびＺ²が各々独立にＯ、Ｓまたは単結合であることを特徴とする［４］に記載の化合物。
［６］ 一般式（５）のＹがＯまたはＮ−Ａｒ³であることを特徴とする［４］または［５］に記載の化合物。 [4] The compound according to [1], which is represented by the general formula (5).

[In General Formula (5), Z ¹ and Z ² each independently represent O, S, C═O, C (R ²¹ ) (R ²² ), Si (R ²³ ) (R ²⁴ ) or a single bond, R ^{21 to} R ²⁴ each independently represents an alkyl group having 1 to 8 carbon atoms. Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aromatic group. Y represents O, S or N—Ar ³ , and Ar ³ represents a substituted or unsubstituted aryl group. R ^{1 to} R ⁸ and R ^{11 to} R ¹⁸ each independently represent a hydrogen atom or a substituent. 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 ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ And R ¹⁴ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , and R ¹⁷ and R ¹⁸ may be bonded to each other to form a cyclic structure. However, when Z ¹ is a single bond, at least one of R ^{1 to} R ⁸ represents a substituted or unsubstituted diarylamino group, and when Z ² is a single bond, at least one of R ^{11 to} R ^18. Represents a substituted or unsubstituted diarylamino group. n1 and n2 each independently represents an integer of 0 to 8, and the sum of n1 and n2 is 1 to 8. ]
[5] The compound according to [4], wherein Z ¹ and Z ^{2 in} the general formula (5) are each independently O, S or a single bond.
[6] The compound according to [4] or [5], wherein Y in the general formula (5) is O or N—Ar ³ .

［一般式（６）において、Ｚ¹はＯ、Ｓ、Ｃ＝Ｏ、Ｃ（Ｒ²¹）（Ｒ²²）、Ｓｉ（Ｒ²³）（Ｒ²⁴）または単結合を表し、Ｒ²¹〜Ｒ²⁴は各々独立に炭素数１〜８のアルキル基を表す。Ａｒ^1'は置換もしくは無置換のアリーレン基を表す。Ａｒ^2'は置換もしくは無置換のアリール基を表す。ＹはＯ、ＳまたはＮ−Ａｒ³を表し、Ａｒ³は置換もしくは無置換のアリール基を表す。Ｒ¹〜Ｒ⁸は各々独立に水素原子または置換基を表す。Ｒ¹とＲ²、Ｒ²とＲ³、Ｒ³とＲ⁴、Ｒ⁵とＲ⁶、Ｒ⁶とＲ⁷、Ｒ⁷とＲ⁸は、それぞれ互いに結合して環状構造を形成していてもよい。ただし、Ｚ¹が単結合であるとき、Ｒ¹〜Ｒ⁸の少なくとも１つは置換もしくは無置換のジアリールアミノ基を表す。］ [7] The compound according to [1], which is represented by the general formula (6).

[In General Formula (6), Z ¹ represents O, S, C═O, C (R ²¹ ) (R ²² ), Si (R ²³ ) (R ²⁴ ) or a single bond, and R ^{21 to} R ²⁴ represent Each independently represents an alkyl group having 1 to 8 carbon atoms. Ar ^{1 ′} represents a substituted or unsubstituted arylene group. Ar ^{2 ′} represents a substituted or unsubstituted aryl group. Y represents O, S or N—Ar ³ , and Ar ³ represents a substituted or unsubstituted aryl group. R ^{1 to} R ⁸ each independently represents a hydrogen atom or a substituent. 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 may be bonded to each other to form a cyclic structure. Good. However, when Z ¹ is a single bond, at least one of R ^{1 to} R ⁸ represents a substituted or unsubstituted diarylamino group. ]

［一般式（７）において、Ｚ¹およびＺ²は各々独立にＯ、Ｓ、Ｃ＝Ｏ、Ｃ（Ｒ²¹）（Ｒ²²）、Ｓｉ（Ｒ²³）（Ｒ²⁴）または単結合を表し、Ｒ²¹〜Ｒ²⁴は各々独立に炭素数１〜８のアルキル基を表す。Ａｒ^1"およびＡｒ^2"は各々独立に置換もしくは無置換のアリーレン基を表す。ＹはＯ、ＳまたはＮ−Ａｒ³を表し、Ａｒ³は置換もしくは無置換のアリール基を表す。Ｒ¹〜Ｒ⁸およびＲ¹¹〜Ｒ¹⁸は各々独立に水素原子または置換基を表す。Ｒ¹とＲ²、Ｒ²とＲ³、Ｒ³とＲ⁴、Ｒ⁵とＲ⁶、Ｒ⁶とＲ⁷、Ｒ⁷とＲ⁸、Ｒ¹¹とＲ¹²、Ｒ¹²とＲ¹³、Ｒ¹³とＲ¹⁴、Ｒ¹⁵とＲ¹⁶、Ｒ¹⁶とＲ¹⁷、Ｒ¹⁷とＲ¹⁸は、それぞれ互いに結合して環状構造を形成していてもよい。ただし、Ｚ¹が単結合であるとき、Ｒ¹〜Ｒ⁸の少なくとも１つは置換もしくは無置換のジアリールアミノ基を表し、Ｚ²が単結合であるとき、Ｒ¹¹〜Ｒ¹⁸の少なくとも１つは置換もしくは無置換のジアリールアミノ基を表す。］
［９］ 一般式（７）のＺ¹とＺ²が同一であり、Ａｒ^1"とＡｒ^2"が同一であり、Ｒ¹とＲ¹¹が同一であり、Ｒ²とＲ¹²が同一であり、Ｒ³とＲ¹³が同一であり、Ｒ⁴とＲ¹⁴が同一であり、Ｒ⁵とＲ¹⁵が同一であり、Ｒ⁶とＲ¹⁶が同一であり、Ｒ⁷とＲ¹⁷が同一であり、Ｒ⁸とＲ¹⁸が同一であることを特徴とする［８］に記載の化合物。
［１０］ 一般式（７）のＺ¹とＺ²が各々独立にＯまたはＳであることを特徴とする［８］または［９］に記載の化合物。 [8] The compound according to [1], which is represented by the following general formula (7).

[In General Formula (7), Z ¹ and Z ² each independently represent O, S, C═O, C (R ²¹ ) (R ²² ), Si (R ²³ ) (R ²⁴ ) or a single bond, R ^{21 to} R ²⁴ each independently represents an alkyl group having 1 to 8 carbon atoms. Ar ^{1 ″} and Ar ^{2 ″} each independently represent a substituted or unsubstituted arylene group. Y represents O, S or N—Ar ³ , and Ar ³ represents a substituted or unsubstituted aryl group. R ^{1 to} R ⁸ and R ^{11 to} R ¹⁸ each independently represent a hydrogen atom or a substituent. 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 ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ And R ¹⁴ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , and R ¹⁷ and R ¹⁸ may be bonded to each other to form a cyclic structure. However, when Z ¹ is a single bond, at least one of R ^{1 to} R ⁸ represents a substituted or unsubstituted diarylamino group, and when Z ² is a single bond, at least one of R ^{11 to} R ^18. Represents a substituted or unsubstituted diarylamino group. ]
[9] Z ¹ and Z ^{2 in} the general formula (7) are the same, Ar ^{1 ″} and Ar ^{2 ″} are the same, R ¹ and R ¹¹ are the same, and R ² and R ¹² are the same. R ³ and R ¹³ are the same, R ⁴ and R ¹⁴ are the same, R ⁵ and R ¹⁵ are the same, R ⁶ and R ¹⁶ are the same, R ⁷ and R ¹⁷ are the same a compound according to, characterized in that R ⁸ and R ¹⁸ are the same [8].
[10] The compound according to [8] or [9], wherein Z ¹ and Z ^{2 in} the general formula (7) are each independently O or S.

[11] A luminescent material comprising the compound according to any one of [1] to [10].
[12] A delayed phosphor comprising the compound according to any one of [1] to [10].
[13] An organic light emitting device comprising a light emitting layer containing the compound according to any one of [1] to [10] as a light emitting material on a substrate.
[14] The organic light-emitting device according to [13], which emits delayed fluorescence.
[15] The organic light-emitting device according to [13] or [14], which is an organic electroluminescence device.

  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 spectrum of a toluene solution of compound 1 of Example 1. 2 is a time-resolved spectrum of a toluene solution of compound 1 of Example 1. 2 is an emission spectrum of a toluene solution of the compound 2 of Example 1. 2 is a time-resolved spectrum of a toluene solution of compound 2 of Example 1. 2 is an emission spectrum of a thin film type organic photoluminescence device using Compound 1 of Example 2. 2 is a time-resolved spectrum of a thin film type organic photoluminescence device using Compound 1 of Example 2. 2 is an emission spectrum of a thin film type organic photoluminescence device using Compound 2 of Example 2. 2 is a time-resolved spectrum of a thin film type organic photoluminescence device using Compound 2 of Example 2. 2 is an emission spectrum of an organic electroluminescence device using Compound 1 of Example 3. 4 is a graph showing voltage-current density characteristics of an organic electroluminescence device using Compound 1 of Example 3. 4 is a graph showing current density-external quantum efficiency characteristics of an organic electroluminescence device using Compound 1 of Example 3. 2 is an emission spectrum of an organic electroluminescence device using the compound 2 of Example 3. 4 is a graph showing voltage-current density characteristics of an organic electroluminescence device using the compound 2 of Example 3. 4 is a graph showing current density-external quantum efficiency characteristics of an organic electroluminescence device using 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.

[Compound represented by general formula (1)]
The compound of the present invention is characterized by having a structure represented by the following general formula (1).

In the general formula (1), D is a group represented by the following general formula (2), and A represents an n-valent group including a structure represented by the following general formula (3).

In the general formula (2), Z ¹ represents O, S, C═O, C (R ²¹ ) (R ²² ), Si (R ²³ ) (R ²⁴ ), or a single bond. R ^{21 to} R ²⁴ each independently represents an alkyl group having 1 to 8 carbon atoms. The alkyl group herein may be either linear or branched, and more preferably has 1 to 6 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. , Isobutyl group, pentyl group, isopentyl group and hexyl group. Specific examples of C (R ²¹ ) (R ²² ) include C (CH ₃ ) (CH ₃ ) and C (C ₂ H ₅ ) (C ₂ H ₅ ), and Si (R ²³ ) (R Specific examples of ²⁴ ) include Si (CH ₃ ) (CH ₃ ) and Si (C ₂ H ₅ ) (C ₂ H ₅ ).

When Z ^{1 in the} general formula (2) is a single bond, the general formula (2) is a group having a carbazole skeleton. At this time, at least one of R ^{1 to} R ⁸ represents a substituted or unsubstituted diarylamino group. The substituted or unsubstituted diarylamino group may be any of R ^{1 to} R ⁸ , but at least one of R ³ or R ⁶ is preferably a substituted or unsubstituted diarylamino group. Two aryl groups constituting the substituted or unsubstituted diarylamino group represented by R ^{1 to} R ⁸ may be the same as or different from each other. The aryl group preferably has 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms. Specific examples include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. For the explanation and preferred range of substituents that can be substituted on the aryl group, reference can be made to the explanation and preferred range of substituents that can be taken by R ^{1 to} R ⁸ described later. Preferred specific examples of the substituted or unsubstituted diarylamino group include a diphenylamino group, a bis (4-methylphenyl) amino group, a bis (3-methylphenyl) amino group, a bis (3,5-dimethylphenyl) amino group, A bis (4-methylphenyl) amino group can be mentioned. The two aryl groups of the diarylamino group may be bonded to each other to form a cyclic structure together with the nitrogen atom of the amino group. For example, a 9-carbazolyl group can be mentioned.

R < ¹ > -R < ⁸ > of General formula (2) represents a hydrogen atom or a substituent each independently. R ^{1 to} R ⁸ may all be hydrogen atoms. Moreover, when two or more are substituents, those substituents may be the same or different. Examples of the substituent include a hydroxy group, a halogen atom, 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, and an alkyl substitution having 1 to 20 carbon atoms. An amino group, an aryl-substituted amino group having 12 to 40 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, a substitution having 12 to 40 carbon atoms, or Unsubstituted carbazolyl group, alkenyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, alkylsulfonyl group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms Haloalkyl group, amide group, alkylamide group having 2 to 10 carbon atoms, trialkylsilyl group having 3 to 20 carbon atoms, trialkylsilylalkyl group having 4 to 20 carbon atoms 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 C3-C40 substituted or unsubstituted heteroaryl group, C1-C10 substituted or unsubstituted dialkylamino group, C12-C40 substituted or unsubstituted diarylamino group, C12-C40 A substituted or unsubstituted carbazolyl group; 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 1 to 10 carbon atoms. Or an unsubstituted dialkylamino group, a substituted or unsubstituted diarylamino group having 12 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms It is a group.

  The alkyl group may be linear, branched, or cyclic, and more preferably has 1 to 6 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and tert-butyl. Group, pentyl group, hexyl group and isopropyl group. The aryl group may be a single ring or a condensed ring, and specific examples thereof include a phenyl group and a naphthyl group. The alkoxy group may be linear, branched or cyclic, and more preferably has 1 to 6 carbon atoms. Specific examples thereof include methoxy group, ethoxy group, propoxy group, butoxy group, tert-butoxy group. A group, a pentyloxy group, a hexyloxy group, and an isopropyloxy group. The two alkyl groups of the dialkylamino group may be the same or different from each other, but are preferably the same. The two alkyl groups of the dialkylamino group may each independently be linear, branched or cyclic, more preferably have 1 to 6 carbon atoms, and specific examples include a methyl group, an ethyl group, Examples thereof include a propyl group, a butyl group, a pentyl group, a hexyl group, and an isopropyl group. Two alkyl groups of the dialkylamino group may be bonded to each other to form a cyclic structure together with the nitrogen atom of the amino group. The aryl group that can be employed as the substituent may be a single ring or a condensed ring, and specific examples thereof include a phenyl group and a naphthyl group. The heteroaryl group may be a single ring or a condensed ring, and specific examples thereof include a pyridyl group, a pyridazyl group, a pyrimidyl group, a triazyl group, a triazolyl group, and a benzotriazolyl group. These heteroaryl groups may be a group bonded through a hetero atom or a group bonded through a carbon atom constituting a heteroaryl ring. The two aryl groups of the diarylamino group may be monocyclic or condensed, and specific examples include a phenyl group and a naphthyl group. Two aryl groups of the diarylamino group may be bonded to each other to form a cyclic structure together with the nitrogen atom of the amino group. For example, a 9-carbazolyl group can be mentioned.

In general formula (2), 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 are bonded to each other to form a cyclic structure. May be formed. 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.

A in the general formula (1) represents an n-valent group including a structure represented by the following general formula (3).

In the general formula (3), Y represents O, S or N—Ar ³ , and Ar ³ represents a substituted or unsubstituted aryl group. The aromatic ring constituting the aryl group represented by Ar ³ may be a single ring or a condensed ring, and specific examples include a benzene ring and a naphthalene ring. The aryl group preferably has 6 to 40 carbon atoms, more preferably 6 to 20 carbon atoms. For the explanation and preferred range of the substituent that can be substituted on the aryl group represented by Ar ^3, the explanation and preferred range of the substituent that can be taken by the above R ^{1 to} R ⁸ can be referred to.

  In General formula (1), n represents the integer in any one of 1-8. n is more preferably 1 to 6, and further preferably 1 to 4. When n is 2 or more, a plurality of D are bonded to A in the general formula (1). Several D may mutually be the same and may differ. If they are the same, there is an advantage that synthesis is easy.

  When n is 1, A containing the structure of the general formula (3) acting as an acceptor and D acting as a donor are bonded to each other one by one. On the other hand, when n is 2 or more, two or more D acting as a donor are bonded to A including the structure of the general formula (3) that acts as an acceptor. When two or more Ds are bonded, there is a general concern that the function as a donor is canceled out, and there is a risk that the molecule does not function effectively as a light emitting material. However, it has been found that by selecting and combining A and D in accordance with the present invention, a light emitting material having high luminous efficiency and excellent effects can be provided. This is presumably because the HOMO and LUMO spreads were controlled at the molecular level to satisfy the preferable conditions for the light-emitting material.

一般式（４）において、ＹはＯ、ＳまたはＮ−Ａｒ³を表す。Ｙの説明と好ましい範囲については、一般式（３）の説明と好ましい範囲を参照することができる。
一般式（４）において、Ａｒ¹およびＡｒ²は各々独立に置換もしくは無置換の芳香族基を表す。ここでいう芳香族基は、芳香環の環骨格を構成する原子によって直接オキサジアゾール環、チオジアゾール環またはトリアゾール環と結合する基を意味する。芳香環は単環であっても、縮合環であってもよい。また、芳香環を構成する環骨格原子は炭素原子のみからなるものであってもよいし、炭素原子とヘテロ原子が混在しているものであってもよい。ヘテロ原子としては、窒素原子、酸素原子、硫黄原子を好ましく例示することができる。Ａｒ¹およびＡｒ²の芳香環の環骨格構成原子数は５〜２０であることが好ましく、５〜１２であることがより好ましい。芳香環として、例えばベンゼン環やナフタレン環を挙げることができる。Ａｒ¹およびＡｒ²が表す芳香族基は、Ｄ以外の基で置換されていてもよい。そのような置換基の説明と好ましい範囲については、上記のＲ¹〜Ｒ⁸がとりうる置換基の説明と好ましい範囲を参照することができる。Ａｒ¹とＡｒ²は同一であっても、異なっていてもよいが、同一であれば合成が容易であるという利点がある。 A in the general formula (1) preferably has a structure represented by the following general formula (4).

In the general formula (4), Y represents O, S or N—Ar ³ . For the explanation and preferred range of Y, the explanation and preferred range of the general formula (3) can be referred to.
In the general formula (4), Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aromatic group. An aromatic group here means the group couple | bonded with an oxadiazole ring, a thiodiazole ring, or a triazole ring directly by the atom which comprises the ring skeleton of an aromatic ring. The aromatic ring may be a single ring or a condensed ring. Further, the ring skeleton atoms constituting the aromatic ring may be composed of only carbon atoms, or may be a mixture of carbon atoms and heteroatoms. Preferred examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. The number of atoms constituting the ring skeleton of the aromatic ring of Ar ¹ and Ar ² is preferably 5-20, and more preferably 5-12. Examples of the aromatic ring include a benzene ring and a naphthalene ring. The aromatic group represented by Ar ¹ and Ar ² may be substituted with a group other than D. For the explanation and preferred ranges of such substituents, reference can be made to the explanations and preferred ranges of the substituents that R ^{1 to} R ⁸ can take. Ar ¹ and Ar ² may be the same or different, but if they are the same, there is an advantage that synthesis is easy.

The position where D is bonded is not particularly limited. For example, D may be bonded to both the aromatic group of Ar ^{1 and} the aromatic group of Ar ² , or may be bonded to only one of them. The number of D bonded to the aromatic group of Ar ¹ and the number of D bonded to the aromatic group of Ar ² may be the same or different. If they are identical, there is an advantage that synthesis is easy. In a preferred embodiment, embodiment one D only aromatic group Ar ¹ is bonded, aspects, one aromatic group Ar ¹ and Ar ² D is attached, an aromatic of Ar ¹ and Ar ² An embodiment in which two D's are bonded to each group and an embodiment in which three D's are bonded to each of the aromatic groups Ar ¹ and Ar ² can be exemplified.

The compound represented by the general formula (1) preferably has a structure represented by the following general formula (5).

In the general formula (5), Z ¹ and Z ² each independently represent O, S, C═O, C (R ²¹ ) (R ²² ), Si (R ²³ ) (R ²⁴ ), or a single bond; ^{21 to} R ²⁴ each independently represents an alkyl group having 1 to 8 carbon atoms. Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aromatic group. Y represents O, S or N—Ar ³ , and Ar ³ represents a substituted or unsubstituted aryl group. R ^{1 to} R ⁸ and R ^{11 to} R ¹⁸ each independently represent a hydrogen atom or a substituent. 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 ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ And R ¹⁴ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , and R ¹⁷ and R ¹⁸ may be bonded to each other to form a cyclic structure. However, when Z ¹ is a single bond, at least one of R ^{1 to} R ⁸ represents a substituted or unsubstituted diarylamino group, and when Z ² is a single bond, at least one of R ^{11 to} R ^18. Represents a substituted or unsubstituted diarylamino group. For the explanation and preferred ranges of Z ¹ , Z ² , Ar ¹ , Ar ² , Y, R ^{1 to} R ⁸ and R ^{11 to} R ^{18 in} the general formula (5), Z in the general formulas (2) to (4) Reference can be made to the description and preferred ranges of ¹ , Ar ¹ , Ar ² , Y and R ^{1 to} R ⁸ .

  N1 and n2 in General formula (5) represent the integer in any one of 0-8 each independently. However, the sum of n1 and n2 is 1-8. When n1 is any integer of 2 to 8, n1 cyclic structures may be the same or different, and when n2 is any integer of 2 to 8, n2 The cyclic structures may be the same or different.

As a preferred embodiment in the general formula (5), when Z ¹ and Z ² are each independently O, S or a single bond, when Y is O or N—Ar ³ , the aromatic represented by Ar ¹ and Ar ² A case where the aromatic ring of the group is a benzene ring can be mentioned. In addition, the case where n1 and n2 are the same, or the case where n1 is 1 and n2 is 0 can also be mentioned.

The compound represented by the general formula (1) preferably has a structure represented by the following general formula (6).

In the general formula (6), Z ¹ represents O, S, C═O, C (R ²¹ ) (R ²² ), Si (R ²³ ) (R ²⁴ ) or a single bond, and R ^{21 to} R ²⁴ each represents Independently represents an alkyl group having 1 to 8 carbon atoms. Ar ^{1 ′} represents a substituted or unsubstituted arylene group. Ar ^{2 ′} represents a substituted or unsubstituted aryl group. Y represents O, S or N—Ar ³ , and Ar ³ represents a substituted or unsubstituted aryl group. R ^{1 to} R ⁸ each independently represents a hydrogen atom or a substituent. 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 may be bonded to each other to form a cyclic structure. Good. However, when Z ¹ is a single bond, at least one of R ^{1 to} R ⁸ represents a substituted or unsubstituted diarylamino group. For the explanation and preferred ranges of Z ¹ , Y, R ^{1 to} R ⁸ in the general formula (6), the explanation and preferred ranges of the corresponding groups in the general formula (2) and the general formula (3) can be referred to. .

The arylene group represented by Ar ^{1 ′ in} formula (6) preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms, constituting the skeleton of the aromatic ring. For example, 1,4-phenylene group, 1,3-phenylene group, 2,6-naphthylene group, and 2,7-naphthylene group can be exemplified, and 1,4-phenylene group and 1,3-phenylene group are preferable. . The aryl group represented by Ar ^{2 ′ in} formula (6) preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms, constituting the skeleton of the aromatic ring. For example, a phenyl group and a naphthyl group can be mentioned. The arylene group represented by Ar ^{1 ′} and the aryl group represented by Ar ^{2 ′} may be substituted with a substituent. For the explanation and preferred range of the substituent, reference can be made to the explanation and preferred range of the substituent that can be taken by the above R ^{1 to} R ⁸ .

The compound represented by the general formula (1) preferably has a structure represented by the following general formula (7).

In the general formula (7), Z ¹ and Z ² each independently represent O, S, C═O, C (R ²¹ ) (R ²² ), Si (R ²³ ) (R ²⁴ ) or a single bond, and R ^{21 to} R ²⁴ each independently represents an alkyl group having 1 to 8 carbon atoms. Ar ^{1 ″} and Ar ^{2 ″} each independently represent a substituted or unsubstituted arylene group. Y represents O, S or N—Ar ³ , and Ar ³ represents a substituted or unsubstituted aryl group. R ^{1 to} R ⁸ and R ^{11 to} R ¹⁸ each independently represent a hydrogen atom or a substituent. 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 ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ And R ¹⁴ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , and R ¹⁷ and R ¹⁸ may be bonded to each other to form a cyclic structure.
However, when Z ¹ is a single bond, at least one of R ^{1 to} R ⁸ represents a substituted or unsubstituted diarylamino group, and when Z ² is a single bond, at least one of R ^{11 to} R ^18. Represents a substituted or unsubstituted diarylamino group.

For the explanation and preferred ranges of Z ¹ , Z ² , Y, R ^{1 to} R ⁸ and R ^{11 to} R ^{18 in} the general formula (7), Z ¹ , Ar ¹ , Ar in the general formulas (2) to (4) Reference can be made to the description and preferred ranges of ² , Y and R ^{1 to} R ⁸ . For the explanation and preferred range of Ar ^{1 ″} and Ar ^{2 ″} in the general formula (7), the explanation and preferred range of Ar ^{1 ′} in the general formula (6) can be referred to.

In the general formula (7), Z ¹ and Z ² are the same, Ar ^{1 ″} and Ar ^{2 ″} are the same, R ¹ and R ¹¹ are the same, R ² and R ¹² are the same, R 1 ³ and R ¹³ are the same, R ⁴ and R ¹⁴ are the same, R ⁵ and R ¹⁵ are the same, R ⁶ and R ¹⁶ are the same, R ⁷ and R ¹⁷ are the same, R ^A compound in which ⁸ and R ¹⁸ are the same has advantages such as easy synthesis.

  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, more preferably 1000 or less, and even more preferably 800 or less. The lower limit of the molecular weight is the molecular weight of the minimum compound represented by the general formula (1).

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, a repeating unit is prepared by preparing a monomer containing a polymerizable functional group in either A or D of the general formula (1) and polymerizing the monomer alone or copolymerizing with another monomer. It is conceivable to obtain a polymer having the above and use the polymer as a light emitting material. Alternatively, it is also possible to obtain a dimer or trimer by coupling compounds having a structure represented by the general formula (1) and use them as a light emitting material.

As an example of the polymer having a repeating unit including the structure represented by the general formula (1), a polymer including a structure represented by the following general formula (8) or (9) can be given.

In the general formulas (8) and (9), 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 formulas (8) and (9), 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 A or D in the structure of the general formula (1) constituting R and R ^{1 to} R ⁸ and R ^{21 to} R ^{24 in} the structure of the general formula (2). Or any ^one of Ar ¹ , Ar ² and Ar ^{3 in} the general formula (4), R ^{1 to} R ⁸ , R ^{11 to} R ¹⁸ , R ^{21 to} R ²⁴ , Ar ¹ , Ar ² , in the general formula (5), one of ^{Ar 3, R 1 ~R 8,} R 21 ~R 24, Ar 1 in the general formula (6) ', Ar ^2', one of Ar ^3, R ¹ ~R ⁸ of the general formula (7), R ^{11 to} R ¹⁸ , R ^{21 to} R ²⁴ , Ar ^{1 ″} , Ar ^{2 ″} and Ar ³ can be bonded. 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 (10) to (13).

In the polymer having a repeating unit containing these formulas (10) to (13), a hydroxy group is introduced into either A or D of the structure of the general formula (1), and the following compound is used as a linker: It can be synthesized by reacting 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.

上式におけるＤ、Ａおよびｎの説明については、一般式（１）における対応する記載を参照することができる。上式におけるＸはハロゲン原子を表し、フッ素原子、塩素原子、臭素原子、ヨウ素原子を挙げることができ、塩素原子、臭素原子、ヨウ素原子が好ましい。
一般式（１）で表される化合物のうち、例えば一般式（５）で表される化合物は以下のスキームにより合成することが可能である。

上式におけるＺ¹、Ｚ²、Ａｒ¹、Ａｒ²、Ｙ、Ｒ¹〜Ｒ⁸、Ｒ¹¹〜Ｒ¹⁸、ｎ１およびｎ２の説明については、一般式（５）における対応する記載を参照することができる。上式におけるＸはハロゲン原子を表す。
上記の２つのスキームにおける反応は、公知のカップリング反応を応用したものであり、公知の反応条件を適宜選択して用いることができる。上記の反応の詳細については、後述の合成例を参考にすることができる。また、一般式（１）で表される化合物は、その他の公知の合成反応を組み合わせることによっても合成することができる。 [Synthesis Method of Compound Represented by General Formula (1)]
The compound represented by the general formula (1) can be synthesized by combining known reactions. For example, it can be synthesized according to the following scheme.

For the explanation of D, A and n in the above formula, the corresponding description in the general formula (1) can be referred to. X in the above formula 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.
Among the compounds represented by the general formula (1), for example, the compound represented by the general formula (5) can be synthesized by the following scheme.

For the explanation of Z ¹ , Z ² , Ar ¹ , Ar ² , Y, R ^{1 to} R ⁸ , R ^{11 to} R ¹⁸ , n1 and n2 in the above formula, see the corresponding description in general formula (5). Can do. X in the above formula represents a halogen atom.
The reactions in the above two schemes apply a known coupling reaction, and can be used by appropriately selecting known reaction conditions. The details of the above reaction can be referred to the synthesis examples described below. The compound represented by the general formula (1) 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. 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, delayed fluorescent materials, after energy transition to an excited triplet state due to intersystem crossing, etc., are then crossed back to an excited singlet state due to triplet-triplet annihilation or absorption of thermal energy, and emit 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, cross the system into excited singlets, and 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 lifetime of light generated (emission lifetime) due to the cross-system crossing from the excited triplet state to the excited singlet state is usually 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 device crosses from the excited triplet state to the excited singlet state sufficiently by the heat of the device and emits 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. 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. 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, R ′, and R _{1 to} R ₁₀ in the structural formulas of the following exemplary compounds each independently represent a hydrogen atom or a substituent. X represents a carbon atom or a hetero atom forming a ring skeleton, n represents an integer of 3 to 5, Y represents a substituent, and m represents an integer of 0 or more.

  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.

窒素置換したな二つ口フラスコに、４−ブロモベンゾイルクロリド（６８．４ｍｍｏｌ，１５．０ｇ）、ヒドラジンモノハイドレート（３４．２ｍｍｏｌ，１．１０ｇ）、クロロホルム２４０ｍｌを加え、氷浴に浸け冷却（０−５℃）し３０分間攪拌した。そこにトリエチルアミン（１３６．８ｍｍｏｌ，１３．８ｇ）を滴下した後、３０分間攪拌し、更に室温で１２時間攪拌した。析出した白色固体を吸引濾過により収集し、水で洗浄した後に真空乾燥することにより目的物であるＮ，Ｎ’−ビス（４−ブロモベンゾイル）−ヒドラジンを得た（収量：９．３４ｇ，収率：６８．６％）。 Synthesis Example 1 Synthesis of Compound 1

4-Bromobenzoyl chloride (68.4 mmol, 15.0 g), hydrazine monohydrate (34.2 mmol, 1.10 g), and 240 ml of chloroform were added to a nitrogen-substituted two-necked flask, and immersed in an ice bath for cooling ( 0-5 ° C) and stirred for 30 minutes. Triethylamine (136.8 mmol, 13.8 g) was added dropwise thereto, followed by stirring for 30 minutes and further stirring at room temperature for 12 hours. The precipitated white solid was collected by suction filtration, washed with water and then vacuum dried to obtain the target N, N′-bis (4-bromobenzoyl) -hydrazine (yield: 9.34 g, yield). (Rate: 68.6%).

窒素置換したな二つ口フラスコに、Ｎ，Ｎ’−ビス（４−ブロモベンゾイル）−ヒドラジン（８．８ｍｍｏｌ，３．５ｇ）、五塩化リン（１９．３ｍｍｏｌ，４．０１ｇ）、トルエン３５ｍｌを加え、３時間加熱・還流した。そこに水３５ｍｌを加え、３０分間攪拌した後、有機層を分液・抽出した。無水硫酸マグネシウムを加え脱水し、溶媒を留去すると黄色固体が得られた。そこにエタノールとヘキサンの混合溶媒を加えて洗浄することにより、目的物であるＮ，Ｎ’−ビス（クロロ（４−ブロモフェニル）メチレン）−ヒドラジンを得た（収量：２．９５ｇ，収率：７７．２％）。

In a nitrogen-substituted two-necked flask, N, N′-bis (4-bromobenzoyl) -hydrazine (8.8 mmol, 3.5 g), phosphorus pentachloride (19.3 mmol, 4.01 g) and 35 ml of toluene were added. In addition, the mixture was heated and refluxed for 3 hours. 35 ml of water was added thereto and stirred for 30 minutes, and then the organic layer was separated and extracted. Anhydrous magnesium sulfate was added for dehydration, and the solvent was distilled off to obtain a yellow solid. A mixed solvent of ethanol and hexane was added thereto and washed to obtain N, N′-bis (chloro (4-bromophenyl) methylene) -hydrazine as a target product (yield: 2.95 g, yield). : 77.2%).

窒素置換したな二つ口フラスコに、Ｎ，Ｎ’−ビス（クロロ（４−ブロモフェニル）メチレン）−ヒドラジン（６．８ｍｍｏｌ，２．９５ｇ）、アニリン（６．８ｍｍｏｌ，６３５ｍｇ）、Ｎ，Ｎ’−ジメチルアニリン１５ｍｌを加え、５時間加熱・還流した。反応溶液を５０ｍｌの１Ｎ希塩酸にゆっくりと加え、３０分間攪拌すると固体が析出した。析出固体を吸引濾過により収集し、トルエンに溶かした後、炭酸水素ナトリウム水溶液を加え、有機層を分液・抽出した。無水硫酸マグネシウムを加え脱水し、溶媒を留去すると得られた固体をエタノールとヘキサンの混合溶媒で再結晶化することにより目的物である３，５−ビス（４−ブロモフェニル）−４−フェニル−４Ｈ−１，２，４−トリアゾールを得た（収量：２．２５ｇ，収率：７２．８％）。

Into a nitrogen-substituted two-necked flask, N, N′-bis (chloro (4-bromophenyl) methylene) -hydrazine (6.8 mmol, 2.95 g), aniline (6.8 mmol, 635 mg), N, N 15 ml of '-dimethylaniline was added and heated and refluxed for 5 hours. The reaction solution was slowly added to 50 ml of 1N dilute hydrochloric acid and stirred for 30 minutes to precipitate a solid. The precipitated solid was collected by suction filtration, dissolved in toluene, an aqueous sodium hydrogen carbonate solution was added, and the organic layer was separated and extracted. Anhydrous magnesium sulfate is added for dehydration, and the solvent is distilled off. The resulting solid is recrystallized with a mixed solvent of ethanol and hexane to give 3,5-bis (4-bromophenyl) -4-phenyl as the target product. -4H-1,2,4-triazole was obtained (yield: 2.25 g, yield: 72.8%).

窒素置換したな二つ口フラスコに、３，５−ス（４−ブロモフェニル）−４−フェニル−４Ｈ−１，２，４−トリアゾール（３．３０ｍｍｏｌ，１．５０ｇ）、フェノキサジン（７．２６ｍｍｏｌ，１．３３ｇ）、炭酸カリウム（２１．８ｍｍｏｌ，３．０１ｇ）、トルエン４０ｍｌを加え、室温下１０分間攪拌した。そこに酢酸パラジウム（II）（０．２２ｍｍｏｌ，４９．４ｍｇ）、トリ−tert−ブチルホスフィン（０．８０ｍｍｏｌ，１６１．９ｍｇ）、トルエン４０ｍｌの混合溶液を加え、２４時間加熱・還流した。室温まで放冷した後、クロロホルムと食塩水を加え、有機層を分液・抽出した。無水硫酸マグネシウムを加え脱水し、溶媒を留去した。クロロホルム：ヘキサン＝１：４の混合溶媒を用い、シリカゲルカラムクロマトグラフィーにより目的物である化合物１（３，５−ビス（４−Ｎ−フェノキサジルフェニル）−４−フェニル−４Ｈ−１，２，４−トリアゾール）を単離・精製した（収量：１．５２ｇ，収率：６９．９％）。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，３００ＭＨｚ，ＴＭＳ，δ）：５．９９（ｄ，４Ｈ），６．６１（ｔ，４Ｈ），６．６８（ｍ，８Ｈ），７．５７（ｄ，４Ｈ），８．３９（ｄ，４Ｈ）
ＭＡＬＤＩ−ＭＳ ｍ／ｚ：５８４

Into a nitrogen-substituted two-necked flask, 3,5-s (4-bromophenyl) -4-phenyl-4H-1,2,4-triazole (3.30 mmol, 1.50 g), phenoxazine (7. 26 mmol, 1.33 g), potassium carbonate (21.8 mmol, 3.01 g) and 40 ml of toluene were added, and the mixture was stirred at room temperature for 10 minutes. Thereto was added a mixed solution of palladium (II) acetate (0.22 mmol, 49.4 mg), tri-tert-butylphosphine (0.80 mmol, 161.9 mg) and 40 ml of toluene, and the mixture was heated and refluxed for 24 hours. After cooling to room temperature, chloroform and brine were added, and the organic layer was separated and extracted. Anhydrous magnesium sulfate was added for dehydration, and the solvent was distilled off. Compound 1 (3,5-bis (4-N-phenoxazylphenyl) -4-phenyl-4H-1,2 which is the target product by silica gel column chromatography using a mixed solvent of chloroform: hexane = 1: 4 , 4-triazole) was isolated and purified (yield: 1.52 g, yield: 69.9%).
¹ H-NMR (CDCl ₃ , 300 MHz, TMS, δ): 5.99 (d, 4H), 6.61 (t, 4H), 6.68 (m, 8H), 7.57 (d, 4H) , 8.39 (d, 4H)
MALDI-MS m / z: 584

窒素置換したな二つ口フラスコに、Ｎ，Ｎ’−ビス（４−ブロモベンゾイル）−ヒドラジン（３．５２ｍｍｏｌ，１．４０ｇ）、塩化ホスホリル（３０８．０ｍｍｏｌ，４７．２ｇ）を加え、１２時間加熱・還流した。反応溶液を室温まで放冷した後、水１５０ｍｌをゆっくり加えると白色固体が析出した。炭酸ナトリウムを加え中和し、吸引濾過により析出固体を収集した。水で洗浄した後、真空乾燥することにより目的物である２，５−ビス（４−ブロモフェニル）−１，３，４−オキサジアゾールを得た（収量：１．１４ｇ，収率：８５．２％）。 Synthesis Example 2 Synthesis of Compound 2

N, N′-bis (4-bromobenzoyl) -hydrazine (3.52 mmol, 1.40 g) and phosphoryl chloride (308.0 mmol, 47.2 g) were added to a nitrogen-substituted two-necked flask for 12 hours. Heated to reflux. After allowing the reaction solution to cool to room temperature, 150 ml of water was slowly added to precipitate a white solid. Sodium carbonate was added for neutralization, and the precipitated solid was collected by suction filtration. After washing with water, vacuum drying was performed to obtain 2,5-bis (4-bromophenyl) -1,3,4-oxadiazole, the target product (yield: 1.14 g, yield: 85). .2%).

窒素置換したな二つ口フラスコに、２，５−ビス（４−ブロモフェニル）−１，３，４−オキサジアゾール（１．６６ｍｍｏｌ，６３０．８ｍｇ）、フェノキサジン（３．６５ｍｍｏｌ，６６８．７ｍｇ）、炭酸カリウム（１１．０ｍｍｏｌ，１．５２ｇ）、トルエン２５ｍｌを加え、室温下１０分間攪拌した。そこに酢酸パラジウム（II）（０．１１ｍｍｏｌ，２５．０ｍｇ）、トリ−tert−ブチルホスフィン（０．４０ｍｍｏｌ，８１．０ｍｇ）、トルエン２５ｍｌの混合溶液を加え、２４時間加熱・還流した。室温まで放冷した後、クロロホルムと食塩水を加え、有機層を分液・抽出した。無水硫酸マグネシウムを加え脱水し、溶媒を留去した。クロロホルムを用いたシリカゲルカラムクロマトグラフィーにより目的物である化合物２（２，５−ビス（４−Ｎ−フェノキサジルフェニル）−１，３，４−オキサジアゾール）を単離・精製した（収量：９６５．２ｍｇ，収率：９９．５％）。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，３００ＭＨｚ，ＴＭＳ，δ）：５．９９（ｄ，４Ｈ），６．６１（ｔ，４Ｈ），６．６８（ｍ，８Ｈ），７．５７（ｄ，４Ｈ），８．３９（ｄ，４Ｈ）
ＭＡＬＤＩ−ＭＳ ｍ／ｚ：５８４

Into a nitrogen-substituted two-necked flask, 2,5-bis (4-bromophenyl) -1,3,4-oxadiazole (1.66 mmol, 630.8 mg), phenoxazine (3.65 mmol, 668. 7 mg), potassium carbonate (11.0 mmol, 1.52 g) and 25 ml of toluene were added, and the mixture was stirred at room temperature for 10 minutes. Thereto was added a mixed solution of palladium (II) acetate (0.11 mmol, 25.0 mg), tri-tert-butylphosphine (0.40 mmol, 81.0 mg) and 25 ml of toluene, and the mixture was heated and refluxed for 24 hours. After cooling to room temperature, chloroform and brine were added, and the organic layer was separated and extracted. Anhydrous magnesium sulfate was added for dehydration, and the solvent was distilled off. The target compound 2 (2,5-bis (4-N-phenoxazylphenyl) -1,3,4-oxadiazole) was isolated and purified by silica gel column chromatography using chloroform (yield) : 965.2 mg, yield: 99.5%).
¹ H-NMR (CDCl ₃ , 300 MHz, TMS, δ): 5.99 (d, 4H), 6.61 (t, 4H), 6.68 (m, 8H), 7.57 (d, 4H) , 8.39 (d, 4H)
MALDI-MS m / z: 584

窒素置換したな二つ口フラスコに、Ｎ，Ｎ’−ビス（４−ブロモベンゾイル）−ヒドラジン（４．００ｍｍｏｌ，１．５９ｇ）、五硫化二リン（１６．０ｍｍｏｌ，３．５６ｇ）、ピリジン１００ｍｌを加え、４日間加熱・還流した。室温まで放冷した後、溶媒を留去し、塩化メチレンを加え、氷浴で冷却すると白色固体が析出した。吸引濾過により析出固体を収集し、濾液を再度冷却し、再結晶化を繰り返した。得られた固体を真空乾燥することにより目的物である２，５−ビス（４−ブロモフェニル）−１，３，４−チアジアゾールを得た（収量：１．１８ｇ，収率：７４．６％）。 (Synthesis Example 3) Synthesis of Compound 3

Into a nitrogen-substituted two-necked flask, N, N′-bis (4-bromobenzoyl) -hydrazine (4.00 mmol, 1.59 g), diphosphorus pentasulfide (16.0 mmol, 3.56 g), pyridine 100 ml And heated to reflux for 4 days. After allowing to cool to room temperature, the solvent was distilled off, methylene chloride was added, and the mixture was cooled in an ice bath to precipitate a white solid. The precipitated solid was collected by suction filtration, the filtrate was cooled again, and recrystallization was repeated. The obtained solid was vacuum-dried to obtain 2,5-bis (4-bromophenyl) -1,3,4-thiadiazole as a target product (yield: 1.18 g, yield: 74.6%). ).

窒素置換したな二つ口フラスコに、２，５−ビス（４−ブロモフェニル）−１，３，４−チアジアゾール（１．２６ｍｍｏｌ，５００ｍｇ）、フェノキサジン（２．７７ｍｍｏｌ，５０７．５ｍｇ）、炭酸カリウム（８．３１ｍｍｏｌ，１．１５ｇ）、トルエン２０ｍｌを加え、室温下１０分間攪拌した。そこに酢酸パラジウム（II）（０．０８ｍｍｏｌ，１９．０ｍｇ）、トリ−tert−ブチルホスフィン（０．３１ｍｍｏｌ，６２．０ｍｇ）、トルエン２０ｍｌの混合溶液を加え、２４時間加熱・還流した。室温まで放冷した後、クロロホルムと食塩水を加え、有機層を分液・抽出した。無水硫酸マグネシウムを加え脱水し、溶媒を留去した。クロロホルムを用い、シリカゲルカラムクロマトグラフィーにより目的物である化合物３（２，５−ビス（４−Ｎ−フェノキサジルフェニル）−１，３，４−チアジアゾール）を単離・精製した（収量：７４５．６ｍｇ，収率：９８．５％）。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，３００ＭＨｚ，ＴＭＳ，δ）：６．０１（ｄ，４Ｈ），６．６１（ｔ，４Ｈ），６．６８（ｍ，８Ｈ），７．５３（ｄ，４Ｈ），８．２７（ｄ，４Ｈ）
ＭＡＬＤＩ−ＭＳ ｍ／ｚ：６０１

Into a nitrogen-substituted two-necked flask, 2,5-bis (4-bromophenyl) -1,3,4-thiadiazole (1.26 mmol, 500 mg), phenoxazine (2.77 mmol, 507.5 mg), carbonic acid were added. Potassium (8.31 mmol, 1.15 g) and 20 ml of toluene were added, and the mixture was stirred at room temperature for 10 minutes. Thereto was added a mixed solution of palladium (II) acetate (0.08 mmol, 19.0 mg), tri-tert-butylphosphine (0.31 mmol, 62.0 mg) and 20 ml of toluene, and the mixture was heated and refluxed for 24 hours. After cooling to room temperature, chloroform and brine were added, and the organic layer was separated and extracted. Anhydrous magnesium sulfate was added for dehydration, and the solvent was distilled off. The target compound 3 (2,5-bis (4-N-phenoxazylphenyl) -1,3,4-thiadiazole) was isolated and purified by silica gel column chromatography using chloroform (yield: 745). .6 mg, yield: 98.5%).
¹ H-NMR (CDCl ₃ , 300 MHz, TMS, δ): 6.01 (d, 4H), 6.61 (t, 4H), 6.68 (m, 8H), 7.53 (d, 4H) , 8.27 (d, 4H)
MALDI-MS m / z: 601

窒素置換した二つ口フラスコに、２，５−ビス（４−ブロモフェニル）−１，３，４−チアジアゾール（１．２６ｍｍｏｌ，５００ｍｇ）、３−ジフェニルアミノカルバゾール（２．７７ｍｍｏｌ，９２６．３ｍｇ）、炭酸カリウム（８．３１ｍｍｏｌ，１．１５ｇ）、トルエン２０ｍｌを加え、室温下１０分間攪拌した。そこに酢酸パラジウム（II）（０．０８ｍｍｏｌ，１９．０ｍｇ）、トリ−tert−ブチルホスフィン（０．３１ｍｍｏｌ，６２．０ｍｇ）、トルエン２０ｍｌの混合溶液を加え、２４時間加熱・還流した。室温まで放冷した後、クロロホルムと食塩水を加え、有機層を分液・抽出した。無水硫酸マグネシウムを加え脱水し、溶媒を留去した。クロロホルムを用い、シリカゲルカラムクロマトグラフィーにより目的物である化合物４（２，５−ビス（４−Ｎ−（３−ジフェニルアミノカルバゾイル）フェニル）−１，３，４−チアジアゾール）を単離・精製した（収量：６５４．８ｍｇ，収率：５７．５％）。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，３００ＭＨｚ，ＴＭＳ，δ）：６．９６（ｔ，４Ｈ），７．１２（ｄ，８Ｈ），７．２３（ｄ，８Ｈ），７．２７（ｍ，４Ｈ），７．４４（ｍ，４Ｈ），７．５１（ｄ，２Ｈ），７．７８（ｄ，４Ｈ），７．９４（ｓ，２Ｈ），８．０１（ｄ，２Ｈ），８．２９（ｄ，４Ｈ）
ＭＡＬＤＩ−ＭＳ ｍ／ｚ：９０３ (Synthesis Example 4) Synthesis of Compound 4

To a nitrogen-substituted two-necked flask, 2,5-bis (4-bromophenyl) -1,3,4-thiadiazole (1.26 mmol, 500 mg), 3-diphenylaminocarbazole (2.77 mmol, 926.3 mg) , Potassium carbonate (8.31 mmol, 1.15 g) and 20 ml of toluene were added, and the mixture was stirred at room temperature for 10 minutes. Thereto was added a mixed solution of palladium (II) acetate (0.08 mmol, 19.0 mg), tri-tert-butylphosphine (0.31 mmol, 62.0 mg) and 20 ml of toluene, and the mixture was heated and refluxed for 24 hours. After cooling to room temperature, chloroform and brine were added, and the organic layer was separated and extracted. Anhydrous magnesium sulfate was added for dehydration, and the solvent was distilled off. Isolation and purification of the target compound 4 (2,5-bis (4-N- (3-diphenylaminocarbazoyl) phenyl) -1,3,4-thiadiazole) by silica gel column chromatography using chloroform (Yield: 654.8 mg, Yield: 57.5%).
¹ H-NMR (CDCl ₃ , 300 MHz, TMS, δ): 6.96 (t, 4H), 7.12 (d, 8H), 7.23 (d, 8H), 7.27 (m, 4H) , 7.44 (m, 4H), 7.51 (d, 2H), 7.78 (d, 4H), 7.94 (s, 2H), 8.01 (d, 2H), 8.29 ( d, 4H)
MALDI-MS m / z: 903

(Example 1) Preparation and evaluation of organic photoluminescence device (solution)
A toluene solution (concentration 10 ⁻⁴ mol / L) of Compound 1 synthesized in Synthesis Example 1 was prepared and irradiated with ultraviolet light at 300 K while bubbling nitrogen. As shown in FIG. 2, the peak wavelength was 462 nm. Fluorescence was observed. Further, after a nitrogen bubble, measurement was performed with a small fluorescence lifetime measuring apparatus (Quantaurus-tau manufactured by Hamamatsu Photonics Co., Ltd.), and the time-resolved spectrum shown in FIG. 3 was obtained (τ1 = 3.26 μs, τ2 = 31.00 μs). . The photoluminescence quantum efficiency of Compound 1 in a toluene solution was measured at 300 K with an absolute PL quantum yield measurement apparatus (Quantaurus-QY manufactured by Hamamatsu Photonics Co., Ltd.), and it was 15.2% after nitrogen bubble.
Similarly, a toluene solution was prepared and evaluated using Compound 2 synthesized in Synthesis Example 2 instead of Compound 1. FIG. 4 shows the emission spectrum, and FIG. 5 shows the time-resolved spectrum after the nitrogen bubble (τ1 = 0.02 μs, τ2 = 13.3 μs). The photoluminescence quantum efficiency was 43.1% after the nitrogen bubble.

(Example 2) Preparation and evaluation of organic photoluminescence device (thin film)
A thin film in which the concentration of Compound 1 is 6.0% by weight on a silicon substrate by vapor deposition of Compound 1 and DPEPO from different deposition sources under a vacuum degree of 5.0 × 10 ⁻⁴ Pa. Was formed at a thickness of 100 nm at 0.3 nm / second to obtain an organic photoluminescence device. An emission spectrum obtained using the same measuring apparatus as in Example 1 is shown in FIG. Further, measurement was performed with a small fluorescent lifetime measuring apparatus (Quantaurus-tau manufactured by Hamamatsu Photonics Co., Ltd.) at 300 K, and the time-resolved spectrum shown in FIG. 7 was obtained. It was confirmed that the fluorescence was a thermally activated delayed fluorescence in which the delayed fluorescence component decreased as the temperature decreased. The photoluminescence quantum efficiency was 42.6% at 300 K under nitrogen flow.
An organic photoluminescence device was prepared using Compound 2 instead of Compound 1, and evaluated in the same manner. FIG. 8 shows an emission spectrum, and FIG. 9 shows a time-resolved spectrum. It was confirmed that the fluorescence was a thermally activated delayed fluorescence in which the delayed fluorescence component decreased as the temperature decreased. The photoluminescence quantum efficiency was 83.8% at 300 K under nitrogen flow.

(Comparative example 1) Preparation and evaluation of organic photoluminescence device (thin film)
When a test was conducted in the same manner as in Example 2 using the following Comparative Compound 1 instead of Compound 1, delayed fluorescence was not observed and the quantum efficiency was low.

Example 3 Production and Evaluation of Organic Electroluminescence Element Each thin film was vacuum-deposited on a glass substrate on which an anode made of indium tin oxide (ITO) having a film thickness of 100 nm was formed by a vacuum deposition method. Lamination was performed at 0 × 10 ⁻⁴ Pa. First, α-NPD was formed to a thickness of 30 nm on ITO, and mCP was formed to a thickness of 10 nm thereon. Next, Compound 1 and DPEPO 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 Compound 1 was 6.0% by weight. Next, DPEPO is formed to a thickness of 10 nm, TPBi is formed to a thickness of 40 nm, lithium fluoride (LiF) is vacuum-deposited to 0.8 nm, and then aluminum (Al) is deposited to a thickness of 100 nm. Thus, a cathode was formed, and an organic electroluminescence element was obtained.
Using the manufactured organic electroluminescence device, a semiconductor parameter analyzer (manufactured by Agilent Technologies: E5273A), an optical power meter measuring device (manufactured by Newport: 1930C), and an optical spectrometer (manufactured by Ocean Optics: USB2000) As a result, 456 nm emission was observed as shown in FIG. The voltage-current density characteristic is shown in FIG. 11, and the current density-external quantum efficiency characteristic is shown in FIG. The organic electroluminescence device using Compound 1 as the light emitting material achieved a high external quantum efficiency of 8.66%.
An organic electroluminescence device was produced in the same manner using Compound 2 instead of Compound 1. However, TPBi was formed to a thickness of 65 nm. FIG. 13 shows the emission spectrum of the produced organic electroluminescent element, FIG. 14 shows the voltage-current density characteristic, and FIG. 15 shows the current density-external quantum efficiency characteristic. The organic electroluminescence device using Compound 2 as the light emitting material achieved a high external quantum efficiency of 14.87%.

  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 (15)

A compound represented by the following general formula (1).
General formula (1)
(D) n-A
[In General Formula (1), D represents a group represented by the following General Formula (2), and A represents an n-valent group including a structure represented by the following General Formula (3). n represents an integer of 1 to 8. ]

[In the general formula (2), Z ¹ represents O, S, C═O, C (R ²¹ ) (R ²² ), Si (R ²³ ) (R ²⁴ ) or a single bond, and R ^{21 to} R ²⁴ represent Each independently represents an alkyl group having 1 to 8 carbon atoms. R ^{1 to} R ⁸ each independently represents a hydrogen atom or a substituent. 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 may be bonded to each other to form a cyclic structure. Good. However, when Z ¹ is a single bond, at least one of R ^{1 to} R ⁸ represents a substituted or unsubstituted diarylamino group. ]

[In General Formula (3), Y represents O, S or N—Ar ³ , and Ar ³ represents a substituted or unsubstituted aryl group. ] The compound according to claim 1, wherein A in the general formula (1) has a structure represented by the following general formula (4).

[In General Formula (4), Y represents O, S or N—Ar ³ , and Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aromatic group. ] N of general formula (1) is an integer in any one of 1-4, The compound of Claim 1 or 2 characterized by the above-mentioned. It is represented by General formula (5), The compound of Claim 1 characterized by the above-mentioned.

[In General Formula (5), Z ¹ and Z ² each independently represent O, S, C═O, C (R ²¹ ) (R ²² ), Si (R ²³ ) (R ²⁴ ) or a single bond, R ^{21 to} R ²⁴ each independently represents an alkyl group having 1 to 8 carbon atoms. Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aromatic group. Y represents O, S or N—Ar ³ , and Ar ³ represents a substituted or unsubstituted aryl group. R ^{1 to} R ⁸ and R ^{11 to} R ¹⁸ each independently represent a hydrogen atom or a substituent. 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 ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ And R ¹⁴ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , and R ¹⁷ and R ¹⁸ may be bonded to each other to form a cyclic structure. However, when Z ¹ is a single bond, at least one of R ^{1 to} R ⁸ represents a substituted or unsubstituted diarylamino group, and when Z ² is a single bond, at least one of R ^{11 to} R ^18. Represents a substituted or unsubstituted diarylamino group. n1 and n2 each independently represents an integer of 0 to 8, and the sum of n1 and n2 is 1 to 8. ] The compound according to claim 4, wherein Z ¹ and Z ^{2 in} the general formula (5) are each independently O, S or a single bond. The compound according to claim 4 or 5, wherein Y in the general formula (5) is O or N-Ar ³ . It is represented by General formula (6), The compound of Claim 1 characterized by the above-mentioned.

[In General Formula (6), Z ¹ represents O, S, C═O, C (R ²¹ ) (R ²² ), Si (R ²³ ) (R ²⁴ ) or a single bond, and R ^{21 to} R ²⁴ represent Each independently represents an alkyl group having 1 to 8 carbon atoms. Ar ^{1 ′} represents a substituted or unsubstituted arylene group. Ar ^{2 ′} represents a substituted or unsubstituted aryl group. Y represents O, S or N—Ar ³ , and Ar ³ represents a substituted or unsubstituted aryl group. R ^{1 to} R ⁸ each independently represents a hydrogen atom or a substituent. 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 may be bonded to each other to form a cyclic structure. Good. However, when Z ¹ is a single bond, at least one of R ^{1 to} R ⁸ represents a substituted or unsubstituted diarylamino group. ] It is represented by following General formula (7), The compound of Claim 1 characterized by the above-mentioned.

[In General Formula (7), Z ¹ and Z ² each independently represent O, S, C═O, C (R ²¹ ) (R ²² ), Si (R ²³ ) (R ²⁴ ) or a single bond, R ^{21 to} R ²⁴ each independently represents an alkyl group having 1 to 8 carbon atoms. Ar ^{1 ″} and Ar ^{2 ″} each independently represent a substituted or unsubstituted arylene group. Y represents O, S or N—Ar ³ , and Ar ³ represents a substituted or unsubstituted aryl group. R ^{1 to} R ⁸ and R ^{11 to} R ¹⁸ each independently represent a hydrogen atom or a substituent. 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 ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ And R ¹⁴ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , and R ¹⁷ and R ¹⁸ may be bonded to each other to form a cyclic structure. However, when Z ¹ is a single bond, at least one of R ^{1 to} R ⁸ represents a substituted or unsubstituted diarylamino group, and when Z ² is a single bond, at least one of R ^{11 to} R ^18. Represents a substituted or unsubstituted diarylamino group. ] In formula (7), Z ¹ and Z ² are the same, Ar ^{1 ″} and Ar ^{2 ″} are the same, R ¹ and R ¹¹ are the same, R ² and R ¹² are the same, R ³ And R ¹³ are the same, R ⁴ and R ¹⁴ are the same, R ⁵ and R ¹⁵ are the same, R ⁶ and R ¹⁶ are the same, R ⁷ and R ¹⁷ are the same, R ⁸ And R ¹⁸ are the same. The compound according to claim 8 or 9, wherein Z ¹ and Z ^{2 in} the general formula (7) are each independently O or S. The luminescent material which consists of a compound as described in any one of Claims 1-10. The delayed fluorescent substance which consists of a compound as described in any one of Claims 1-10. An organic light emitting device comprising a light emitting layer containing the compound according to claim 1 as a light emitting material on a substrate. The organic light emitting device according to claim 13, which emits delayed fluorescence. The organic light-emitting device according to claim 13, wherein the organic light-emitting device is an organic electroluminescence device.

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