WO2021220952A1 - Nitrogen-containing heterocyclic compound and use thereof - Google Patents

Abstract

Provided are a nitrogen-containing heterocyclic compound and technology relating to use of the same. The nitrogen-containing heterocyclic compound is a compound represented by the formula: Cz-L-Ar (1) [in the formula, Cz is a group represented by formula (2): (in the formula, Z is a single bond, etc., R²² and R^27} are each electron-withdrawing groups, R²³ and R²⁶ are each electron-donating groups, R²¹, R²⁴, R²⁵, and R²⁸ are each a hydrogen atom, an electron-withdrawing group, or an electron-donating group, and the wavy line indicates the bonding site with L), L is a single bond or an optionally substituted phenylene group, Ar is a group selected from the group consisting of aryl groups and heteroaryl groups, and said group may have at least one substituent selected from optionally substituted N,N-diarylamino groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups, and optionally substituted heteroaryl groups (however, Ar is not a group represented by formula (2)].

Description

Nitrogen-containing heterocyclic compounds and their use

The nitrogen-containing heterocyclic compound and the technology related to its use are disclosed.

A search for light emitting materials for organic light emitting elements such as organic light emitting diodes (OLEDs) is being conducted. As the light emitting material, it is required that various characteristics such as light emitting color (for example, light emitting maximum wavelength, full width at half maximum), light emitting efficiency, and durability are preferable. Among the light emitting materials for OLED, compounds showing Thermally Activated Delayed Fluorescence (TADF) show high luminous efficiency while being pure organic substances, and are expected as next-generation light emitting materials.

As a TADF material, for example, Patent Document 1 describes the following formula:

(In the formula, Y is a cyano group or a trifluoromethyl group.)
The compounds represented by are described. Further, in Patent Document 2, the following formula:

The compounds represented by are described.

International Publication No. 2018/0479848 JP-A-2017-103440

The compounds described in Patent Documents 1 and 2 are useful as TADF materials, but there is room for improvement in terms of luminous efficiency and durability. A main object of the present invention is to provide a nitrogen-containing heterocyclic compound having excellent luminous efficiency and durability and a technique relating to its use.

As a result of diligent studies to solve the above problems, the present inventors have found that the luminous efficiency and durability can be improved by adopting the structure represented by the following formula (1) as the structure of the compound. :
Cz-L-Ar (1)
[During the ceremony,
Cz is calculated by the following equation (2):

(During the ceremony,
Z is absent, single bond, -C (R ^29a ) (R ^29b )-, -O-, -S-, or -N (R ^29c )-.
R ²² and R ²⁷ are electron-attracting groups, respectively, and
R ²³ and R ²⁶ are electron-donating groups, respectively.
R ²¹ , R ²⁴ , R ²⁵ , R ²⁸ , R ^29a , R ^29b , and R ^29c are hydrogen atoms, electron attracting groups, or electron donating groups, respectively.
The wavy line indicates the binding site with L)
It is a group represented by
L is a phenylene group which may have a single bond or a substituent, and is a phenylene group.
Ar is a group selected from the group consisting of an aryl group and a heteroaryl group, and the group may have an N, N-diarylamino group or a substituent which may have a substituent. It may have at least one substituent selected from a cycloalkyl group, an aryl group which may have a substituent, and a heteroaryl group which may have a substituent (where Ar is. , Not a group represented by equation (2))]
The present invention has been further studied and completed based on this finding.

The present invention includes the following aspects.
Item 1.
Compound represented by the following formula (1):
Cz-L-Ar (1)
[During the ceremony,
Cz is calculated by the following equation (2):

(During the ceremony,
Z is absent, single bond, -C (R ^29a ) (R ^29b )-, -O-, -S-, or -N (R ^29c )-.
R ²² and R ²⁷ are electron-attracting groups, respectively, and
R ²³ and R ²⁶ are electron-donating groups, respectively.
R ²¹ , R ²⁴ , R ²⁵ , R ²⁸ , R ^29a , R ^29b , and R ^29c are hydrogen atoms, electron attracting groups, or electron donating groups, respectively.
The wavy line indicates the binding site with L)
It is a group represented by
L is a phenylene group which may have a single bond or a substituent, and is a phenylene group.
Ar is a group selected from the group consisting of an aryl group and a heteroaryl group, and the group may have an N, N-diarylamino group or a substituent which may have a substituent. It may have at least one substituent selected from a cycloalkyl group, an aryl group which may have a substituent, and a heteroaryl group which may have a substituent (where Ar is. , Not a group represented by equation (2))].
Item 2.
Ar is a group selected from the group consisting of a phenyl group, a fused bi to hexacyclic aryl group, and a nitrogen-containing heteroaryl group, and the group may have a substituent N, N-diaryl. At least one substituent selected from an amino group, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, and a heteroaryl group which may have a substituent. (However, Ar is not a group represented by the formula (2)), the compound according to Item 1.
Item 3.
Ar is the following formula (3):

(During the ceremony,
X ³¹ to X ³⁵ are -N = or -C (R ³ ) =, respectively.
R ³ is a hydrogen atom, an N, N-diarylamino group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or It is a heteroaryl group that may have a substituent and
The two R ³ which may be present in a positional relationship ortho to each other, may form an aromatic ring bonded to each other, the aromatic ring may have a substituent N, N-diarylamino group Has at least one substituent selected from a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, and a heteroaryl group which may have a substituent. You may be
The wavy line indicates the binding site with L)
Item 2. The compound according to Item 1 or 2, which is a group represented by.
Item 4.
The groups represented by the formula (3) are the following formulas (3-1) to (3-4):

(During the ceremony,
R ³¹¹ and R ³¹² , R ³²¹ to R ³²³ , R ³³¹ to R ³³⁶ , and R ³⁴¹ to R ³⁴⁶ , respectively, have a hydrogen atom and an N, N-diarylamino group and a substituent which may have a substituent. A cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.
The wavy line indicates the binding site with L)
Item 3. The compound according to Item 3, which is a group represented by any of the above.
Item 5.
Item 3 or 4 in which L is a phenylene group which may have at least one substituent selected from the group consisting of a group represented by the formula (2) and a group represented by the formula (3). The compound described in.
Item 6.
Item 2. The compound according to any one of Items 1 to 5, wherein Z is a single bond.
Item 7.
Item 6. The compound according to any one of Items 1 to 6, wherein R ²² and R ^{27 are perfluoroalkyl groups or cyano groups, respectively.}
Item 8.
R ²³ and R ²⁶ each have an alkyl group, an alkoxy group, a trialkylsilyl group, an N, N-diarylamino group which may have a substituent, a cycloalkyl group which may have a substituent, and the like. Item 2. The compound according to any one of Items 1 to 7, which is an aryl group which may have a substituent or a heteroaryl group which may have a substituent.
Item 9.
R ²¹ , R ²⁴ , R ²⁵ , and R ²⁸ are hydrogen atoms, or R ²¹ and R ²⁸ are electron donating groups, respectively, and R ²⁴ and R ²⁵ are electron attracting groups, respectively. Is,
Item 2. The compound according to any one of Items 1 to 8.
Item 10.
Compound represented by the following formula (4):

[During the ceremony,
X ⁴¹ to X ⁴³ are -N = or -C (R ⁴⁴ ) =, respectively.
R ⁴¹ to R ⁴⁴ may have a hydrogen atom, an N, N-diarylamino group which may have a substituent, a cycloalkyl group which may have a substituent, and a substituent, respectively. A good aryl group or a heteroaryl group which may have a substituent (provided ^{that at least one of R 41} to R ⁴³ is a group represented by the formula (2))];
Compound represented by the following formula (5):

[During the ceremony,
X ⁵¹ to X ⁵³ are -N = or -C (R ⁵⁸ ) =, respectively.
R ⁵¹ , R ⁵² , and R ⁵⁸ each have a hydrogen atom, an N, N-diarylamino group which may have a substituent, a cycloalkyl group which may have a substituent, and a substituent, respectively. It is an aryl group which may have a substituent or a heteroaryl group which may have a substituent.
Each of R ⁵³ to R ⁵⁷ is a hydrogen atom or a group represented by the formula (2) (however ^{, at least one of R 53} to R ⁵⁷ is a group represented by the formula (2))]. ;
Compound represented by the following formula (6):

[During the ceremony,
X ⁶¹ to X ⁶⁷ are -N = or -C (R ⁶⁶ ) =, respectively.
R ⁶¹ to R ⁶⁵ are hydrogen atoms or groups represented by the formula (2), respectively (however ^{, at least one of R 61} to R ⁶⁵ is a group represented by the formula (2)).
R ⁶⁶ is a hydrogen atom, an N, N-diarylamino group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or It is a heteroaryl group that may have a substituent];
Compound represented by the following formula (7):

[During the ceremony,
X ⁷¹ to X ⁷⁶ are -N = or -C (R ⁷⁹ ) =, respectively.
R ⁷¹ to R ⁷⁴ and R ⁷⁹ each have a hydrogen atom, an N, N-diarylamino group which may have a substituent, a cycloalkyl group which may have a substituent, and a substituent, respectively. It is an aryl group that may be present, or a heteroaryl group that may have a substituent, and is
R ⁷⁵ to R ⁷⁸ are hydrogen atoms or groups represented by the formula (2) (provided ^{that at least one of R 75} to R ⁷⁸ is a group represented by the formula (2))]; Compound represented by the following formula (8):

[During the ceremony,
X ⁸¹ to X ⁸⁶ are −N = or −C (R ⁸⁹ ) =, respectively.
R ⁸¹ to R ⁸⁴ and R ⁸⁹ each have a hydrogen atom, an N, N-diarylamino group which may have a substituent, a cycloalkyl group which may have a substituent, and a substituent, respectively. It is an aryl group that may be present, or a heteroaryl group that may have a substituent, and is
R ⁸⁵ to R ⁸⁸ are hydrogen atoms or groups represented by the formula (2) (however ^{, at least one of R 85} to R ⁸⁸ is a group represented by the formula (2))].
Item 2. The compound according to Item 1, which is selected from the group consisting of.
Item 11.
A delayed fluorescent material containing the compound according to any one of Items 1 to 10.
Item 12.
An organic light emitting device containing the compound according to any one of Items 1 to 10.
Item 13.
Item 2. The organic light emitting element according to Item 12, which is an organic EL element.
Item 14.
The following formula (9):

(During the ceremony,
R ⁹¹ and R ⁹⁴ are perfluoroalkyl groups or cyano groups, respectively.
R ⁹² and R ⁹³ are an alkyl group, an alkoxy group, a trialkylsilyl group, an N, N-diarylamino group which may have a substituent, and a cycloalkyl group which may have a substituent, respectively. An aryl group which may have a substituent or a heteroaryl group which may have a substituent.
Z ⁹ is absent, single bond, -C (R ⁹⁵ ) (R ⁹⁶ )-, -O-, -S-, or -N (R ⁹⁷ )-, and
R ⁹⁵ to R ⁹⁷ are a hydrogen atom, an electron attracting group, or an electron donating group, respectively)
Compounds represented by (where Z ⁹ is absent, R ⁹¹ and R ⁹⁴ are trifluoromethyl groups, R ⁹² and R ⁹³ are methoxy groups, and Z ⁹ is absent. , R ⁹¹ and R ⁹⁴ are cyano groups, and R ⁹² and R ⁹³ are phenyl groups).

According to the present invention, a nitrogen-containing heterocyclic compound having excellent luminous efficiency and durability and a technique related to its use are provided.

^{FIG. 1 is a diagram showing a 1} H NMR spectrum of 3,6-dibromo-2,7-bis (trifluoromethyl) -9H-carbazole. ^{FIG. 2 is a diagram showing a 19} F NMR spectrum of 3,6-dibromo-2,7-bis (trifluoromethyl) -9H-carbazole. FIG. 3 is ^{a diagram showing a 1} H NMR spectrum of intermediate D1. FIG. 4 is ^{a diagram showing a 19} F NMR spectrum of intermediate D1. FIG. 5 is ^{a diagram showing a 1} H NMR spectrum of intermediate D2. FIG. 6 is ^{a diagram showing a 19} F NMR spectrum of intermediate D2. FIG. 7 is ^{a diagram showing a 1} H NMR spectrum of intermediate D3. FIG. 8 is ^{a diagram showing a 19} F NMR spectrum of intermediate D3. FIG. 9 is ^{a diagram showing a 1} H NMR spectrum of intermediate D5. FIG. 10 is ^{a diagram showing a 19} F NMR spectrum of Intermediate D5. FIG. 11 is ^{a diagram showing a 1} H NMR spectrum of Intermediate A2. FIG. 12 is ^{a diagram showing a 1} H NMR spectrum of Intermediate A3. FIG. 13 is ^{a diagram showing a 19} F NMR spectrum of Intermediate A3. FIG. 14 is ^{a diagram showing a 1} H NMR spectrum of Intermediate A4. FIG. 15 is ^{a diagram showing a 19} F NMR spectrum of Intermediate A4. FIG. 16 is ^{a diagram showing a 1} H NMR spectrum of Intermediate A5. FIG. 17 is ^{a diagram showing a 19} F NMR spectrum of Intermediate A5. FIG. 18 is ^{a diagram showing a 1} H NMR spectrum of Intermediate A6. FIG. 19 is ^{a diagram showing a 19} F NMR spectrum of Intermediate A6. FIG. 20 is ^{a diagram showing a 1} H NMR spectrum of Intermediate A7. FIG. 21 is ^{a diagram showing a 19} F NMR spectrum of Intermediate A7. FIG. 22 is ^{a diagram showing a 1} H NMR spectrum of Intermediate A8. FIG. 23 is ^{a diagram showing a 1} H NMR spectrum of Intermediate A9. FIG. 24 is ^{a diagram showing a 19} F NMR spectrum of Intermediate A9. FIG. 25 is ^{a diagram showing a 1} H NMR spectrum of Example 1. FIG. 26 is ^{a diagram showing a 19} F NMR spectrum of Example 1. FIG. 27 is ^{a diagram showing a 1} H NMR spectrum of Example 2. FIG. 28 is ^{a diagram showing a 19} F NMR spectrum of Example 2. FIG. 29 is ^{a diagram showing a 1} H NMR spectrum of Example 3. FIG. 30 is ^{a diagram showing a 19} F NMR spectrum of Example 3. FIG. 31 is ^{a diagram showing a 1} H NMR spectrum of Example 4. FIG. 32 is ^{a diagram showing a 19} F NMR spectrum of Example 4. FIG. 33 is ^{a diagram showing a 1} H NMR spectrum of Comparative Example 5. FIG. 34 is ^{a diagram showing a 1} H NMR spectrum of Comparative Example 6. FIG. 35 is ^{a diagram showing a 19} F NMR spectrum of Comparative Example 6. FIG. 36 is ^{a diagram showing a 1} H NMR spectrum of Comparative Example 10. FIG. 37 is ^{a diagram showing a 13} C NMR spectrum of Comparative Example 10. FIG. 38 is ^{a diagram showing a 1} H NMR spectrum of Comparative Example 11. FIG. 39 is ^{a diagram showing a 19} F NMR spectrum of Comparative Example 11. FIG. 40 is ^{a diagram showing a 1} H NMR spectrum of Comparative Example 13. FIG. 41 is ^{a diagram showing a 19} F NMR spectrum of Comparative Example 13.

<Definition>
In the present specification, unless otherwise specified, "halogen atom" is used in the sense of including a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

In the present specification, unless otherwise specified, the "alkyl group" means a linear or branched saturated hydrocarbon group, and specifically, for example, a methyl group, an ethyl group, or a propyl group (n). -Propyl group, isopropyl group), butyl group (n-butyl group, isobutyl group, sec-butyl group, tert-butyl group), pentyl group, hexyl group and other C _1-20 alkyl groups.

In the present specification, unless otherwise specified, the "perfluoroalkyl group" means a group in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms, and specifically, for example, a trifluoromethyl group. , Pentafluoroethyl group, heptafluoropropyl group (heptafluoro n-propyl group or heptafluoro i-propyl group) and other perfluoroC _1-12 alkyl groups.

In the present specification, unless otherwise specified, the "alkoxy group" means a group in which an oxygen atom is bonded to the terminal of the alkyl group, and specifically, for example, a methoxy group, an ethoxy group, or a propoxy group (n). _{-C 1-12} alkoxy groups such as propoxy group (propoxy group, isopropoxy group), butoxy group (n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group) can be mentioned.

In the present specification, unless otherwise specified, the "alkylsulfanyl group" means a group in which a sulfur atom is bonded to the terminal of the alkyl group, and specifically, for example, a methylsulfanyl group, an ethylsulfanyl group, or a propyl. _{Examples thereof include a C 1-12} alkyl sulfanyl group such as a sulfanyl group (n-propyl sulfanyl group, isopropyl sulfanyl group) and a butyl sulfanyl group.

In the present specification, unless otherwise specified, the "alkylcarbonyl group" means a group in which a carbonyl group (-C (= O)-) is bonded to the end of the alkyl group, and specifically, for example, for example. _{Examples thereof include (C 1-12} alkyl) carbonyl groups such as methylcarbonyl group, ethylcarbonyl group, propylcarbonyl group (n-propylcarbonyl group, isopropylcarbonyl group) and butylcarbonyl group.

In the present specification, unless otherwise specified, the "alkylsulfonyl group" means a group in which a sulfonyl group (-S (= O) _2- ) is bonded to the end of the alkyl group, and specifically, for example. , Methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group (n-propylsulfonyl group, isopropylsulfonyl group), butylsulfonyl group and other C _1-12 alkylsulfonyl groups.

In the present specification, unless otherwise specified, the "cycloalkyl group" includes a cycloC _5-20 alkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.

In the present specification, unless otherwise specified, the "trialkylsilyl group" means a group in which the three alkyl groups are bonded to a silicon atom, and specifically, for example, a trimethylsilyl group and a triethylsilyl group. _{Examples thereof include a tri-C 1-4} alkylsilyl group such as a triisopropylsilyl group and a tert-butyldimethylsilyl group.

In the present specification, unless otherwise specified, "aromatic ring" is used in the sense of including an arene ring and a heteroarene ring.

The number of carbon atoms in the arene ring is not particularly limited, but is, for example, 6 to 40, preferably 6 to 30, more preferably 6 to 28, and even more preferably 6 to 26. The arene ring is preferably a benzene ring or a fused ring having a structure in which a plurality of benzene rings are condensed. Examples of the arene ring include a benzene ring, a naphthalene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, a fluoranthene ring, a tetracene ring, a tetraphen ring, a chrysene ring, a triphenylene ring, a pyrene ring, a benzopyrene ring, a perylene ring, and a coronene ring. Examples include a coronene ring, a phenalene ring, and a trianglene ring.

The number of ring-constituting atoms in the heteroarene ring is not particularly limited, but is, for example, 5 to 40 members. The heteroarene ring may be a monocyclic type or a polycyclic type (for example, a two- to four-ring type). The heteroarene ring is preferably a heteroarene ring containing at least one heteroatom selected from an oxygen atom, a sulfur atom, and a nitrogen atom as a ring-constituting atom. Examples of the heteroarene ring include an oxygen-containing heteroarene ring (eg, furan ring, benzofuran ring, dibenzo [b, d] furan ring) and a sulfur-containing heteroarene ring (eg, thiophene ring, benzothiophene ring, dibenzo [b]. , D] Thiophen ring), nitrogen-containing heteroarene ring (eg, pyrrole ring, pyrazole ring, imidazole ring, 1,2,3-triazole ring, 1,2,4-triazole ring, pyridine ring, pyridazine ring, pyrimidine ring) , Pyrazine ring, 1,3,5-triazole ring, indole ring, indazole ring, benzimidazole ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phthalazine ring, naphthylidine ring, purine ring, acrydin ring, 9,10 -Dihydroaclydin ring, phenazine ring, 5,10-dihydrophenazine ring, phenanthridin ring, phenanthroline ring, acenaft [1,2-b] pyrazine ring), oxygen and nitrogen-containing heteroarene ring (eg, oxazole ring, iso) Oxazole ring, benzoxazole ring, phenoxazine ring), sulfur and nitrogen-containing heteroarene ring (eg, thiazole ring, isothiazole ring, benzothiazole ring, phenothiazine ring).

The aryl group is a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring (arene ring) in the aromatic ring. The aryl group may be a monocyclic aryl group or a fused cyclic aryl group (for example, a fused bi to hexacyclic aryl group). Examples of the monocyclic aryl group include a phenyl group. Examples of the fused cyclic aryl group include a naphthyl group, a fluorenyl group, an anthrasenyl group, a triphenylenyl group, and a pyrenyl group. As the aryl group, a C _6-18 aryl group is preferable.

The heteroaryl group is a group obtained by removing one hydrogen atom from the aromatic heterocycle (heteroarene ring) in the aromatic ring. The heteroaryl group may be a monocyclic heteroaryl group (eg, a 5- or 6-membered monocyclic heteroaryl group) or a fused cyclic heteroaryl group (eg, a fused 2- to 6-cyclic aryl group). May be. Examples of the monocyclic heteroaryl group include a monocyclic oxygen-containing heteroaryl group such as a frill group; a monocyclic sulfur-containing heteroaryl group such as a thienyl group; a pyrrolyl group, a pyrazolyl group, an imidazolyl group, a triazil group and a pyridyl group. Examples thereof include monocyclic nitrogen-containing heteroaryl groups such as a pyridazyl group, a pyrimidyl group, a pyrazil group and a triazinyl group. Examples of the fused cyclic heteroaryl group include a fused cyclic oxygen-containing heteroaryl group such as a benzofuryl group and a dibenzofuryl group; a fused cyclic sulfur-containing heteroaryl group such as a benzothienyl group and a dibenzothienyl group; an indrill group and a quinolyl group. Fused cyclic nitrogen-containing heteroaryl groups such as groups, isoquinolyl groups, carbazolyl groups, acrizyl groups, 9,10-dihydroacrylidyl groups, phenadyl groups, 5,10-dihydrophenadyl groups; fused cyclic oxygen such as phenoxazyl groups. And nitrogen-containing heteroaryl groups; fused cyclic sulfur such as phenothiazil groups and nitrogen-containing heteroaryl groups can be mentioned.

In the present specification, unless otherwise specified, the "electron donating group (donor group)" represents a group in which Hammett's σp is negative. Hansch, C.et.al., Chem.Rev., 91,165-195 (1991) can be referred to for a description of Hammett's σp and the numerical values of each group. Examples of the electron donating group include an alkyl group such as a methyl group, an isopropyl group and a tertiary butyl group, a cycloalkyl group such as a cyclohexyl group, a phenyl group, a naphthyl group, an anthracenyl group, a triphenylenyl group, a pyrenyl group and a fluorenyl group. Aryl group, alkoxy group such as methoxy group, alkylsulfanyl group such as methionyl group, trialkylsilyl group such as trimethylsilyl group, pyridyl group, imidazolyl group, pyrazolyl group, oxazolyl group, thiazolyl group, indolyl group, pyrrolyl group, quinolyl. Heteroaryl group, N , N, N-diarylamino group such as N-diphenylamino group.

In the present specification, unless otherwise specified, the "electron-attracting group (acceptor group)" means a group other than an electron-donating group, for example, an alkylcarbonyl group (acyl group), an alkylsulfonyl group, and the like. Examples thereof include a perfluoroalkyl group, a cyano group and a nitro group.

<Compound>
In one embodiment, the compound of the present invention is preferably a compound represented by the following formula (1):
Cz-L-Ar (1)
[During the ceremony,
Cz is calculated by the following equation (2):

(During the ceremony,
Z is absent, single bond, -C (R ^29a ) (R ^29b )-, -O-, -S-, or -N (R ^29c )-.
R ²² and R ²⁷ are electron-attracting groups, respectively, and
R ²³ and R ²⁶ are electron-donating groups, respectively.
R ²¹ , R ²⁴ , R ²⁵ , R ²⁸ , R ^29a , R ^29b , and R ^29c are hydrogen atoms, electron attracting groups, or electron donating groups, respectively.
The wavy line indicates the binding site with L)
It is a group represented by
L is a phenylene group which may have a single bond or a substituent, and is a phenylene group.
Ar is a group selected from the group consisting of an aryl group and a heteroaryl group, and the group may have an N, N-diarylamino group or a substituent which may have a substituent. It may have at least one substituent selected from a cycloalkyl group, an aryl group which may have a substituent, and a heteroaryl group which may have a substituent (where Ar is. , Not a group represented by equation (2))].

Cz (Equation (2))
Z is preferably a single bond, -C (R ^29a ) (R ^29b )-, -O-, -S-, or -N (R ^29c )-, and more preferably a single bond.

In the formula (2), the present inventors consider that when R ²² and R ²⁷ are electron attracting groups and R ²³ and R ²⁶ are electron donating groups, R ²² and R ²⁷ are electron seeking groups. Emission compared to the case where R ²³ and R ²⁶ are hydrogen atoms and where R ²² and R ²⁷ are hydrogen atoms and R ²³ and R ^{26 are electron donating groups.} We have found that the half-price range of the peak can be further narrowed.

If R ²² , R ²⁷ , and R ²¹ , R ²⁴ , R ²⁵ , R ²⁸ , and R ^29a to R ^29c are electron-attracting groups, the electron-attracting groups are, respectively.
It is preferably a perfluoroalkyl group or a cyano group.
More preferably, it is a perfluoroC _1-4 alkyl group or a cyano group.
More preferably, it is a perfluoroC _1-3 alkyl group or a cyano group.
Even more preferably, it is a perfluoroC _1-2 alkyl group or a cyano group.
Particularly preferably, it is a trifluoromethyl group or a cyano group.

If R ²³ , R ²⁶ , and R ²¹ , R ²⁴ , R ²⁵ , R ²⁸ , and R ^29a to R ^29c are electron-donating groups, the electron-donating groups are, respectively.
It preferably has an alkyl group, an alkoxy group, a trialkylsilyl group, an N, N-diarylamino group which may have a substituent, a cycloalkyl group which may have a substituent, or a substituent. It may have an aryl group or a heteroaryl group which may have a substituent, and more preferably a C _1-6 alkyl group, a C _1-6 alkoxy group, a tri C _1-6 alkylsilyl group and a substituent. May have N, N-di C _6-18 arylamino group, may have substituent C _5-12 cycloalkyl group, may have substituent C _6-18 aryl A 5- or 6-membered monocyclic heteroaryl group which may have a group, a substituent, or a fused 2- to tetracyclic heteroaryl group which may have a substituent.
More preferably, it may have a C _1-4 alkyl group, a C _1-4 alkoxy group, a tri C _1-4 alkylsilyl group, a substituent N, N-di C _6-14 arylamino group, C _{5 A -7} cycloalkyl group, a C _6-14 aryl group, a 5- or 6-membered monocyclic nitrogen-containing heteroaryl group which may have a substituent, or a condensed 2-4 which may have a substituent. It is a cyclic nitrogen-containing heteroaryl group.
The substituent arbitrarily contained in the N, N-diarylamino group is preferably an electron attracting group and an electron donating group. The cycloalkyl group, the aryl group, and the substituent optionally contained in the heteroaryl group are preferably an aryl group or a heteroaryl group, more preferably an aryl group, and further preferably a C _6-12 aryl group. It is particularly preferably a C _6-10 aryl group. It is also preferable that the substituent arbitrarily contained in the heteroaryl group is an electron-attracting group and an electron-donating group. The number of the substituents is, for example, 0, 1, 2, 3, or 4.
The electron donating group is also preferably a group represented by the formula (2).

As a combination of ^{R 21} , R ²⁴ , R ²⁵ , and R ^28,
R ²¹ , R ²⁴ , R ²⁵ , and R ²⁸ are combinations of hydrogen atoms; or R ²¹ and R ²⁸ are electron donating groups, respectively, and R ²⁴ and R ²⁵ are electron attracting groups, respectively. The base combination is preferred.

The group represented by the formula (2) is preferably a group selected from the following group:

(In the formula, Me is a methyl group, i-Pr is an isopropyl group, t-Bu is a tertiary butyl group, Ph is a phenyl group, and a wavy line indicates a binding site with L).

Ar
Ar is
It is preferably a group selected from an aryl group and a heteroaryl group (however, it is not a group represented by the formula (2)).
More preferably, it is a _{group selected from a C 6-18} aryl group, a 5-membered or 6-membered monocyclic heteroaryl group, and a fused 2- to tetracyclic heteroaryl group (however, it is represented by the formula (2)). Not the basis),
More preferably, it is a _{group selected from a C 6-16} aryl group, a 5-membered or 6-membered monocyclic nitrogen-containing heteroaryl group, and a condensed 2- to tetracyclic nitrogen-containing heteroaryl group (however, the formula (2)). It is not a group represented by).
These groups may have an N, N-diarylamino group (for example, a group represented by the formula (2) in which Z is absent), which may have a substituent, and a cyclo which may have a substituent. An alkyl group (preferably a C _5-12 cycloalkyl group), an _{aryl group optionally} having a substituent (preferably a C 6-12 aryl group), and a heteroaryl group optionally having a substituent (preferably a C 5-12 cycloalkyl group). Preferably at least one selected from a 5- or 6-membered monocyclic heteroaryl group or a fused 2- to tetracyclic heteroaryl group (eg, a group represented by formula (2) in which Z is other than absent). It may have a substituent of.
The substituent arbitrarily contained in the cycloalkyl group, the aryl group, and the heteroaryl group is not particularly limited, but is, for example, an aryl group (for example, C _6-12 aryl group) or a heteroaryl group (for example, 5 members). Alternatively, it may be a 6-membered monocyclic heteroaryl group, a fused bi to tetracyclic heteroaryl group), or a group represented by the formula (2).

Ar is preferably a group represented by the following formula (3):

(During the ceremony,
X ³¹ to X ³⁵ are -N = or -C (R ³ ) =, respectively.
R ³ is a hydrogen atom, an N, N-diarylamino group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or It is a heteroaryl group that may have a substituent and
The two R ³ which may be present in a positional relationship ortho to each other, may form an aromatic ring bonded to each other, the aromatic ring may have a substituent N, N-diarylamino group Has at least one substituent selected from a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, and a heteroaryl group which may have a substituent. You may be
The wavy line indicates the binding site with L).

In the formula (3), as a combination of ^{X 31} to X ^35,
A combination in which X ³¹ , X ³³ , and X ³⁵ are -N = and X ³² and X ³⁴ are -C (R ³ ) =;
A combination in which X ³¹ and X ³⁵ are -N = and X ³² to X ³⁴ are -C (R ³ ) =; or a combination in which X ³¹ to X ³⁵ are -C (R ³ ) = is preferable.

R ³ is preferably a hydrogen atom, an N, N-di C _6-12 arylamino group which may have a substituent (for example, a group represented by the formula (2) in which Z is absent), a substituent. A C _5-12 cycloalkyl group which may have a _{group, a C 6-12} aryl group which may have a substituent, and a 5-membered or 6-membered monocyclic hetero which may have a substituent. It is a fused bi to tetracyclic heteroaryl group which may have an aryl group or a substituent (for example, a group represented by the formula (2) in which Z is other than absent). Examples of the substituent include an aryl group (for example, C _6-12 aryl group) or a heteroaryl group (for example, a 5-membered or 6-membered monocyclic heteroaryl group, a condensed 2- to 4-cyclic heteroaryl group). It may be a group represented by the formula (2).

The group represented by the formula (3), when forming the aromatic ring, e.g., represented by the following formula (3a) or (3b) bonded to each other two R ³ which may be present in a positional relationship ortho to one another May be a base:

(In the equation, X ³⁶ to X ³⁹ are -N = or -C (R ³ ) = ^{, respectively, and X 31} to X ³³ , X ³⁵ , and R ³ are the same as described above).

In the formula (3a), the combination of ^{X 31} to X ³³ and X ³⁶ to X ^{39 is}
A combination in which X ³¹ to X ³³ are -C (R ³ ) = and X ³⁶ to X ³⁹ are -N = or -C (R ³ ) = is preferable.
A combination in which X ³¹ to X ³³ and X ³⁶ to X ³⁸ are -C (R ³ ) = and X ³⁹ is -N =; or X ³¹ to X ³³ and X ³⁶ to X ³⁹ are -C (R ^3). The combination of) = is more preferable.

In formula (3b), ^{the combination of X 31} , X ³² , and X ³⁵ to X ³⁹ is as a combination.
A combination in which X ³¹ , X ³² , and X ³⁵ are -C (R ³ ) = and X ³⁶ to X ³⁹ are -N = or -C (R ³ ) = is preferable.
A combination in which X ³¹ , X ³² and X ³⁵ to X ³⁸ are -C (R ³ ) = and X ³⁹ is -N =; or X ³¹ , X ³² and X ³⁵ to X ³⁹ are -C (R ^3). The combination of) = is more preferable.

The group represented by the formula (3) is preferably a group represented by any of the following formulas (3-1) to (3-4):

(In the formula, R ³¹¹ , R ³¹² , R ³²¹ to R ³²³ , R ³³¹ to R ³³⁶ , and R ³⁴¹ to R ³⁴⁶ , respectively, may have a hydrogen atom and a substituent N, N-diarylamino. A group, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.
The wavy line indicates the binding site with L).

^{R 311, R 312, R 321} ~ R 323, R 331 ~ R 336, and ^R 341 ^{~ R 346} are each preferably a hydrogen atom, which may have a substituent N, N-di _{C 6- A} 12arylamino group (for example, a group represented by the formula (2) in which Z is absent), a C _5-12 cycloalkyl group which may have a substituent, and a C which may have a substituent. _{A 6-12} aryl group, a 5- or 6-membered monocyclic heteroaryl group which may have a substituent, and a fused 2- to tetracyclic heteroaryl group which may have a substituent (for example, Z is not). It is a group represented by the formula (2) that is other than existence). Examples of the substituent include an aryl group (for example, C _6-12 aryl group) or a heteroaryl group (for example, a 5-membered or 6-membered monocyclic heteroaryl group, a condensed 2- to 4-cyclic heteroaryl group). It may be a group represented by the formula (2).

L
When L is a phenylene group which may have a substituent, the phenylene group may be any of 1,2-phenylene group, 1,3-phenylene group, and 1,4-phenylene group.
The substituent is
Preferably, it is an N, N-diarylamino group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.
More preferably, it may have an N, N-di C _6-18 arylamino group which may have _{a substituent, a C 6-18} aryl group which may have a substituent, and a substituent. A fused 2- to tetracyclic heteroaryl group which may have a 5- or 6-membered monocyclic heteroaryl group or a substituent, and is a fused two- to tetracyclic heteroaryl group.
More preferably, it is a group represented by the formula (2) or a group represented by the formula (3).
The number of the substituents is, for example, 0, 1, 2, 3, or 4.

In one embodiment, the compound represented by the formula (1) is preferably a compound in which L is a single bond, and Ar is substituted with one or more groups represented by the formula (2) that can be replaced by one or more. It is more preferable that the compound is a compound represented by the following formula (4):

[During the ceremony,
X ⁴¹ to X ⁴³ are -N = or -C (R ⁴⁴ ) =, respectively.
R ⁴¹ to R ⁴⁴ may have a hydrogen atom, an N, N-diarylamino group which may have a substituent, a cycloalkyl group which may have a substituent, and a substituent, respectively. A good aryl group or a heteroaryl group which may have a substituent (provided ^{that at least one of R 41} to R ⁴³ is a group represented by the formula (2)).

As a combination of ^{X 41} to X ^43,
A ^{combination in which X 41} to X ⁴³ are -N =; or a combination ^{in which any two of X 41} to X ⁴³ is -N = and the remaining one is -C (R ⁴⁴ ) = is preferable.

R ⁴¹ to R ⁴⁴ are represented by the formula (2) in which Z is absent, for example _{, N, N-di C 6-12} arylamino groups which may have a hydrogen atom and a substituent, respectively. Group), C _5-12 cycloalkyl group which may have _{a substituent, C 6-12} aryl group which may have a substituent, 5 members or 6 which may have a substituent. It is a member monocyclic heteroaryl group or a fused bi to tetracyclic heteroaryl group which may have a substituent (for example, a group represented by the formula (2) in which Z is other than absent). Examples of the substituent include an aryl group (for example, C _6-12 aryl group) or a heteroaryl group (for example, a 5-membered or 6-membered monocyclic heteroaryl group, a condensed 2- to 4-cyclic heteroaryl group). It may be a group represented by the formula (2).

The compound represented by the formula (4) is preferably a compound represented by the following formula (4-1) or (4-2):

(In the formula, each Cz is the same or different from each other and is a group represented by the formula (2), and X ⁴¹ to X ⁴³ and R ⁴¹ are the same as described above).

In one embodiment, the compound represented by the formula (1) is preferably a compound in which L is a phenylene group which may have a substituent, and has one or more Ars on the benzene ring and one or more formulas (1 or more). A compound in which the group represented by 2) is substituted (the total number of Ars and the number of substitutions of the groups represented by the formula (2) is 2 or more and 6 or less) is more preferable, and one Ar and one Ar in the benzene ring and A compound in which one or more and five or less groups represented by the formula (2) are substituted is more preferable, and a compound represented by the following formula (5) is particularly preferable:

[During the ceremony,
X ⁵¹ to X ⁵³ are -N = or -C (R ⁵⁸ ) =, respectively.
R ⁵¹ , R ⁵² , and R ⁵⁸ each have a hydrogen atom, an N, N-diarylamino group which may have a substituent, a cycloalkyl group which may have a substituent, and a substituent, respectively. It is an aryl group which may have a substituent or a heteroaryl group which may have a substituent.
Each of R ⁵³ to R ⁵⁷ is a hydrogen atom or a group represented by the formula (2) (however ^{, at least one of R 53} to R ⁵⁷ is a group represented by the formula (2))]. ..

As a combination of ^{X 51} to X ^53,
A ^{combination in which X 51} to X ⁵³ are -N =; or a combination in which X ⁵¹ is -C (R ⁵⁸ ) = and X ⁵² and X ⁵³ are -N = is preferable.

R ⁵¹ , R ⁵² , and R ⁵⁸ _{each preferably have an N, N-di C 6-12} arylamino group (eg, Z is absent), which may have a hydrogen atom and a substituent, respectively (eg, formula (2) in which Z is absent. ), C _5-12 cycloalkyl group which may have _{a substituent, C 6-12} aryl group which may have a substituent, and may have a substituent. A five- or six-membered monocyclic heteroaryl group or a fused two- to tetracyclic heteroaryl group which may have a substituent (for example, a group represented by the formula (2) in which Z is other than absent). Is. Examples of the substituent include an aryl group (for example, C _6-12 aryl group) or a heteroaryl group (for example, a 5-membered or 6-membered monocyclic heteroaryl group, a condensed 2- to 4-cyclic heteroaryl group). It may be a group represented by the formula (2).

The compound represented by the formula (5) is preferably a compound represented by any of the following formulas (5-1) to (5-14):

(In the formula, Cz is a group represented by the formula (2), and when a plurality of Cz exists, the plurality of Cz may be the same or different from each other, and X ⁵¹ to X ⁵³ , R ^51. , And R ⁵² are the same as above).

In one embodiment, the compound represented by the formula (1) is preferably a compound represented by the following formula (6):

[During the ceremony,
X ⁶¹ to X ⁶⁷ are -N = or -C (R ⁶⁶ ) =, respectively.
R ⁶¹ to R ⁶⁵ are hydrogen atoms or groups represented by the formula (2), respectively (however ^{, at least one of R 61} to R ⁶⁵ is a group represented by the formula (2)).
R ⁶⁶ is a hydrogen atom, an N, N-diarylamino group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or It is a heteroaryl group that may have a substituent].

As a combination of ^{X 61} to X ^67,
A combination in which X ⁶¹ to X ⁶⁵ and X ⁶⁷ are -C (R ⁶⁶ ) = and X ⁶⁶ is -N =; or a combination in which X ⁶¹ to X ⁶⁷ is -C (R ⁵⁸ ) = is preferred.

R ⁶⁶ is preferably a hydrogen atom, an N, N-di C _6-12 arylamino group which may have a substituent (for example, a group represented by the formula (2) in which Z is absent), a substituent. A C _5-12 cycloalkyl group which may have a _{group, a C 6-12} aryl group which may have a substituent, and a 5-membered or 6-membered monocyclic hetero which may have a substituent. A fused bi- to tetracyclic heteroaryl group which may have an aryl group or a substituent (for example, a group represented by the formula (2) in which Z is other than absent). Examples of the substituent include an aryl group (for example, C _6-12 aryl group) or a heteroaryl group (for example, a 5-membered or 6-membered monocyclic heteroaryl group, a condensed 2- to 4-cyclic heteroaryl group). It may be a group represented by the formula (2).

The compound represented by the formula (6) is preferably a compound represented by the following formula (6-1):

(In the formula, Cz is a group represented by the formula (2), and the two Cz may be the same or different from each other, and X ⁶¹ to X ⁶⁷ are the same as described above).

In one embodiment, the compound represented by the formula (1) is preferably a compound in which L is a phenylene group which may have a substituent, and has two Ars on the benzene ring and one or more and four or less. A compound in which the group represented by the formula (2) is substituted is more preferable, and a compound represented by the following formula (7) is further preferable:

[During the ceremony,
X ⁷¹ to X ⁷⁶ are -N = or -C (R ⁷⁹ ) =, respectively.
R ⁷¹ to R ⁷⁴ and R ⁷⁹ each have a hydrogen atom, an N, N-diarylamino group which may have a substituent, a cycloalkyl group which may have a substituent, and a substituent, respectively. It is an aryl group that may be present, or a heteroaryl group that may have a substituent, and is
R ⁷⁵ to R ⁷⁸ are hydrogen atoms or groups represented by the formula (2) (however ^{, at least one of R 75} to R ⁷⁸ is a group represented by the formula (2))].

As a combination of ^{X 71} to X ^76,
Combinations where X ⁷¹ to X ⁷⁶ are -N =; or combinations where X ⁷¹ , X ⁷³ , X ⁷⁴ , and X ⁷⁶ are -N = and X ⁷² and X ⁷⁵ are -C (R ⁷⁹ ) = preferable.

R ⁷¹ to R ⁷⁴ and R ⁷⁹ each preferably have a hydrogen atom and a substituent, respectively, N, N-di C _6-12 arylamino groups (for example, formula (2) in which Z is absent). Group represented by), C _5-12 cycloalkyl group which may have _{a substituent, C 6-12} aryl group which may have a substituent, and may have a substituent 5 A fused two- to tetracyclic heteroaryl group which may have a member or 6-membered monocyclic heteroaryl group or a substituent (for example, a group represented by the formula (2) in which Z is other than absent). be. Examples of the substituent include an aryl group (for example, C _6-12 aryl group) or a heteroaryl group (for example, a 5-membered or 6-membered monocyclic heteroaryl group, a condensed 2- to 4-cyclic heteroaryl group). It may be a group represented by the formula (2).

The compound represented by the formula (7) is preferably a compound represented by any of the following formulas (7-1) to (7-3):

(In the formula, Cz is a group represented by the formula (2), and when a plurality of Cz exists, the plurality of Cz may be the same or different from each other, and X ⁷¹ to X ⁷⁶ and R ^71. ~ R ⁷⁴ is the same as above).

In one embodiment, the compound represented by the formula (1) is preferably a compound represented by the following formula (8):

[During the ceremony,
X ⁸¹ to X ⁸⁶ are −N = or −C (R ⁸⁹ ) =, respectively.
R ⁸¹ to R ⁸⁴ and R ⁸⁹ each have a hydrogen atom, an N, N-diarylamino group which may have a substituent, a cycloalkyl group which may have a substituent, and a substituent, respectively. It is an aryl group that may be present, or a heteroaryl group that may have a substituent, and is
R ⁸⁵ to R ⁸⁸ are hydrogen atoms or groups represented by the formula (2) (provided ^{that at least one of R 85} to R ⁸⁸ is a group represented by the formula (2))].

As a combination of ^{X 81} to X ^86,
A ^{combination in which X 81} to X ⁸⁶ are -N =; or a combination in which X ⁸¹ , X ⁸³ , X ⁸⁴ , and X ⁸⁶ are -N = and X ⁸² and X ⁸⁵ are -C (R ⁸⁹ ) = preferable.

R ⁸¹ to R ⁸⁴ and R ⁸⁹ _{preferably have an N, N-diC 6-12} arylamino group which may have a hydrogen atom and a substituent, respectively (for example, formula (2) in which Z is absent). Group represented by), C _5-12 cycloalkyl group which may have _{a substituent, C 6-12} aryl group which may have a substituent, and may have a substituent 5 A fused two- to tetracyclic heteroaryl group which may have a member or 6-membered monocyclic heteroaryl group or a substituent (for example, a group represented by the formula (2) in which Z is other than absent). be. Examples of the substituent include an aryl group (for example, C _6-12 aryl group) or a heteroaryl group (for example, a 5-membered or 6-membered monocyclic heteroaryl group, a condensed 2- to 4-cyclic heteroaryl group). It may be a group represented by the formula (2).

The compound represented by the formula (8) is preferably a compound represented by any of the following formulas (8-1) to (8-6):

(In the formula, Cz is a group represented by the formula (2), and when a plurality of Cz exists, the plurality of Cz may be the same or different from each other, and X ⁸¹ to X ⁸⁶ and R ^81. ~ R ⁸⁴ is the same as above).

The half width of the emission peak of the compound of the present invention may be preferably 90 nm or less, more preferably 85 nm or less, further preferably 80 nm or less, or 10 nm or more. ^{The full width at half maximum can be determined by measuring the emission spectrum when a solution (concentration: 1 × 10-5} M) in which the compound of the present invention is dissolved is irradiated with excitation light at 340 nm at room temperature. In the emission spectrum, the spectrum width of half the peak top intensity is defined as the half width (FWHM, Full Width Half Maximum).

The luminous efficiency (PLQY) of the compound of the present invention is preferably 50% or more, more preferably 55% or more, still more preferably 60% or more. Luminous efficiency (PLQY) is a value when a solution (concentration: 1 × ^10-5 M) in which the compound of the present invention is dissolved is irradiated with excitation light at 340 nm at room temperature, and is an absolute PL quantum yield measuring device (for example). , Hamamatsu Photonics Quantaurus-QY C11347-01) can be used for measurement.

The HOMO level of the compound of the present invention may preferably be -5.0 eV or less or -5.5 eV or less, and is -7.0 eV or more, -6.5 eV or more, or -6.4 eV or more. May be good. Due to such a HOMO level, compatibility with peripheral materials such as host materials is excellent. The HOMO level can be measured using an atmospheric photoelectron spectrometer (for example, AC-3 manufactured by RIKEN Keiki Co., Ltd.).

From the viewpoint of luminous efficiency, the orientation parameter S of the compound of the present invention may be preferably 0.002 or more, 0.003 or more, 0.004 or more, or 0.005 or more, and is 0.05 or less. There may be. The orientation parameter S is in the range of 45 to 75 degrees (in 5 degree increments) using a spectroscopic ellipsometer (JA Woollam Japan product) by forming a single film (film thickness of about 30 nm) of the light emitting material on a bare silicon substrate. It can be calculated by performing spectrum measurement and fitting analysis of the obtained spectrum.

From the viewpoint of durability, the redox characteristic ΔE of the compound of the present invention may be preferably 0.1 eV or less, 0.08 eV or less, 0.06 eV or less, or 0.05 eV or less, and is 0.01 eV or more. There may be. ΔE can be calculated by performing cyclic voltammetry measurement under the following measurement conditions.
<Measurement conditions>
Working electrode: Glassy carbon Counter electrode: Platinum wire Reference electrode: Ag / AgNO ₃ Acetonitrile solution Solvent: THF
Electrolyte: Bu ₄ NPF ₆
Running speed: 50 meV / s
Luminescent material concentration: 1 mM
Electrolyte concentration: 100 mM

Method for producing a compound represented by the formula (1) The compound represented by the formula (1) is not particularly limited, but for example, the following formula (11):

(In the formula, Z and R ²¹ to R ²⁸ are the same as above)
The compound represented by the following formula (12):
Ar-L- (Q ¹ ) _n (12)
(During the ceremony,
Q ¹ is a halogen atom
Ar and L are the same as above,
When L is a single bond, n is an integer greater than or equal to 1 selected according to the valence of Ar.
When L is a phenylene group which may have a substituent, n is an integer of 1 or more selected according to the valence of L).
It can be produced by a method including a step of reacting with a compound represented by.

The compound represented by the formula (11) The compound represented by the formula (11) can be produced by a combination of known reactions. For example, the compound represented by the formula (11) is represented by the following formula (13):

(In the formula, Q ² and Q ³ are halogen atoms, respectively, and R ²¹ , R ²² , R ²⁴ , R ²⁵ , R ²⁷ , and R ²⁸ are the same as above).
The compound represented by the following formula (14):

(In the formula, R ²³ is the same as above)
The compound represented by, and the following formula (15):

(In the formula, R ²⁶ is the same as above)
It can be produced by a method including a step of reacting with a compound represented by.

In formula (13), Q ² and Q ³ may be the same or different from each other, and are preferably fluorine atoms, chlorine atoms, or bromine atoms, respectively.

In the formulas (14) and (15), −B (OH) ₂ is expressed by the following formula:

It may be a group represented by.

The total amount of the compounds represented by the formulas (14) and (15) used is 2 mol or more, 2.5 mol or more, or 3 mol or more with respect to 1 mol of the compound represented by the formula (13). It is preferably 6 mol or less, 5 mol or less, or 4 mol or less.

The reaction is preferably carried out in the presence of a catalyst. Examples of the catalyst include a transition metal catalyst, and specific examples thereof include a palladium catalyst, a copper catalyst, a nickel catalyst, and a cobalt catalyst. These catalysts can be used alone or in combination of two or more. When these catalysts are used, International Publication No. 2011/08902, International Publication No. 2015/137472, and the like can be referred to.

The reaction is preferably carried out in the presence of a base. Examples of the base include n-butyllithium, NaH, t-butoxysodium, KOH, K ₂ CO ₃ , K ₃ PO ₄ , t-butoxy potassium, potassium acetate, Cs ₂ CO _{3. and the} like. These bases can be used alone or in combination of two or more. When these bases are used, International Publication No. 2008/1178226, Chemistry of Materials, 2010, 22 (7), 2403-2410, Korean Patent Application Publication No. 2018-063708, etc. can be referred to.

The reaction is preferably carried out in the presence of a solvent. The solvent is not particularly limited as long as the reaction component can be dissolved, and is, for example, ether (eg, diethyl ether, dipropyl ether, dibutyl ether, 1,4-dioxane, tetrahydrofuran), aromatic hydrocarbon (eg, tetrahydrofuran). Examples include toluene, xylene), amines (eg, chain amines such as triethylamine, cyclic amines such as N-methylpyrrolidone), amides (eg, dimethylformamide), sulfoxides (eg, dimethylsulfoxide) and the like. As the solvent, one type can be used alone or two or more types can be mixed and used.

The reaction temperature and reaction time of the reaction are not particularly limited as long as the reaction proceeds. The reaction temperature may be, for example, 0 ° C. or higher, 15 ° C. or higher, or 25 ° C. or higher, or 200 ° C. or lower, 150 ° C. or lower, or 100 ° C. or lower. The reaction time may be, for example, 1 hour or more, 2 hours or more, or 5 hours or more, and may be 50 hours or less, 30 hours or less, or 10 hours or less.

Equation (12) Compound Q ¹ represented by the fluorine atom is preferably a chlorine atom, or bromine atom.

The compound represented by the formula (12) can be produced by a combination of known reactions. For example, among the compounds represented by the formula (12), the compound in which L is a single bond can be a commercially available product as it is, and the compound in which L is a phenylene group which may have a substituent may be used. , The following formula (16):
Ar-Q ⁴ (16)
(Wherein, ^{Q 4} is a halogen atom)
The compound represented by the following formula (17):
(Q ¹ ) _n- LB (OH) ₂ (17)
(In the formula, L and Q ¹ are the same as above)
It can be produced by a method including a step of reacting with a compound represented by.

In the formula (17), −B (OH) ₂ is expressed by the following formula:

It may be a group represented by.

For the reaction, the same reaction conditions as the reaction of the compounds represented by the formulas (13) to (15) can be adopted.

Reaction of the compound represented by the formula (11) and the compound represented by the formula (12) The reaction may adopt the same reaction conditions as the reaction of the compounds represented by the formulas (13) to (15). can.
In the reaction of the compounds represented by the formulas (11) and (12), the compounds represented by the formulas (13) to (15) are reacted, and then the compound represented by the formula (11) is continuously purified. It may be a reaction (one-pot reaction) in which the compound represented by the formula (12) is reacted (without), and after the compounds represented by the formulas (16) and (17) are reacted, the reaction (without the formula (12)) is continued. It may be a reaction (one-pot reaction) in which the compound represented by the formulas (13) to (15) is reacted without purifying the compound represented by 12).

<Delayed fluorescent material>
In one embodiment, the delayed fluorescent material of the present invention preferably comprises the compound of the present invention. The delayed fluorescent material can be suitably used, for example, as a light emitting material for an organic light emitting device described later.

<Organic light emitting element>
In one embodiment, the organic light emitting device of the present invention preferably contains the compound of the present invention.

Examples of the organic light emitting element include an organic photoluminescence element (organic PL element) and an organic electroluminescence element (organic EL element). The organic light emitting element is preferably an organic EL element.

The organic EL element preferably has an anode, a cathode, and an organic layer formed between the anode and the cathode.

The organic layer preferably contains at least a light emitting layer, and may be composed of only a light emitting layer, or may include one or more other organic layers in addition to the light emitting layer. Other organic layers include, for example, injection layers (eg, hole injection layer, electron injection layer), blocking layers (eg, electron blocking layer, hole blocking layer, exciton blocking layer), transport layers (eg, positive). Hole transport layer, electron transport layer) and the like. 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.

The organic EL element may be a bottom emission type that extracts the light generated in the light emitting layer from the substrate side, or may be a top emission type that extracts the light generated in the light emitting layer from the opposite side of the substrate. In any type, the electrode formed on the substrate side may be an anode or a cathode. The electrode on the side that extracts light is preferably transparent, and the electrode on the opposite side may or may not be transparent.

The organic EL element is preferably supported by a substrate. The substrate is not particularly limited as long as it is conventionally used for organic EL elements, and for example, a substrate made of glass, transparent plastic, quartz, silicon, or the like can be used.

As the anode in the organic EL element, a metal having a large work function (for example, 4 eV or more), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material are preferably used. Specific examples of such electrode materials include metals such as Au and transparent conductive materials such as _{CuI, indium tin oxide (ITO), SnO 2, and ZnO.} Further, a material capable of producing an amorphous transparent conductive film such as IDIXO (In ₂ O _{3-ZnO) may be used.} For the anode, a thin film may be formed by a method such as vapor deposition or sputtering of the electrode material to form a pattern having a desired shape by a photolithography method. May be formed. Alternatively, when a coatable material such as an organic conductive compound is used, a wet film forming method such as a printing method or a coating method can also be used. When extracting light from the anode, it is desirable to increase the transmittance to more than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. The film thickness of the anode depends on the material, but is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.

As the cathode, a metal having a small work function (for example, 4 eV or less) (electron-injectable metal), an alloy, an electrically conductive compound, or a mixture thereof as an electrode material is preferably 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 ) A mixture, a lithium / aluminum mixture, aluminum and the like are suitable. The cathode can be produced by forming a thin film of an electrode material by a method such as thin film deposition or sputtering. Further, the sheet resistance as a cathode is preferably several hundred Ω / □ or less. The film thickness of the cathode is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm. It is preferable that either the anode or the cathode of the organic EL element is transparent or translucent because the emission brightness is improved. Further, by using the transparent conductive material mentioned in the description of the anode for the cathode, a transparent or translucent cathode can be produced, and an element in which both the anode and the cathode have transparency can be produced.

The light emitting layer is a layer that emits light (eg, fluorescent light emission, delayed fluorescent light emission, or both) after excitons are generated by recombination of holes and electrons injected from each of the anode and cathode. Is preferable. The light emitting layer may be a layer containing a light emitting material alone, but is preferably a layer containing a light emitting material and a host material. As the light emitting material, the compound of the present invention (one type or two or more types) can be used. The host material is not particularly limited, but it is preferable to use an organic compound in which at least one of the excitation singlet energy and the excitation triplet energy has a value higher than that of the compound of the present invention. Further, the host material is preferably an organic compound having a hole transporting ability and an electron transporting ability, preventing a long wavelength of light emission, and having a high glass transition temperature.

Further, when a compound exhibiting TADF property is included in the light emitting layer as a third component (assist dopant compound) in the light emitting layer containing the host material and the light emitting material, it is effective in developing high luminous efficiency (H. Nakanоtani, et al. , Nature Compound, 2014, 5, 4016-4022). By generating 25% singlet excitons and 75% triplet excitons on the assist dopant compound by electric field excitation, the triplet excitons generate singlet excitons with inverse intersystem crossing (RISC). can do. The energy of the singlet excitons is transferred to the light emitting material, and the light emitting material can emit light. Therefore, theoretically 100% of the exciton energy can be used to make the light emitting material emit light, and high luminous efficiency is exhibited.

The content of the compound of the present invention in the light emitting layer is preferably 0.1% by mass or more, more preferably 1% by mass or more, and preferably 50% by mass or less, preferably 20% by mass. It is more preferably 10% by mass or less, and further preferably 10% by mass or less.

The injection layer is preferably a layer provided between the electrode and the organic layer in order to reduce the driving voltage or improve the emission brightness. The injection layer includes a hole injection layer and an electron injection layer. The injection layer may be provided between the anode and the light emitting layer or the hole transport layer, and between the cathode and the light emitting layer or the electron transport layer.

The blocking layer is preferably a layer capable of blocking the 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 arranged between the light emitting layer and the hole transporting layer, and can prevent electrons from passing through the light emitting layer toward the hole transporting layer. Similarly, the hole blocking layer can be placed between the light emitting layer and the electron transporting layer to prevent holes from passing through the light emitting layer towards the electron transporting layer. The electron blocking layer and the hole blocking layer can also function as exciton blocking layers, respectively. The electron blocking layer or exciton blocking layer referred to in the present specification is used in the sense that one layer includes a layer having the functions of an electron blocking layer and an exciton blocking layer.

The hole blocking layer has the function of an electron transport layer in a broad sense. The hole blocking layer has a role of blocking the holes from reaching the electron transporting layer while transporting electrons, which can improve the recombination probability of electrons and holes in the light emitting layer. As the material of the hole blocking layer, a material of the electron transport layer described later can be used as needed.

The electron blocking layer has a function of transporting holes in a broad sense. The electron blocking layer has a role of blocking electrons from reaching the hole transporting layer while transporting holes, which can improve the probability of recombination of electrons and holes in the light emitting layer. ..

The exciton blocking layer is preferably a layer for blocking excitons generated by recombination of holes and electrons in the light emitting layer from diffusing into the charge transport layer. By inserting the exciton blocking layer, excitons can be efficiently confined in the light emitting layer, and the luminous efficiency of the element can be improved. The exciton blocking layer can be inserted into either the anode side or the cathode side adjacent to the light emitting layer, and both can be inserted at the same time. That is, when the exciton blocking layer is provided on the anode side, the layer can be inserted between the hole transport layer and the light emitting layer adjacent to the light emitting layer, and when inserted on the cathode side, the light emitting layer and the light emitting layer can be inserted. The layer can be inserted adjacent to the light emitting layer between the cathode and the light emitting layer. Further, a hole injection layer, an electron blocking layer and the like can be provided between the anode and the exciton blocking layer adjacent to the anode side of the light emitting layer. An electron injection layer, an electron transport layer, a hole blocking layer, and the like can be provided between the cathode and the exciton blocking layer adjacent to the cathode side of the light emitting layer. When the blocking layer is arranged, it is preferable that at least one of the excitation singlet energy and the excitation triplet energy of the material used as the blocking layer is higher than the excitation singlet energy and the excitation triplet energy of the light emitting material.

The hole transport layer is preferably 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. As the hole transporting material, a material having any of hole injection or transport and electron barrier property is preferable, and either an organic substance or an inorganic substance may be used. Examples of the hole transporting material that can be used include triazole derivative, oxadiazole derivative, imidazole derivative, carbazole derivative, indolocarbazole derivative, polyarylalkane derivative, pyrazoline derivative and pyrazolone derivative, phenylenediamine derivative, arylamine derivative, and amino. Examples thereof include substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilben derivatives, silazane derivatives, aniline-based copolymers, and conductive polymer oligomers, particularly thiophene oligomers. As the hole transport material, it is preferable to use a porphyrin compound, an aromatic tertiary amine compound, and a styrylamine compound, and it is more preferable to use an aromatic tertiary amine compound. Inorganic semiconductors such as molybdenum oxide can also be used as the hole transport material.

The electron transport layer is preferably made of a material having a function of transporting electrons, and the electron transport layer can be provided with a single layer or a plurality of layers. The electron transporting material (which may also serve as a hole blocking material) preferably has a function of transferring electrons injected from the cathode to the light emitting layer. Examples of the electron transporting layer that can be used include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimides, freolenidenemethane derivatives, anthracinodimethane and anthron derivatives, and oxadiazole derivatives. Further, among the above oxadiazole derivatives, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is replaced with a sulfur atom, and a quinoxalin derivative having a quinoxalin ring known as an electron attractant can also be used as an electron transport material. .. Further, 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. Further, an inorganic semiconductor such as zinc oxide can also be used as an electron transport material.

When producing an organic EL device, the compound of the present invention may be used not only for the light emitting layer but also for a layer other than the light emitting layer. At that time, the compound of the present invention used for the light emitting layer and the compound of the present invention used for the layer other than the light emitting layer may be the same or different. For example, the compound of the present invention may be used for the above-mentioned injection layer, blocking layer (eg, hole blocking layer, electron blocking layer, exciton blocking layer), hole transport layer, electron transport layer and the like.

The film forming method for these layers is not particularly limited, and may be formed by either a dry process or a wet process.

Hereinafter, preferable materials that can be used for the organic electroluminescence device will be specifically exemplified. However, the materials that can be used in the present invention are not limitedly interpreted by the following exemplary compounds. Further, even a compound exemplified as a material having a specific function can be diverted as a material having another function. In addition, R, R', and R ₁ to R ₁₀ in the structural formulas of the following exemplified compounds each independently represent a hydrogen atom or a substituent. X represents a carbon atom or a complex 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.

Preferred compounds that can also be used as host material for the light emitting layer are listed. In order to match the HOMO / LUMO level of the luminescent material to be used, the HOMO / LUMO level of the host material can be adjusted by appropriately introducing a substituent into the basic skeleton of the following exemplified compound. For example, by introducing a cyano group or a perfluoroalkyl group into the basic skeleton of the following exemplified compound, a compound having a deepened HOMO / LUMO level can be obtained, which can be used as a host material or a peripheral compound. As the host material, it is also a bipolar character (flow good both holes and electrons) may be a unipolar resistance, but high excited triplet energy level E _T1 than the light emitting material Is preferable. More preferred host material has a bipolar property, those high excited triplet energy level E _T1 than the light emitting material.

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

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

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

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

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

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

Examples of preferable compounds as materials that can be further added are given. For example, it can be added as a stabilizing material.

The organic EL 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. The organic light emitting device such as the organic EL device of the present invention can be further applied to various applications. For example, it is possible to manufacture an organic electroluminescence display device using the organic EL element of the present invention. For details, see "Organic EL Display" by Shizushi Tokito, Chihaya Adachi, and Hideyuki Murata (Ohmsha). Can be referred to. In particular, the organic EL device of the present invention can also be applied to organic electroluminescence lighting and backlight, which are in great demand. Further, the organic light emitting device of the present invention can be applied to an organic light emitting diode.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

(Synthesis of intermediate D1)

In a nitrogen atmosphere, 2,7-bis (trifluoromethyl) -9H-carbazole (4.55 g) and triphenylphosphine sulfide (220 mg) were placed in a 200 mL eggplant flask and dissolved in DMF (100 mL). N-Bromosuccinimide (10.8 g) was added in two portions with stirring at room temperature. After stirring at room temperature for 23 hours, a saturated aqueous sodium hydrogen sulfite solution (40 mL) and a 1N aqueous sodium hydroxide solution (50 mL) were added to the reaction solution. The precipitate was collected by filtration and sublimated and purified to obtain 3,6-dibromo-2,7-bis (trifluoromethyl) -9H-carbazole (5.8 g, yield 84%). ^{The 1} H NMR spectrum and the ¹⁹ F NMR spectrum of the compound are shown in FIGS. 1 and 2, respectively.

3. In a nitrogen atmosphere, in a 50 mL eggplant flask, 3,6-dibromo-2,7-bis (trifluoromethyl) -9H-carbazole (1.38 g), phenylboronic acid (1.46 g), potassium phosphate (5. 12 g), tri-tert-butylphosphonium tetrafluoroborate (87 mg) and tris (dibenzylideneacetone) dipalladium-chloroform complex (155 mg) were added and dissolved in xylene (25 mL). After degassing the reaction solvent, the mixture was stirred at 110 ° C. for 17 hours. The reaction solution was allowed to cool, water was added, and the solution was separated. The aqueous layer was extracted with ethyl acetate, the organic layers were combined and concentrated under reduced pressure, and the obtained crude product was subjected to a silica gel column (hexane: chloroform = 1: 1) to obtain intermediate D1 (1.05 g, yield). 77%) was obtained. ^{The 1} H NMR spectrum and the ¹⁹ F NMR spectrum of the intermediate D1 are shown in FIGS. 3 and 4, respectively.

(Synthesis of intermediate D2)

In a 30 mL eggplant flask under a nitrogen atmosphere, 3,6-dibromo-2,7-bis (trifluoromethyl) -9H-carbazole (461 mg), methylboronic acid (239 mg), potassium phosphate (10.6 g), dichloro ( 1,1'-Bis (diphenylphosphino) ferrocene) palladium (73 mg) was added, and 1,4-dioxane (10 mL) and water (3 mL) were added and dissolved. After degassing the reaction solvent, the mixture was stirred with heating under reflux for 13 hours. The reaction mixture was allowed to cool, ethyl acetate and saturated aqueous sodium chloride solution were added, and the layers were separated. The aqueous layer was extracted with ethyl acetate, the organic layers were combined and concentrated under reduced pressure. The obtained crude product was subjected to a silica gel filtration column (ethyl acetate) and then washed with hexane to obtain intermediate D2 (125 mg, yield). 38%) was obtained. ^{The 1} H NMR spectrum and the ¹⁹ F NMR spectrum of the intermediate D2 are shown in FIGS. 5 and 6, respectively.

(Synthesis of intermediate D3)

3,6-Dibromo-2,7-bis (trifluoromethyl) -9H-carbazole (1.73 g), dibenzofuran-4-boronic acid (1.79 g), potassium carbonate (1.79 g) in a 50 mL eggplant flask under a nitrogen atmosphere. 1.99 g) and tetrakistriphenylphosphine palladium (266 mg) were added, and toluene (26.5 mL) and water (10 mL) were added to dissolve the mixture. After degassing the reaction solvent, the mixture was stirred with heating under reflux for 16 hours. The reaction mixture was allowed to cool, ethyl acetate and water were added, and the layers were separated. The aqueous layer was extracted with ethyl acetate, the organic layers were combined and concentrated under reduced pressure, and the obtained crude product was subjected to a silica gel column (hexane / ethyl acetate = 4/1) and used as an intermediate D3 (1.84 g, yield 77). %) Was obtained. ^{The 1} H NMR spectrum and the ¹⁹ F NMR spectrum of the intermediate D3 are shown in FIGS. 7 and 8, respectively.

(Synthesis of intermediate D4)

In a 50 mL eggplant flask under a nitrogen atmosphere, 3,6-dibromo-2,7-bis (trifluoromethyl) -9H-carbazole (461 mg), 9-phenylcarbazole-3-boronic acid (860 mg), potassium phosphate (860 mg) 1.06 g), dichloro (1,1'-bis (diphenylphosphino) ferrocene) palladium (70 mg) was added, and 1,4-dioxane (9 mL) and water (3 mL) were added and dissolved. After degassing the reaction solvent, the mixture was stirred with heating under reflux for 17 hours. The reaction mixture was allowed to cool, ethyl acetate and water were added, and the layers were separated. The aqueous layer was extracted with ethyl acetate, the organic layers were combined and concentrated under reduced pressure, and the obtained crude product was subjected to a silica gel column (hexane: chloroform = 1: 1) to obtain intermediate D4 (650 mg, yield 75%). Obtained. The m / z of the target object was observed by mass spectrometry (ASAP, positive).

(Synthesis of intermediate D5)

4-Methyl-3-trifluoromethylaniline (96 mg), 4-bromo-2-trifluoromethyltoluene (120 mg), tert-butoxynatrim (96 mg), tris (dibenzilidenacetone) in a 10 mL Schlenck tube under a nitrogen atmosphere. ) Dipalladium / chloroform complex (51 mg) and Xphos (48 mg) were added, and 1,4-dioxane (2 mL) was added and suspended. After degassing the reaction solvent, the mixture was stirred at 80 ° C. for 15 hours. The reaction mixture was allowed to cool, ethyl acetate and saturated aqueous sodium chloride solution were added, and the layers were separated. The aqueous layer was extracted with ethyl acetate, the organic layers were combined and concentrated under reduced pressure, and the obtained crude product was subjected to a silica gel column (hexane: chloroform = 1: 1) to obtain intermediate D5 (218 mg, yield 65%). Got ^{The 1} H NMR spectrum and the ¹⁹ F NMR spectrum of the intermediate D5 are shown in FIGS. 9 and 10, respectively.

(Synthesis of intermediate A1)

In a nitrogen atmosphere, in a 50 mL eggplant flask, 2-chloro-4,6-diphenyl-1,3,5-triazine (803 mg), 3,4,5-trifluorophenylboronic acid (528 mg), potassium carbonate (1. 24 g) and tetrakistriphenylphosphine palladium (174 mg) were added, and THF (22 mL) and water (7 mL) were added to dissolve the mixture. The reaction mixture was degassed and heated to reflux for 24 hours. The reaction mixture was allowed to cool, and ethyl acetate (15 mL) and water (15 mL) were added. The insoluble material was collected by filtration and washed with ethyl acetate and acetone to obtain Intermediate A1 (902 mg, yield 83%).

(Synthesis of intermediate A2)

In a nitrogen atmosphere, in a 50 mL eggplant flask, 1,4-dibromo-2,5-difluorobenzene (1.00 g), bispinacolato diboron (2.02 g), potassium acetate (1.81 g), dichloro (1,1) 1'-bis (diphenylphosphino) ferrocene) palladium (150 mg) was added and suspended in 1,4-dioxane (25 mL). After degassing the reaction solvent, the mixture was stirred at 100 ° C. for 20 hours. The reaction mixture was concentrated and then subjected to a silica gel filtration column (ethyl acetate). By concentrating the filtrate and washing with hexane, 2,2'-(2,5-difluoro-1,4-phenylene) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) ) (806 mg, yield 60%) was obtained.
2,2'-(2,5-difluoro-1,4-phenylene) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (366 mg) in a 50 mL eggplant flask under a nitrogen atmosphere. ), 2-Chloro-4,6-diphenyl-1,3,5-triazine (615 mg), potassium carbonate (690 mg), tetrakistriphenylphosphine palladium (57 mg), and dissolved in THF (20 mL) and water (6 mL). I let you. After degassing the reaction solvent, the mixture was stirred under heating under reflux for 14 hours. The reaction solution was allowed to cool and water was added. The precipitate was collected by filtration and washed with ethyl acetate to obtain Intermediate A2 (495 mg, yield 86%). ^{The 1} H NMR spectrum and the ¹⁹ F NMR spectrum of the intermediate A2 are shown in FIG.

(Synthesis of intermediate A3)

In a nitrogen atmosphere, in a 50 mL eggplant flask, 1,5-dibromo-2,4-difluorobenzene (1.00 g), bispinacolato diboron (2.02 g), potassium acetate (1.81 g), dichloro (1,1) 1'-bis (diphenylphosphino) ferrocene) palladium (150 mg) was added and suspended in 1,4-dioxane (25 mL). After degassing the reaction solvent, the mixture was stirred at 100 ° C. for 23 hours. The reaction mixture was concentrated and then subjected to a silica gel filtration column (ethyl acetate). By concentrating the filtrate, a crude product (1) of 2,2'-(4,6-difluoro-1,3-phenylene) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) .93 g, crude yield 143%) was obtained. Purification was performed after the next reaction.
A crude product of 2,2'-(4,6-difluoro-1,3-phenylene) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) in a 50 mL eggplant flask under a nitrogen atmosphere. (523 mg), 2-chloro-4,6-diphenyl-1,3,5-triazine (615 mg), potassium carbonate (690 mg), tetrakistriphenylphosphine palladium (57 mg), THF (20 mL), water ( It was dissolved in 6 mL). After degassing the reaction solvent, the mixture was stirred under heating under reflux for 14 hours. The reaction solution was allowed to cool and water was added. The precipitate was collected by filtration and washed with ethyl acetate and chloroform to obtain Intermediate A3 (297 mg, 2-step yield 52%). ^{The 1} H NMR spectrum and the ¹⁹ F NMR spectrum of Intermediate A3 are shown in FIGS. 12 and 13, respectively.

(Synthesis of intermediate A4)

2-Bromo-4,6-diphenyl-1,3,5-triazine (623 mg), 2,4,6-trifluorophenylboronic acid (387 mg), potassium carbonate (982 mg) in a 50 mL eggplant flask under a nitrogen atmosphere. , Tris (dibenzylideneacetone) dipalladium (0) chloroform adduct (109 mg) and triphenylphosphine (63 mg) were added, and THF (15 mL) and water (5 mL) were added and dissolved. After degassing the reaction solvent, the mixture was stirred with heating under reflux for 20 hours. The reaction mixture was allowed to cool and subjected to a silica gel filtration column (ethyl acetate). The solid precipitated in the filtrate was collected by filtration to obtain Intermediate A4 (308 mg, yield 42%). ^{The 1} H NMR spectrum and the ¹⁹ F NMR spectrum of the intermediate A4 are shown in FIGS. 14 and 15, respectively.

(Synthesis of intermediate A5)

2-Bromo-4,6-diphenylpyrimidine (611 mg), 2,4,6-trifluorophenylboronic acid (482 mg), potassium carbonate (1.33 g), tris (dibenzylidene) in a 20 mL eggplant flask under a nitrogen atmosphere. Acelatin) dipalladium (0) chloroform adduct (124 mg) and tri-tert-butylphosphonium tetrafluoroborate (156 mg) were added, and DMF (10 mL) was added to dissolve the mixture. After degassing the reaction solvent, the mixture was stirred with heating under reflux for 20 hours. The reaction mixture was allowed to cool, and toluene and water were added to separate the solutions. The aqueous layer was extracted with toluene, the organic layers were combined and concentrated under reduced pressure, and the obtained crude product was subjected to a silica gel column (hexane / ethyl acetate = 95/5) to provide intermediate A5 (522 mg, yield 73%). ) Was obtained. ^{The 1} H NMR spectrum and the ¹⁹ F NMR spectrum of Intermediate A5 are shown in FIGS. 16 and 17, respectively.

(Synthesis of intermediate A6)

In a nitrogen atmosphere, 6-iodoquinoline (509 mg), 3,5-difluorophenylboronic acid (471 mg), potassium carbonate (1.08 g), and tetrakistriphenylphosphine palladium (132 mg) were placed in a 20 mL eggplant flask, and toluene (toluene) was added. 8 mL) and water (3 mL) were added and dissolved. After degassing the reaction solvent, the mixture was stirred with heating under reflux for 21 hours. The reaction mixture was allowed to cool, ethyl acetate and water were added, and the layers were separated. The aqueous layer was extracted with ethyl acetate, and the organic layers were combined and concentrated under reduced pressure. The obtained crude product was subjected to a silica gel column (hexane / ethyl acetate = 3/2) to obtain Intermediate A6 (463 mg, yield 87%). ^{The 1} H NMR spectrum and the ¹⁹ F NMR spectrum of Intermediate A6 are shown in FIGS. 18 and 19, respectively.

(Synthesis of Intermediate A7)

In a nitrogen atmosphere, 6-iodoquinoline (613 mg), 3-bromo-5-fluorophenylboronic acid (796 mg), potassium carbonate (1.28 g), and tetrakistriphenylphosphine palladium (150 mg) were placed in a 30 mL eggplant flask. Toluene (10 mL) and water (4 mL) were added and dissolved. After degassing the reaction solvent, the mixture was stirred with heating under reflux for 17 hours. The reaction mixture was allowed to cool, ethyl acetate and water were added, and the layers were separated. The aqueous layer was extracted with ethyl acetate, and the organic layers were combined and concentrated under reduced pressure. The obtained crude product was subjected to a silica gel column (hexane / ethyl acetate = 3/2) to obtain Intermediate A7 (461 mg, yield 63%). ^{The 1} H NMR spectrum and the ¹⁹ F NMR spectrum of Intermediate A7 are shown in FIGS. 20 and 21, respectively.

(Synthesis of Intermediate A8)

2,2'-(2,5-difluoro-1,4-phenylene) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (183 mg) in a 20 mL Schlenk tube under a nitrogen atmosphere ), 2-Chloro-4,6-diphenyl-pyrimidine (307 mg), potassium carbonate (207 mg) and tetrakistriphenylphosphine palladium (29 mg) were added and dissolved in THF (10 mL) and water (3 mL). After degassing the reaction solvent, the mixture was stirred under heating under reflux for 23 hours. The reaction solution was allowed to cool and water was added. The precipitate was collected by filtration and washed with water and acetone to obtain Intermediate A8 (216 mg, yield 75%). ^{The 1} H NMR spectrum of Intermediate A8 is shown in FIG.

(Synthesis of Intermediate A9)

Under a nitrogen atmosphere, in a 100 mL four-necked flask, 1,4-dibromo-2-fluorobenzene (1.80 g), bispinacholate diboron (3.88 g), potassium acetate (3.53 g), [1,1 ′ -Bis (diphenylphosphino) ferrocene] Dichloropalladium (II) (291 mg) was added, and 1,4-dioxane (36 mL) was added and dissolved. After degassing the reaction solvent, the mixture was stirred with heating under reflux for 17 hours. The reaction mixture was allowed to cool, subjected to a silica gel filtration column (ethyl acetate), and the filtrate was concentrated under reduced pressure. Hexane was added to the obtained crude product, and the precipitate was collected by filtration to obtain 2,2'-(2-fluoro-1,4-phenylene) bis (4,4,5,5-tetramethyl-1). , 3,2-Dioxaborolane) (1.79 g, yield 72%) was obtained.

In a nitrogen atmosphere, in a 10 mL Schlenk tube, 2,2'-(2-fluoro-1,4-phenylene) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (200 mg), Add 2-bromo-4,6-diphenyl-1,3,5-triazine (565 mg), potassium carbonate (557 mg), tetrakistriphenylphosphine palladium (45 mg), and add THF (4 mL) and water (1.3 mL). In addition, it was dissolved. After degassing the reaction solvent, the mixture was stirred with heating under reflux for 17 hours. After allowing the reaction solution to cool, water was added to precipitate a white solid. The precipitate was collected by filtration and washed with ethyl acetate to obtain Intermediate A9 (321 mg, yield 100%). ^{The 1} H NMR spectrum and the ¹⁹ F NMR spectrum of Intermediate A9 are shown in FIGS. 23 and 24, respectively.

(Synthesis of Example 1)

Intermediate D1 (170 mg), intermediate A1 (38 mg) and cesium carbonate (182 mg) were placed in a 10 mL Schlenk tube under a nitrogen atmosphere and dissolved in DMSO (2 mL). After reacting at 80 ° C. for 2 hours, the mixture was allowed to cool. Water (5 mL) was added to the reaction solution, and the precipitate was collected by filtration. Example 1 (120 mg, yield 69%) was obtained by subjecting the filtrate to a silica gel column (hexane: chloroform = 1: 1). ^{The 1} H NMR spectrum and the ¹⁹ F NMR spectrum of Example 1 are shown in FIGS. 25 and 26, respectively.

(Synthesis of Example 2)

Intermediate D1 (285 mg), intermediate A2 (144 mg) and cesium carbonate (305 mg) were placed in a 10 mL Schlenk tube under a nitrogen atmosphere and suspended in NMP (15 mL). After the reaction at 130 ° C. for 21 hours, the mixture was allowed to cool. Water (5 mL) was added to the reaction solution, and the precipitate was collected by filtration. Example 2 (346 mg, yield 96%) was obtained by sublimating and purifying the filtrate. ^{The 1} H NMR spectrum and the ¹⁹ F NMR spectrum of Example 2 are shown in FIGS. 27 and 28, respectively.

(Synthesis of Examples 3 and 4)

(Example 3: R = Ph, Example 4: R = Me)

Intermediate D1 (285 mg), intermediate A3 (144 mg) and cesium carbonate (305 mg) were placed in a 10 mL Schlenk tube under a nitrogen atmosphere and suspended in NMP (15 mL). After the reaction at 130 ° C. for 21 hours, the mixture was allowed to cool. Water (5 mL) was added to the reaction solution, and the precipitate was collected by filtration. Example 3 (355 mg, yield 98%) was obtained by sublimating and purifying the filtrate. ^{The 1} H NMR spectrum and the ¹⁹ F NMR spectrum of Example 3 are shown in FIGS. 29 and 30, respectively.
Intermediate D2 (125 mg), intermediate A3 (87 mg) and cesium carbonate (184 mg) were placed in a 10 mL Schlenk tube under a nitrogen atmosphere and suspended in NMP (5 mL). After reacting at 130 ° C. for 2 hours, the mixture was allowed to cool. Water (5 mL) was added to the reaction solution, and the precipitate was collected by filtration. Example 4 (58 mg, yield 27%) was obtained by sublimating and purifying the filtrate. ^{The 1} H NMR spectrum and the ¹⁹ F NMR spectrum of Example 4 are shown in FIGS. 31 and 32, respectively.

(Synthesis of Example 5)

Under a nitrogen atmosphere, intermediate D2 (125 mg), intermediate A8 (86 mg), and cesium carbonate (184 mg) were placed in a 10 mL Schlenk tube and dissolved in NMP (5 mL). The reaction was carried out at 150 ° C. for 22 hours. When the reaction solution was allowed to cool and water was added, a flesh-colored solid was precipitated. The precipitate was collected by filtration and then sublimated and purified to give Example 5 (89 mg, yield 50%). It was identified by mass spectrometry (ASAP, positive).

(Synthesis of Example 6)

Under a nitrogen atmosphere, intermediate A9 (287 mg), intermediate D3 (360 mg), and cesium carbonate (591 mg) were placed in a 10 mL Schlenk tube and dissolved in NMP (5.8 mL). The reaction was carried out at 130 ° C. for 22 hours. When the reaction solution was allowed to cool and water was added, a flesh-colored solid was precipitated. The precipitate was collected by filtration and then sublimated and purified to give Example 6 (417 mg, yield 70%). It was identified by mass spectrometry (ASAP, positive).

(Comparative Example 1)
Comparative Example 1 has the following formula:

It is a compound represented by Lumtec (http://www.lumtec.com.tw/portal_c1_cnt_page.php?owner_num=c1_290785&button_num=c1&folder_id=36067&cnt_id=396136&search_field Will & Search_word = & search_field2 = & search_word2 = & search_field3 = & search_word & bool2 = & search_type = 1 & up_page = 3)
It was used.

(Comparative Examples 2 to 4)
Comparative Examples 2 to 4 have the following formulas, respectively:

It is a compound represented by, and was synthesized by the method described in International Publication No. 2018047948.

(Synthesis of Comparative Example 5)

As the first step of the reaction, intermediate A1 (500 mg), 2,7-bistrifluoromethylcarbazole (444 mg) and cesium carbonate (961 mg) were placed in a 30 mL eggplant flask under a nitrogen atmosphere and dissolved in DMSO (20 mL). rice field. After stirring at 85 ° C. for 3 hours, the mixture was allowed to cool to room temperature. Water (12 mL) and chloroform (10 mL) were added to the reaction solution, and the mixture was allowed to stand for 10 minutes. The precipitated gray crystals were collected by filtration and washed with water (2 mL) and chloroform (3 mL) to form 9- (4- (4,6-diphenyl-1,3,5-triazine-2-yl)-. 2,6-Difluorophenyl) -2,7-bis (trifluoromethyl) -9H-carbazole (766 mg, yield 86%) was obtained. As the second step of the reaction, 9-(4- (4,6-diphenyl-1,3,5-triazine-2-yl) -2,6-difluorophenyl) -2 was placed in a 30 mL eggplant flask under a nitrogen atmosphere. , 7-Bis (trifluoromethyl) -9H-carbazole (499 mg), carbazole (274 mg) and cesium carbonate (1.158 g) were added and dissolved in DMSO (20 mL). After stirring at 120 ° C. for 18 hours, the mixture was allowed to cool to room temperature. Next, water (15 mL) was added to the reaction solution, and the mixture was allowed to stand for 40 minutes. The precipitated gray crystals were collected by filtration and washed with cold chloroform (2 mL) to obtain Comparative Example 5 (515 mg, yield 71%). ^{The 1} H NMR spectrum of Comparative Example 5 is shown in FIG. 33.

(Synthesis of Comparative Example 6)

In a nitrogen atmosphere, in a 30 mL eggplant flask, 9- (4- (4,6-diphenyl-1,3,5-triazine-2-yl) -2,6-difluorophenyl) -2,7-bis (trifluoro) Methyl) -9H-carbazole (65 mg), 3,6-diphenylcarbazole (80 mg) and cesium carbonate (82 mg) were added and dissolved in DMSO (3 mL). After stirring at 100 ° C. for 18 hours, the mixture was allowed to cool to room temperature. Next, water (15 mL) was added to the reaction solution, and the mixture was allowed to stand for 40 minutes. The precipitated gray crystals were collected by filtration, washed with IPA (2 mL), and then sublimated to obtain Comparative Example 6 (85 mg, yield 68%). ^{The 1} H NMR spectrum and the ¹⁹ F NMR spectrum of Comparative Example 6 are shown in FIGS. 34 and 35, respectively.

(Synthesis of Comparative Examples 7 to 9)
Comparative Examples 7 to 9 have the following formulas, respectively:

It is a compound represented by, and was synthesized by the method described in Nature 2012, 492 (13), 234-238.

(Synthesis of Comparative Example 10)
Comparative Example 10 has the following formula:

It is a compound represented by, and was synthesized by the method described in Chinese Patent Application Publication No. 107384364. ^{The 1} H NMR spectrum and the ¹³ C NMR spectrum of Comparative Example 10 are shown in FIGS. 36 and 37, respectively.

(Synthesis of Comparative Example 11)
Comparative Example 11 has the following formula:

It is a compound represented by, and was synthesized by the method described in International Publication No. 2019087936. ^{The 1} H NMR spectrum and the ¹⁹ F NMR spectrum of Comparative Example 11 are shown in FIGS. 38 and 39, respectively.

(Synthesis of Comparative Example 12)
Comparative Example 12 has the following formula:

In the synthesis of Comparative Example 11, the compound represented by was synthesized using 2,7-bis (trifluoromethyl) carbazole instead of the raw material 3,6-bis (trifluoromethyl) carbazole. The m / z of the target object was confirmed by mass spectrometry (ASAP, positive).

(Synthesis of Comparative Example 13)

Intermediate D1 (170 mg), 4,5-difluorophthalonitrile (24 mg) and cesium carbonate (182 mg) were placed in a 10 mL Schlenk tube under a nitrogen atmosphere and dissolved in DMSO (2 mL). After reacting at 80 ° C. for 2 hours, the mixture was allowed to cool. Water (5 mL) was added to the reaction solution, and the precipitate was collected by filtration. Comparative Example 13 (20 mg, yield 13%) was obtained by subjecting the filtrate to a silica gel column (hexane: chloroform = 1: 1). ^{The 1} H NMR spectrum and the ¹⁹ F NMR spectrum of Comparative Example 13 are shown in FIGS. 40 and 41, respectively.

(Maximum emission wavelength (λmax), full width at half maximum)
Λmax, full width at half maximum, and CIE of Comparative Examples and Examples ^{show the emission spectrum when a toluene solution of luminescent material (luminescent material concentration: 1 × 10-5} M) is irradiated with excitation light at 340 nm at room temperature. It was measured using Fluoromax 4 manufactured by Fluoromax 4 manufactured by Fluoromax 4 and measured as follows based on the emission spectrum.
λmax was measured by the wavelength of the peak top.
The full width at half maximum was measured by the spectral width of half the value of the peak top intensity.

(Luminous efficiency (PLQY))
The PLQY of Comparative Examples and Examples is a value when a toluene solution of a light emitting material (light emitting material concentration: 1 × ^10-5 M) is irradiated with excitation light of 340 nm at room temperature, and is an absolute PL quantum yield measuring device (absolute PL quantum yield measuring device). It was measured using Quantaurus-QY C11347-01) manufactured by Hamamatsu Photonics.

(HOMO level)
The HOMO levels of Comparative Examples and Examples were measured using an atmospheric photoelectron spectrometer (AC-3 manufactured by RIKEN Keiki Co., Ltd.). As the measurement sample, a light emitting material vacuum-deposited on an ITO substrate so as to have a film thickness of 50 nm was used. The measurement was carried out with an ultraviolet light intensity of 10 nW and a measurement range of -4.00 eV to -7.00 eV (in increments of 0.05 eV), and the energy threshold value of photoelectron emission during ultraviolet irradiation was set as the HOMO level.

(Orientation parameter S)
The orientation parameter S of Comparative Examples and Examples is 45 to 75 degrees (5) using a spectroscopic ellipsometer (JA Woollam Japan product) after forming a single film (thickness of about 30 nm) of the light emitting material on a bare silicon substrate. The spectrum was measured in the range of (in increments), and the spectrum was calculated by fitting analysis of the obtained spectrum.

(Redox characteristic ΔE)
The redox characteristics of Comparative Examples and Examples were calculated by performing cyclic voltammetry measurement under the following measurement conditions.
<Measurement conditions>
Working electrode: Glassy carbon Counter electrode: Platinum wire Reference electrode: Ag / AgNO ₃ Acetonitrile solution Solvent: THF
Electrolyte: Bu ₄ NPF ₆
Running speed: 50 meV / s
Luminescent material concentration: 1 mM
Electrolyte concentration: 100 mM

The results are shown in Table 1.

Claims (14)

1. Compound represented by the following formula (1):
   Cz-L-Ar (1)
   [During the ceremony,
   Cz is calculated by the following equation (2):
   

   

   (During the ceremony,
   Z is absent, single bond, -C (R ^29a ) (R ^29b )-, -O-, -S-, or -N (R ^29c )-.
   R ²² and R ²⁷ are electron-attracting groups, respectively, and
   R ²³ and R ²⁶ are electron-donating groups, respectively.
   R ²¹ , R ²⁴ , R ²⁵ , R ²⁸ , R ^29a , R ^29b , and R ^29c are hydrogen atoms, electron attracting groups, or electron donating groups, respectively.
   The wavy line indicates the binding site with L)
   It is a group represented by
   L is a phenylene group which may have a single bond or a substituent, and is a phenylene group.
   Ar is a group selected from the group consisting of an aryl group and a heteroaryl group, and the group may have an N, N-diarylamino group or a substituent which may have a substituent. It may have at least one substituent selected from a cycloalkyl group, an aryl group which may have a substituent, and a heteroaryl group which may have a substituent (where Ar is. , Not a group represented by equation (2))].
2. Ar is a group selected from the group consisting of a phenyl group, a fused bi to hexacyclic aryl group, and a nitrogen-containing heteroaryl group, and the group may have a substituent N, N-diaryl. At least one substituent selected from an amino group, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, and a heteroaryl group which may have a substituent. (However, Ar is not a group represented by the formula (2)), and the compound according to claim 1.
3. Ar is the following formula (3):
   

   

   (During the ceremony,
   X ³¹ to X ³⁵ are -N = or -C (R ³ ) =, respectively.
   R ³ is a hydrogen atom, an N, N-diarylamino group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or It is a heteroaryl group that may have a substituent and
   The two R ³ which may be present in a positional relationship ortho to each other, may form an aromatic ring bonded to each other, the aromatic ring may have a substituent N, N-diarylamino group Has at least one substituent selected from a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, and a heteroaryl group which may have a substituent. You may be
   The wavy line indicates the binding site with L)
   The compound according to claim 1 or 2, which is a group represented by.
4. The groups represented by the formula (3) are the following formulas (3-1) to (3-4):
   

   

   (During the ceremony,
   R ³¹¹ and R ³¹² , R ³²¹ to R ³²³ , R ³³¹ to R ³³⁶ , and R ³⁴¹ to R ³⁴⁶ , respectively, have a hydrogen atom and an N, N-diarylamino group and a substituent which may have a substituent. A cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.
   The wavy line indicates the binding site with L)
   The compound according to claim 3, which is a group represented by any of the above.
5. Claim 3 or claim L is a phenylene group which may have at least one substituent selected from the group consisting of a group represented by the formula (2) and a group represented by the formula (3). The compound according to 4.
6. The compound according to any one of claims 1 to 5, wherein Z is a single bond.
7. The compound according to any one of claims 1 to 6, wherein R ²² and R ^{27 are perfluoroalkyl groups or cyano groups, respectively.}
8. R ²³ and R ²⁶ each have an alkyl group, an alkoxy group, a trialkylsilyl group, an N, N-diarylamino group which may have a substituent, a cycloalkyl group which may have a substituent, and the like. The compound according to any one of claims 1 to 7, which is an aryl group which may have a substituent or a heteroaryl group which may have a substituent.
9. R ²¹ , R ²⁴ , R ²⁵ , and R ²⁸ are hydrogen atoms, or R ²¹ and R ²⁸ are electron donating groups, respectively, and R ²⁴ and R ²⁵ are electron attracting groups, respectively. Is,
   The compound according to any one of claims 1 to 8.
10. Compound represented by the following formula (4):
    

    

    [During the ceremony,
    X ⁴¹ to X ⁴³ are -N = or -C (R ⁴⁴ ) =, respectively.
    R ⁴¹ to R ⁴⁴ may have a hydrogen atom, an N, N-diarylamino group which may have a substituent, a cycloalkyl group which may have a substituent, and a substituent, respectively. A good aryl group or a heteroaryl group which may have a substituent (provided ^{that at least one of R 41} to R ⁴³ is a group represented by the formula (2))];
    Compound represented by the following formula (5):
    

    

    [During the ceremony,
    X ⁵¹ to X ⁵³ are -N = or -C (R ⁵⁸ ) =, respectively.
    R ⁵¹ , R ⁵² , and R ⁵⁸ each have a hydrogen atom, an N, N-diarylamino group which may have a substituent, a cycloalkyl group which may have a substituent, and a substituent, respectively. It is an aryl group which may have a substituent or a heteroaryl group which may have a substituent.
    Each of R ⁵³ to R ⁵⁷ is a hydrogen atom or a group represented by the formula (2) (however ^{, at least one of R 53} to R ⁵⁷ is a group represented by the formula (2))]. ;
    Compound represented by the following formula (6):
    

    

    [During the ceremony,
    X ⁶¹ to X ⁶⁷ are -N = or -C (R ⁶⁶ ) =, respectively.
    R ⁶¹ to R ⁶⁵ are hydrogen atoms or groups represented by the formula (2), respectively (however ^{, at least one of R 61} to R ⁶⁵ is a group represented by the formula (2)).
    R ⁶⁶ is a hydrogen atom, an N, N-diarylamino group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or It is a heteroaryl group that may have a substituent];
    Compound represented by the following formula (7):
    

    

    [During the ceremony,
    X ⁷¹ to X ⁷⁶ are -N = or -C (R ⁷⁹ ) =, respectively.
    R ⁷¹ to R ⁷⁴ and R ⁷⁹ each have a hydrogen atom, an N, N-diarylamino group which may have a substituent, a cycloalkyl group which may have a substituent, and a substituent, respectively. It is an aryl group that may be present, or a heteroaryl group that may have a substituent, and is
    R ⁷⁵ to R ⁷⁸ are hydrogen atoms or groups represented by the formula (2) (provided ^{that at least one of R 75} to R ⁷⁸ is a group represented by the formula (2))]; Compound represented by the following formula (8):
    

    

    [During the ceremony,
    X ⁸¹ to X ⁸⁶ are −N = or −C (R ⁸⁹ ) =, respectively.
    R ⁸¹ to R ⁸⁴ and R ⁸⁹ each have a hydrogen atom, an N, N-diarylamino group which may have a substituent, a cycloalkyl group which may have a substituent, and a substituent, respectively. It is an aryl group that may be present, or a heteroaryl group that may have a substituent, and is
    R ⁸⁵ to R ⁸⁸ are hydrogen atoms or groups represented by the formula (2) (however ^{, at least one of R 85} to R ⁸⁸ is a group represented by the formula (2))].
    The compound according to claim 1, which is selected from the group consisting of.
11. A delayed fluorescent material containing the compound according to any one of claims 1 to 10.
12. An organic light emitting device containing the compound according to any one of claims 1 to 10.
13. The organic light emitting element according to claim 12, which is an organic EL element.
14. The following formula (9):
    

    

    (During the ceremony,
    R ⁹¹ and R ⁹⁴ are perfluoroalkyl groups or cyano groups, respectively.
    R ⁹² and R ⁹³ are an alkyl group, an alkoxy group, a trialkylsilyl group, an N, N-diarylamino group which may have a substituent, and a cycloalkyl group which may have a substituent, respectively. An aryl group which may have a substituent or a heteroaryl group which may have a substituent.
    Z ⁹ is absent, single bond, -C (R ⁹⁵ ) (R ⁹⁶ )-, -O-, -S-, or -N (R ⁹⁷ )-, and
    R ⁹⁵ to R ⁹⁷ are a hydrogen atom, an electron attracting group, or an electron donating group, respectively)
    Compounds represented by (where Z ⁹ is absent, R ⁹¹ and R ⁹⁴ are trifluoromethyl groups, R ⁹² and R ⁹³ are methoxy groups, and Z ⁹ is absent. , R ⁹¹ and R ⁹⁴ are cyano groups, and R ⁹² and R ⁹³ are phenyl groups).

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