Nitrogen-containing heterocyclic compound and its use

Abstract

To provide a technique regarding a nitrogen-containing heterocyclic compound having excellent luminous efficiency and durability and use thereof.SOLUTION: A nitrogen-containing heterocyclic compound according to the present invention is a compound represented by the formula: Cz-L-Ar (1) [in the formula (1), Cz is a group represented by the formula (2) (in the formula (2), Z denotes a single bond or the like, R22 and R27 each denote an electron-withdrawing group, R23 and R26 each denote an electron-donating group, R21, R24, R25, and R28 each denote H, an electron-withdrawing group, or an electron-donating group, a wave line denotes a binding site to L), L denotes a single bond or a phenylene group, Ar denotes a group selected from the group consisting of an aryl group and a heteroaryl group].SELECTED DRAWING: None

Description

Technical Field

[0001] Techniques related to nitrogen-containing heterocyclic compounds and their uses are disclosed.

Background Art

[0002] Searching for luminescent materials for organic light-emitting devices such as Organic Light Emitting Diodes (OLEDs) is underway. As luminescent materials, various characteristics such as emission color (e.g., emission peak wavelength, full width at half maximum), luminous efficiency, and durability are required to be favorable. Among the luminescent materials for OLEDs, compounds showing Thermally Activated Delayed Fluorescence (TADF) are expected as next-generation luminescent materials because they show high luminous efficiency while being pure organic substances.

[0003] As a TADF material, for example, Patent Document 1 describes the following formula:

Chem.

Chem.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] Although the compounds described in Patent Documents 1 and 2 are useful as TADF materials, there is room for improvement in terms of luminescence efficiency and durability. The main object of the present invention is to provide a technology related to a nitrogen-containing heterocyclic compound excellent in luminescence efficiency and durability and its use.

Means for Solving the Problems

[0006] As a result of intensive studies to solve the above problems, the present inventors have found that by adopting the structure represented by the following formula (1) as the structure of the compound, the luminescence efficiency and durability can be improved: Cz-L-Ar (1) [In the formula, Cz is represented by the following formula (2):

Chemical formula

[0007] The present invention includes the following aspects. Item 1. A compound represented by the following formula (1): Cz-L-Ar (1) [wherein, Cz is the following formula (2): [Chemical formula] (wherein, Z is absent, a single bond, -C(R 29a )(R 29b )-, -O-, -S-, or -N(R 29c )-, R 22 and R 27 are each an electron-withdrawing group, R 23 and R 26 are each an electron-donating group, R 21 , R 24 , R 25 , R 28 , R 29a , R 29b , and R 29c are each a hydrogen atom, an electron-withdrawing group, or an electron-donating group, The wavy line indicates the bonding site with L) is a group represented by, L is a single bond or a phenylene group which may have a substituent, Ar is a group selected from the group consisting of an aryl group and a heteroaryl group, and the group may have at least one substituent selected from 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, and a heteroaryl group which may have a substituent (however, Ar is not a group represented by formula (2)). Item 2. The compound according to item 1, wherein Ar is a group selected from the group consisting of a phenyl group, a condensed bicyclic to hexacyclic aryl group, and a nitrogen-containing heteroaryl group, and the group may have at least one substituent selected from 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, and a heteroaryl group which may have a substituent (however, Ar is not a group represented by formula (2)). Item 3. Ar is a group represented by the following formula (3):

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chem.

Chem.

Chem.

Chemical formula

Advantages of the Invention

[0008] According to the present invention, a technique related to a nitrogen-containing heterocyclic compound excellent in luminous efficiency and durability and its use is provided.

Brief Description of the Drawings

[0009]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Figure 10

Figure 11

Figure 12

Figure 13

Figure 14

Figure 15

Figure 16

Figure 17

Figure 18

Figure 19

Figure 20

Figure 21

Figure 22

Figure 23

Figure 24

Figure 25

Figure 26

Figure 27

Figure 28

Figure 29

Figure 30

Figure 31

Figure 32

Figure 33

Figure 34

Figure 35

Figure 36

Figure 37

Figure 38

Figure 39

Figure 40

Figure 41

Mode for Carrying Out the Invention

[0010] <Definition> In this specification, unless otherwise specified, the "halogen atom" is used to mean an atom including a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.

[0011] In this specification, unless otherwise specified, the "alkyl group" means a linear or branched saturated hydrocarbon group. Specifically, for example, C alkyl groups such as a methyl group, an ethyl group, a propyl group (n-propyl group, isopropyl group), a butyl group (n-butyl group, isobutyl group, sec-butyl group, tert-butyl group), a pentyl group, a hexyl group, etc. 1-20 can be mentioned.

[0012] In this specification, unless otherwise specified, the "perfluoroalkyl group" means a group in which all hydrogen atoms of the alkyl group are substituted by fluorine atoms. Specifically, for example, perfluoro C alkyl groups such as a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group (heptafluoro n-propyl group or heptafluoro i-propyl group), etc. 1-12 can be mentioned.

[0013] In this specification, unless otherwise specified, the "alkoxy group" means a group in which an oxygen atom is bonded to the end of the alkyl group. Specifically, for example, C alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group (n-propoxy group, isopropoxy group), a butoxy group (n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group), etc. 1-12 can be mentioned.

[0014] In this specification, unless otherwise specified, the "alkylsulfanyl group" means a group in which a sulfur atom is bonded to the end of the alkyl group. Specifically, for example, C alkylsulfanyl groups such as a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group (n-propylsulfanyl group, isopropylsulfanyl group), a butylsulfanyl group, etc. 1-12 can be mentioned.

[0015] In this 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. Specifically, for example, (C 1-12 alkyl)carbonyl groups such as methylcarbonyl group, ethylcarbonyl group, propylcarbonyl group (n-propylcarbonyl group, isopropylcarbonyl group), butylcarbonyl group, etc. are included.

[0016] In this 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. Specifically, for example, C 1-12 alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group (n-propylsulfonyl group, isopropylsulfonyl group), butylsulfonyl group, etc. are included.

[0017] In this specification, unless otherwise specified, the "cycloalkyl group" means cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, etc. 5-20 alkyl groups are included.

[0018] In this specification, unless otherwise specified, the "trialkylsilyl group" means a group in which three of the above alkyl groups are bonded to a silicon atom. Specifically, for example, triC 1-4 alkylsilyl groups such as trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, tert-butyldimethylsilyl group, etc. are included.

[0019] In this specification, unless otherwise specified, the "aromatic ring" is used to mean including an arene ring and a heteroarene ring.

[0020] 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 still more preferably 6 to 26. The arene ring is preferably a benzene ring or a condensed 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 tetraphene ring, a chrysene ring, a triphenylene ring, a pyrene ring, a benzopyrene ring, a perylene ring, a coronene ring, a corannulene ring, a phenalene ring, and a triangulene ring.

[0021] The number of ring-constituting atoms in the heteroarene ring is not particularly limited, but is, for example, 5-membered to 40-membered. The heteroarene ring may be monocyclic or polycyclic (e.g., bicyclic to tetracyclic). 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 (e.g., furan ring, benzofuran ring, dibenzo[b,d]furan ring), a sulfur-containing heteroarene ring (e.g., thiophene ring, benzothiophene ring, dibenzo[b,d]thiophene ring), a nitrogen-containing heteroarene ring (e.g., 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-triazine ring, indole ring, indazole ring, benzimidazole ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phthalazine ring, naphthyridine ring, purine ring, acridine ring, 9,10-dihydroacridine ring, phenazine ring, 5,10-dihydrophenazine ring, phenanthridine ring, phenanthroline ring, acenaphtho[1,2-b]pyrazine ring), an oxygen- and nitrogen-containing heteroarene ring (e.g., oxazole ring, isoxazole ring, benzoxazole ring, phenoxazine ring), and a sulfur- and nitrogen-containing heteroarene ring (e.g., thiazole ring, isothiazole ring, benzothiazole ring, phenothiazine ring).

[0022] An aryl group is a group formed by removing one hydrogen atom from an aromatic hydrocarbon ring (arene ring) among the aforementioned aromatic rings. The aryl group may be a monocyclic aryl group or a condensed-ring aryl group (for example, a condensed bi- to hexacyclic aryl group). Examples of the monocyclic aryl group include a phenyl group. Examples of the condensed-ring aryl group include a naphthyl group, a fluorenyl group, an anthracenyl group, a triphenylenyl group, and a pyrenyl group. As the aryl group, C 6-18 The aryl group is preferred.

[0023] A heteroaryl group is a group formed by removing one hydrogen atom from an aromatic heterocyclic ring (heteroarene ring) among the aforementioned aromatic rings. The heteroaryl group may be a monocyclic heteroaryl group (for example, a 5- or 6-membered monocyclic heteroaryl group) or a condensed-ring heteroaryl group (for example, a condensed bi- to hexacyclic aryl group). Examples of the monocyclic heteroaryl group include monocyclic oxygen-containing heteroaryl groups such as a furyl group; monocyclic sulfur-containing heteroaryl groups such as a thienyl group; monocyclic nitrogen-containing heteroaryl groups such as a pyrrolyl group, a pyrazolyl group, an imidazolyl group, a triazyl group, a pyridyl group, a pyridazyl group, a pyrimidinyl group, a pyrazyl group, and a triazinyl group. Examples of the condensed-ring heteroaryl group include condensed-ring oxygen-containing heteroaryl groups such as a benzofuryl group and a dibenzofuryl group; condensed-ring sulfur-containing heteroaryl groups such as a benzothienyl group and a dibenzothienyl group; condensed-ring nitrogen-containing heteroaryl groups such as an indolyl group, a quinolyl group, an isoquinolyl group, a carbazolyl group, an acridyl group, a 9,10-dihydroacridyl group, a phenazinyl group, and a 5,10-dihydrophenazinyl group; condensed-ring oxygen- and nitrogen-containing heteroaryl groups such as a phenoxazinyl group; and condensed-ring sulfur- and nitrogen-containing heteroaryl groups such as a phenothiazinyl group.

[0024] In this specification, unless otherwise specified, the "electron-donating group (donor group)" represents a group with a negative Hammett's σp. For the explanation of Hammett's σp and the numerical values of each group, reference can be made to Hansch, C. et al., Chem. Rev., 91, 165 - 195 (1991). Examples of electron-donating groups include alkyl groups such as methyl group, isopropyl group, tertiary butyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group, naphthyl group, anthracenyl group, triphenylenyl group, pyrenyl group, fluorenyl group, alkoxy groups such as methoxy group, alkylsulfanyl groups such as methionyl group, trialkylsilyl groups such as trimethylsilyl group, heteroaryl groups such as pyridyl group, imidazolyl group, pyrazolyl group, oxazolyl group, thiazolyl group, indolyl group, pyrrolyl group, quinolyl group, benzofuryl group, dibenzofuryl group, benzothienyl group, dibenzothienyl group, carbazolyl group, 9,10-dihydroacridyl group, 5,10-dihydrophenazinyl group, phenoxazinyl group, phenothiazinyl group, and N,N-diarylamino groups such as N,N-diphenylamino group.

[0025] In this specification, unless otherwise specified, the "electron-withdrawing group (acceptor group)" means a group other than an electron-donating group, and examples include alkylcarbonyl groups (acyl groups), alkylsulfonyl groups, perfluoroalkyl groups, cyano groups, and nitro groups.

[0026] <Compound> In one embodiment, the compound of the present invention is preferably a compound represented by the following formula (1): Cz-L-Ar (1) [wherein, Cz is represented by the following formula (2):

Chemical formula

[0027] Cz (Formula (2)) Z is preferably a single bond, -C(R 29a )(R 29b )-, -O-, -S-, or -N(R 29c )-, and more preferably a single bond.

[0028] The inventors have found that in formula (2), when R 22 and R 27 are electron-withdrawing groups, and R 23 and R 26 are electron-donating groups, then when R 22 and R 27 are electron-withdrawing groups, and R 23 and R 26 are hydrogen atoms, as well as when R 22 and R 27 are hydrogen atoms and R 23 and R26 It has been found that the full width at half maximum of the emission peak can be made even narrower as compared with the case where it is an electron-donating group.

[0029] R 22 、R 27 、and R 21 、R 24 、R 25 、R 28 、and R 29a ~R 29c When R 22 to R 29c are electron-withdrawing groups, each of the electron-withdrawing groups is preferably a perfluoroalkyl group or a cyano group, more preferably a perfluoroC 1-4 alkyl group or a cyano group, even more preferably a perfluoroC 1-3 alkyl group or a cyano group, even more preferably a perfluoroC 1-2 alkyl group or a cyano group, particularly preferably a trifluoromethyl group or a cyano group.

[0030] R 23 、R 26 、and R 21 、R 24 、R 25 、R 28 、and R 29a ~R 29c When R 23 to R 29c are electron-donating groups, each of the electron-donating groups is preferably 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 an aryl group which may have a substituent, a heteroaryl group which may have a substituent, more preferably a C 1-6 alkyl group, a C 1-6 alkoxy group, a triC 1-6 alkylsilyl group, an N,N-diC 6-18 arylamino group which may have a substituent, a C 5-12 cycloalkyl group which may have a substituent, a C6-18 an aryl group, a 5- or 6-membered monocyclic heteroaryl group which may have a substituent, or a condensed bicyclic to tetracyclic heteroaryl group which may have a substituent, more preferably C 1-4 an alkyl group, C 1-4 an alkoxy group, triC 1-4 an alkylsilyl group, an N,N-diarylamino group which may have a substituent, C 6-14 an arylamino group, C 5-7 a cycloalkyl group, C 6-14 an aryl group, a 5- or 6-membered monocyclic nitrogen-containing heteroaryl group which may have a substituent, or a condensed bicyclic to tetracyclic nitrogen-containing heteroaryl group which may have a substituent. The substituent which the N,N-diarylamino group optionally has is preferably an electron-withdrawing group and an electron-donating group. The substituent which the cycloalkyl group, the aryl group, and the heteroaryl group optionally have is preferably an aryl group or a heteroaryl group, more preferably an aryl group, still more preferably C 6-12 an aryl group, particularly preferably C 6-10 an aryl group. It is also preferable that the substituent which the heteroaryl group optionally has is an electron-withdrawing group and an electron-donating group. The number of the substituents is, for example, 0, 1, 2, 3, or 4. It is also preferable that the electron-donating group is a group represented by the formula (2).

[0031] R 21 、R 24 、R 25 、and R 28 The combination of is as follows: R 21 、R 24 、R 25 、and R 28 is a combination in which they are hydrogen atoms; or R 21 and R 28 are each an electron-donating group, and R 24 and R 25 are each an electron-withdrawing group. is preferable.

[0032] The group represented by formula (2) is preferably a group selected from the following group: [Chemical formula] (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 the wavy line indicates the bonding site with L).

[0033] Ar Ar is preferably a group selected from an aryl group and a heteroaryl group (however, it is not the group represented by formula (2)), more preferably a group selected from a C 6-18 aryl group, a 5- or 6-membered monocyclic heteroaryl group, and a condensed bicyclic to tetracyclic heteroaryl group (however, it is not the group represented by formula (2)), even more preferably a group selected from a C 6-16 aryl group, a 5- or 6-membered monocyclic nitrogen-containing heteroaryl group, and a condensed bicyclic to tetracyclic nitrogen-containing heteroaryl group (however, it is not the group represented by formula (2)). These groups may have at least one substituent selected from a N,N-diarylamino group which may have a substituent (for example, the group represented by formula (2) where Z is absent), a cycloalkyl group which may have a substituent (preferably a C 5-12 cycloalkyl group), an aryl group which may have a substituent (preferably a C 6-12 aryl group), and a heteroaryl group which may have a substituent (preferably a 5- or 6-membered monocyclic heteroaryl group, or a condensed bicyclic to tetracyclic heteroaryl group) (for example, the group represented by formula (2) where Z is other than absent). The substituents optionally possessed by the cycloalkyl group, aryl group, and heteroaryl group are not particularly limited. For example, they may be an aryl group (for example, a C 6-12 aryl group) or a heteroaryl group (for example, a 5- or 6-membered monocyclic heteroaryl group, a condensed bicyclic to tetracyclic heteroaryl group), or may be the group represented by formula (2).

[0034] Ar is preferably a group represented by the following formula (3):

Chemical formula

[0035] In formula (3), as the combination of X 31 ~X 35 are: X 31 , X 33 , and X 35 are -N=, and X 32 and X 34 are -C(R 3 )=; X 31 and X 35 are -N=, and X 32 ~X 34 are -C(R 3 )=; or X 31 ~X 35 are -C(R 3 )= is preferred.

[0036] R 3 is preferably a hydrogen atom, an N,N-diC which may have a substituent 6-12 aryl amino group (for example, the group represented by formula (2) where Z is absent), a C which may have a substituent 5-12 cycloalkyl group, a C which may have a substituent 6-12 aryl group, a 5- or 6-membered monocyclic heteroaryl group which may have a substituent, a condensed bicyclic to tetracyclic heteroaryl group which may have a substituent (for example, the group represented by formula (2) where Z is other than absent). Examples of the said substituent include, for example, an aryl group (for example, a C 6-12 aryl group) or a heteroaryl group (for example, a 5- or 6-membered monocyclic heteroaryl group, a condensed bicyclic to tetracyclic heteroaryl group), and may also be a group represented by formula (2).

[0037] When two Rs which can exist in an ortho positional relationship to each other in the group represented by formula (3) are bonded to each other to form an aromatic ring, for example, it may be a group represented by the following formula (3a) or (3b): 3 : [Chemical formula] (In the formula, X 36 ~X 39 are each -N= or -C(R 3 )=, and X 31 ~X 33 , X 35 , and R 3 are the same as those described above).

[0038] In formula (3a), as the combination of X 31 ~X 33 and X 36 ~X 39 , the combination where X 31 ~X 33 is -C(R 3 )= and X 36 ~X 39 is -N= or -C(R 3 )= is preferable, X 31 ~X33 and X 36 ~X 38 is -C(R 3 )=, and X 39 is -N=; or X 31 ~X 33 and X 36 ~X 39 is -C(R 3 )= is more preferable.

[0039] In formula (3b), the combination of X 31 , X 32 , and X 35 ~X 39 is preferably a combination where X 31 , X 32 , and X 35 is -C(R 3 )=, and X 36 ~X 39 is -N= or -C(R 3 )=; X 31 , X 32 and X 35 ~X 38 is -C(R 3 )=, and X 39 is -N=; or X 31 , X 32 and X 35 ~X 39 is -C(R 3 )= is more preferable.

[0040] The group represented by formula (3) is preferably a group represented by any of the following formulas (3-1) to (3-4):

Chemical formula

[0041] R 311 、R 312 、R 321 ~R 323 、R 331 ~R 336 、and R 341 ~R 346 are each preferably a hydrogen atom, an N,N-diC 6-12 arylamino group which may have a substituent (for example, the group represented by formula (2) where Z is absent), a C 5-12 cycloalkyl group which may have a substituent, a C 6-12 aryl group, a 5- or 6-membered monocyclic heteroaryl group which may have a substituent, a condensed bicyclic to tetracyclic heteroaryl group which may have a substituent (for example, the group represented by formula (2) where Z is other than absent). Examples of the substituent include an aryl group (for example, a C 6-12 aryl group) or a heteroaryl group (for example, a 5- or 6-membered monocyclic heteroaryl group, a condensed bicyclic to tetracyclic heteroaryl group), and may also be a group represented by formula (2).

[0042] L When L is a phenylene group which may have a substituent, the phenylene group may be any of a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group. The substituent is preferably 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 an N,N-diC 6-18 arylamino group which may have a substituent, a C 6-18An aryl group, a 5- or 6-membered monocyclic heteroaryl group which may have a substituent, or a condensed bicyclic to tetracyclic heteroaryl group which may have a substituent, More preferably, it is a group represented by formula (2) or a group represented by formula (3). The number of the substituents is, for example, 0, 1, 2, 3, or 4.

[0043] In one embodiment, the compound represented by formula (1) is preferably a compound in which L is a single bond, more preferably a compound in which the group represented by formula (2) having a maximum number of one or more substituents is substituted on Ar, and even more preferably a compound represented by the following formula (4):

Chemical formula

[0044] X 41 ~X 43 As the combination of, X 41 ~X 43 is a combination in which it is -N=; or X 41 ~X 43 Among them, a combination in which any two are -N= and the remaining one is -C(R 44 )= is preferred.

[0045] R 41 ~R 44is each preferably a hydrogen atom, an N,N-diC which may have a substituent 6-12 aryl amino group (for example, the group represented by formula (2) where Z is absent), a C which may have a substituent 5-12 cycloalkyl group, a C which may have a substituent 6-12 aryl group, a 5- or 6-membered monocyclic heteroaryl group which may have a substituent, or a condensed bicyclic to tetracyclic heteroaryl group which may have a substituent (for example, the group represented by formula (2) where Z is other than absent). Examples of the said substituent include, for example, an aryl group (for example, a C 6-12 aryl group) or a heteroaryl group (for example, a 5- or 6-membered monocyclic heteroaryl group, a condensed bicyclic to tetracyclic heteroaryl group), or may be a group represented by formula (2).

[0046] The compound represented by formula (4) is preferably a compound represented by the following formula (4-1) or (4-2):

Chemical formula

[0047] In one embodiment, the compound represented by formula (1) is preferably a compound in which L is a phenylene group which may have a substituent, more preferably a compound in which one or more Ar and one or more groups represented by formula (2) are substituted on the benzene ring (the total number of substituents of Ar and the group represented by formula (2) is 2 or more and 6 or less), still more preferably a compound in which one Ar and one or more and five or less groups represented by formula (2) are substituted on the benzene ring, and particularly preferably a compound represented by the following formula (5):

Chemical formula

[0048] X 51 ~X 53 As the combination of, X 51 ~X 53 is a combination where -N=; or X 51 is -C(R 58 ) =, and X 52 and X 53 is a combination where -N= is preferred.

[0049] R 51 R 52 , and R 58 are each preferably a hydrogen atom, an N,N-diC 6-12 arylamino group (for example, a group represented by formula (2) where Z is absent), a C 5-12 cycloalkyl group which may have a substituent, a C 6-12 aryl group which may have a substituent, a 5- or 6-membered monocyclic heteroaryl group which may have a substituent, or a condensed bicyclic to tetracyclic heteroaryl group which may have a substituent (for example, a group represented by formula (2) where Z is other than absent). Examples of the said substituent may be an aryl group (for example, a C 6-12 aryl group) or a heteroaryl group (for example, a 5- or 6-membered monocyclic heteroaryl group, a condensed bicyclic to tetracyclic heteroaryl group), and may also be a group represented by formula (2).

[0050] The compound represented by formula (5) is preferably a compound represented by any of the following formulas (5-1) to (5-14):

Chemical formula

[0051] In one embodiment, the compound represented by formula (1) is preferably a compound represented by the following formula (6):

Chemical formula

[0052] X 61 ~X 67 As the combination of X 61 ~X 65 , and X 67 is -C(R 66 )= and X 66 is -N=; or X 61 ~X 67 is -C(R 58) = is a combination is preferred.

[0053] R 66 is preferably a hydrogen atom, an N,N - diC which may have a substituent 6-12 aryl amino group (for example, the group represented by formula (2) where Z is absent), a C which may have a substituent 5-12 cycloalkyl group, a C which may have a substituent 6-12 aryl group, a 5 - or 6 - membered monocyclic heteroaryl group which may have a substituent, or a condensed bicyclic to tetracyclic heteroaryl group which may have a substituent (for example, the group represented by formula (2) where Z is other than absent). Examples of the said substituent include, for example, an aryl group (for example, a C 6-12 aryl group) or a heteroaryl group (for example, a 5 - or 6 - membered monocyclic heteroaryl group, a condensed bicyclic to tetracyclic heteroaryl group), and may also be a group represented by formula (2).

[0054] The compound represented by formula (6) is preferably a compound represented by the following formula (6 - 1):

Chemical formula

[0055] In one embodiment, the compound represented by formula (1) is preferably a compound in which L is a phenylene group which may have a substituent, more preferably a compound in which two Ar and one or more and four or less groups represented by formula (2) are substituted on the benzene ring, and even more preferably a compound represented by the following formula (7):

Chemical formula

[0056] X 71 ~X 76 The combinations of X 71 ~X 76 being -N=; or X 71 X 73 X 74 and X 76 being -N=, and X 72 and X 75 being -C(R 79 )= are preferred. is preferred.

[0057] R 71 ~R 74 and R 79 each preferably represents a hydrogen atom, an N,N-diC 6-12 arylamino group which may have a substituent (for example, a group represented by formula (2) where Z is absent), a C 5-12 cycloalkyl group which may have a substituent, a C 6-12 aryl group which may have a substituent, a 5- or 6-membered monocyclic heteroaryl group which may have a substituent, or a condensed bicyclic to tetracyclic heteroaryl group which may have a substituent (for example, a group represented by formula (2) where Z is other than absent). Examples of the said substituent include an aryl group (for example, a C 6-12 aryl group) or a heteroaryl group (for example, a 5- or 6-membered monocyclic heteroaryl group, a condensed bicyclic to tetracyclic heteroaryl group), and may also be a group represented by formula (2).

[0058] The compound represented by formula (7) is preferably a compound represented by any of the following formulas (7-1) to (7-3):

Chemical formula

[0059] In one embodiment, the compound represented by formula (1) is preferably a compound represented by the following formula (8):

Chemical formula

[0060] X 81 ~X 86 As the combination of, X 81 ~X 86 is a combination where it is -N=; or X 81 、X 83 、X 84 、and X86 is -N=, and X 82 and X 85 is -C(R 89 )= is a preferred combination is preferred.

[0061] R 81 ~R 84 and R 89 are each preferably a hydrogen atom, an N,N - diC 6-12 aryl amino group which may have a substituent (for example, a group represented by formula (2) where Z is absent), a C 5-12 cycloalkyl group which may have a substituent, a C 6-12 aryl group which may have a substituent, a 5 - or 6 - membered monocyclic heteroaryl group which may have a substituent, or a condensed bicyclic to tetracyclic heteroaryl group which may have a substituent (for example, a group represented by formula (2) where Z is other than absent). Examples of the said substituent include, for example, an aryl group (for example, a C 6-12 aryl group) or a heteroaryl group (for example, a 5 - or 6 - membered monocyclic heteroaryl group, a condensed bicyclic to tetracyclic heteroaryl group), or a group represented by formula (2).

[0062] The compound represented by formula (8) is preferably a compound represented by any of the following formulas (8 - 1) to (8 - 6):

Chemical formula

[0063] The full - width at half - maximum of the emission peak of the compound of the present invention is preferably 90 nm or less, more preferably 85 nm or less, still more preferably 80 nm or less, and may also be 10 nm or more. The full - width at half - maximum is measured for a solution (concentration: 1×10 -5It can be determined by measuring the emission spectrum when the excitation light of 340 nm is irradiated on (M) at room temperature. In the emission spectrum, the spectral width at half the peak top intensity is defined as the full width at half maximum (FWHM).

[0064] The luminescence efficiency (PLQY) of the compound of the present invention is preferably 50% or more, more preferably 55% or more, and still more preferably 60% or more. The luminescence efficiency (PLQY) is the value when the solution (concentration: 1×10 -5 M) is irradiated with excitation light of 340 nm at room temperature, and can be measured using an absolute PL quantum yield measuring device (for example, Quantaurus-QY C11347-01 manufactured by Hamamatsu Photonics K.K.).

[0065] 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 may also be -7.0 eV or more, -6.5 eV or more, or -6.4 eV or more. Due to such a HOMO level, the 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.).

[0066] The orientation parameter S of the compound of the present invention may preferably be 0.002 or more, 0.003 or more, 0.004 or more, or 0.005 or more, and may also be 0.05 or less from the viewpoint of luminescence efficiency. The orientation parameter S is obtained by preparing a single film (film thickness: about 30 nm) of the luminescent material on a bare silicon substrate, performing spectral measurement in the range of 45 to 75 degrees (in 5-degree increments) using a spectroscopic ellipsometer (product of J.A. Woollam Japan), and calculating by fitting analysis of the obtained spectrum.

[0067] The oxidation-reduction characteristic ΔE of the compound of the present invention is preferably 0.1 eV or less, 0.08 eV or less, 0.06 eV or less, or 0.05 eV or less, and may be 0.01 eV or more, from the viewpoint of durability. 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 / AgNO3 acetonitrile solution Solvent: THF Electrolyte: Bu4NPF6 Sweeping rate: 50 meV / s Concentration of luminescent material: 1 mM Concentration of electrolyte: 100 mM

[0068] Method for producing the compound represented by formula (1) The compound represented by formula (1) is not particularly limited. For example, the following formula (11):

Chemical formula

[0069] Compound represented by formula (11) The compound represented by formula (11) can be produced by a combination of known reactions. For example, the compound represented by formula (11) can be obtained from the following formula (13): [Chemical formula] (wherein Q 2 and Q 3 are each a halogen atom, and R 21 , R 22 , R 24 , R 25 , R 27 , and R 28 are the same as defined above) and the compound represented by the following formula (14): [Chemical formula] (wherein R 23 is the same as defined above) and the compound represented by the following formula (15): [Chemical formula] (wherein R 26 is the same as defined above) through a process that includes reacting them.

[0070] In formula (13), Q 2 and Q 3 may be the same or different from each other, and are preferably each a fluorine atom, a chlorine atom, or a bromine atom.

[0071] In formulas (14) and (15), -B(OH)2 may be a group represented by the following formula: [Chemical formula]

[0072] ​The total amount of the compounds represented by Formula (14) and (15) is preferably 2 moles or more, 2.5 moles or more, or 3 moles or more, and preferably 6 moles or less, 5 moles or less, or 4 moles or less, per 1 mole of the compound represented by Formula (13).

[0073] The reaction is preferably carried out in the presence of a catalyst. Examples of the catalyst include transition metal catalysts, and specific examples thereof include palladium catalysts, copper catalysts, nickel catalysts, cobalt catalysts and the like. These catalysts can be used alone or in combination of two or more. When using these catalysts, reference can be made to International Publication No. 2011 / 08902, International Publication No. 2015 / 137472, etc.

[0074] The reaction is preferably carried out in the presence of a base. Examples of the base include n-butyllithium, NaH, sodium t-butoxide, KOH, K2CO3, K3PO4, potassium t-butoxide, potassium acetate, Cs2CO3 and the like. These bases can be used alone or in combination of two or more. When using these bases, reference can be made to International Publication No. 2008 / 117826, Chemistry of Materials, 2010, 22(7), 2403~2410, Korean Patent Application Publication No. 2018-063708, etc.

[0075] The reaction is preferably carried out in the presence of a solvent. The solvent is not particularly limited as long as it can dissolve the reaction components, and examples thereof include ethers (e.g., diethyl ether, dipropyl ether, dibutyl ether, 1,4-dioxane, tetrahydrofuran), aromatic hydrocarbons (e.g., toluene, xylene), amines (e.g., chain amines such as triethylamine, cyclic amines such as N-methylpyrrolidone), amides (e.g., dimethylformamide), sulfoxides (e.g., dimethyl sulfoxide) and the like. The solvent can be used alone or as a mixture of two or more.

[0076] 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, and may also be 200°C or lower, 150°C or lower, or 100°C or lower. The reaction time may be, for example, 1 hour or longer, 2 hours or longer, or 5 hours or longer, and may also be 50 hours or shorter, 30 hours or shorter, or 10 hours or shorter.

[0077] Compound represented by formula (12) Q 1 is preferably a fluorine atom, a chlorine atom, or a bromine atom.

[0078] The compound represented by formula (12) can be produced by a combination of known reactions. For example, among the compounds represented by formula (12), a compound in which L is a single bond can be used as a commercially available product as it is, and a compound in which L is a phenylene group which may have a substituent is represented by 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 -L-B(OH)2(17) (wherein L and Q 1 are the same as above) can be produced by a method including a step of reacting with the compound represented by the formula.

[0079] In formula (17), -B(OH)2 may be a group represented by the following formula:

Chemical formula

[0080]

[0081] Reaction between the compound represented by formula (11) and the compound represented by formula (12) ​For this reaction, reaction conditions similar to those for the reactions of the compounds represented by formulas (13) to (15) can be adopted. The reaction of the compounds represented by formulas (11) and (12) may be a reaction (one-pot reaction) in which, after reacting the compounds represented by formulas (13) to (15), the compound represented by formula (12) is subsequently reacted (without purifying the compound represented by formula (11)), or may be a reaction (one-pot reaction) in which, after reacting the compounds represented by formulas (16) and (17), the compounds represented by formulas (13) to (15) are subsequently reacted (without purifying the compound represented by formula (12)).

[0082] <Delayed fluorescence material> In one embodiment, the delayed fluorescence material of the present invention preferably contains the compound of the present invention. The delayed fluorescence material can be suitably used, for example, as a light-emitting material for an organic light-emitting device described below.

[0083] <Organic light-emitting device> In one embodiment, the organic light-emitting device of the present invention preferably contains the compound of the present invention.

[0084] Examples of the organic light-emitting device include an organic photoluminescence device (organic PL device), an organic electroluminescence device (organic EL device), and the like. The organic light-emitting device is preferably an organic EL device.

[0085] The organic EL device preferably has an anode, a cathode, and an organic layer formed between the anode and the cathode.

[0086] The organic layer preferably contains at least a light-emitting layer, and may consist only of the light-emitting layer, or may contain one or more other organic layers in addition to the light-emitting layer. Examples of the other organic layers include an injection layer (e.g., a hole injection layer, an electron injection layer), a blocking layer (e.g., an electron blocking layer, a hole blocking layer, an exciton blocking layer), a transport layer (e.g., a hole transport layer, an 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.

[0087] The organic EL element may be of a bottom emission type that extracts the light generated in the light emitting layer from the substrate side, or may be of a top emission type that extracts the light generated in the light emitting layer from the side opposite to the substrate. In either type, the electrode formed on the substrate side may be an anode or a cathode. The electrode on the side where the light is extracted is preferably transparent, and the electrode on the opposite side may or may not be transparent.

[0088] The organic EL element is preferably supported by a substrate. There are no particular restrictions on the substrate, and any substrate that has been conventionally used for organic EL elements may be used. For example, substrates made of glass, transparent plastic, quartz, silicon, etc. can be used.

[0089] As the anode in the organic EL element, those using metals, alloys, electrically conductive compounds, and mixtures thereof having a large work function (e.g., 4 eV or more) as electrode materials 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), SnO2, and ZnO. Also, materials capable of forming an amorphous and transparent conductive film such as IDIXO (In2O3-ZnO) may be used. The anode may form a thin film by a method such as vapor deposition or sputtering of the electrode material and form a pattern of a desired shape by photolithography, or may form a pattern through a mask of a desired shape during vapor deposition or sputtering of the electrode material. Alternatively, when a material that can be applied such as an organic conductive compound is used, wet film formation methods such as printing or coating can also be used. When extracting light from the anode, it is desirable to make the transmittance greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / sq or less. The film thickness of the anode varies depending on the material, but is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.

[0090] As the cathode, those using a metal (electron-injecting metal), alloy, electrically conductive compound, or a mixture thereof with a small work function (e.g., 4 eV or less) as the electrode material are 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 (Al2O3) mixture, lithium / aluminum mixture, aluminum, etc. The cathode can be fabricated by forming a thin film of the electrode material by methods such as evaporation or sputtering. Also, the sheet resistance as the cathode is preferably several hundred Ω / sq 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. Note that it is preferable if either the anode or the cathode of the organic EL element is transparent or semi-transparent in order to improve the emission luminance. Also, a transparent or semi-transparent cathode can be fabricated by using the transparent conductive material mentioned in the description of the anode for the cathode, and an element in which both the anode and the cathode have permeability can be fabricated.

[0091] The light-emitting layer is preferably a layer that emits light (e.g., fluorescence, delayed fluorescence, or both) after excitons are generated by the recombination of holes and electrons injected from the anode and the cathode, respectively. 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 (one or more) of the present invention 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 singlet excitation energy and the triplet excitation energy has a higher value than the compound of the present invention. Also, the host material is preferably an organic compound having hole-transporting ability, electron-transporting ability, preventing the emission wavelength from shifting to a longer wavelength, and having a high glass transition temperature.

[0092] Furthermore, when a compound exhibiting thermally activated delayed fluorescence (TADF) is included in a light-emitting layer containing a host material and a light-emitting material as a third component (assist dopant compound), it is effective for achieving high luminous efficiency (H. Nakanotani, et al., Nature Communicaion, 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 can generate singlet excitons with reverse intersystem crossing (RISC). The energy of the singlet excitons is transferred to the light-emitting material, enabling the light-emitting material to emit light. Therefore, theoretically, it is possible to cause the light-emitting material to emit light using 100% of the exciton energy, resulting in high luminous efficiency.

[0093] 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, more preferably 20% by mass or less, and even more preferably 10% by mass or less.

[0094] The injection layer is preferably a layer provided between the electrode and the organic layer to reduce the driving voltage or improve the emission luminance. 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.

[0095] The blocking layer is preferably a layer that can prevent the diffusion of charges (electrons or holes) and / or excitons present in the light-emitting layer outside the light-emitting layer. The electron blocking layer can be disposed between the light-emitting layer and the hole transport layer and can prevent electrons from passing through the light-emitting layer toward the hole transport layer. Similarly, the hole blocking layer can be disposed between the light-emitting layer and the electron transport layer and can prevent holes from passing through the light-emitting layer toward the electron transport layer. The electron blocking layer and the hole blocking layer can each also serve as an exciton blocking layer. The electron blocking layer or exciton blocking layer as used herein is used in the sense of including a layer having the functions of an electron blocking layer and an exciton blocking layer in one layer.

[0096] The hole-blocking layer has the function of an electron transport layer in a broad sense. The hole-blocking layer plays a role in transporting electrons while preventing holes from reaching the electron transport layer, thereby improving the recombination probability of electrons and holes in the light-emitting layer. As the material of the hole-blocking layer, the materials of the electron transport layer described later can be used as needed.

[0097] The electron-blocking layer has the function of transporting holes in a broad sense. The electron-blocking layer plays a role in transporting holes while preventing electrons from reaching the hole transport layer, thereby improving the probability of recombination of electrons and holes in the light-emitting layer.

[0098] The exciton-blocking layer is preferably a layer for preventing excitons generated by the recombination of holes and electrons in the light-emitting layer from diffusing into the charge transport layer. By inserting the exciton-blocking layer, it becomes possible to efficiently confine excitons within the light-emitting layer, thereby improving the light-emitting efficiency of the device. The exciton-blocking layer can be inserted on either the anode side or the cathode side adjacent to the light-emitting layer, and it is also possible to insert both simultaneously. That is, when the exciton-blocking layer is on the anode side, it can be inserted adjacent to the light-emitting layer between the hole transport layer and the light-emitting layer. When inserted on the cathode side, it can be inserted adjacent to the light-emitting layer between the light-emitting layer and the cathode. Also, between the anode and the exciton-blocking layer adjacent to the anode side of the light-emitting layer, a hole injection layer, an electron-blocking layer, etc. can be provided. Between the cathode and the exciton-blocking layer adjacent to the cathode side of the light-emitting layer, an electron injection layer, an electron transport layer, a hole-blocking layer, etc. can be provided. When arranging the blocking layer, at least one of the singlet excitation energy and the triplet excitation energy of the material used as the blocking layer is preferably higher than the singlet excitation energy and the triplet excitation energy of the light-emitting material.

[0099] The hole transport layer preferably consists of a hole transport material having the function of transporting holes, and the hole transport layer can be provided as a single layer or multiple layers. As the hole transport material, those having any one of hole injection or transport and electron barrier properties are preferable, and it may be either an organic or inorganic material. Examples of hole transport materials that can be used include triazole derivatives, oxadiazole derivatives, imidazole derivatives, carbazole derivatives, indolocarbazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline-based copolymers, and conductive polymer oligomers, particularly thiophene oligomers. As the hole transport material, it is preferable to use porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds, and it is more preferable to use aromatic tertiary amine compounds. In addition, inorganic semiconductors such as molybdenum oxide can also be used as the hole transport material.

[0100] The electron transport layer preferably consists of a material having the function of transporting electrons, and the electron transport layer can be provided as a single layer or multiple layers. The electron transport material (which may also serve as a hole blocking material) preferably has the function of transmitting electrons injected from the cathode to the light-emitting layer. Examples of electron transport layers that can be used include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimide, fluorenylidene methane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, etc. Furthermore, in the above oxadiazole derivatives, thiadiazole derivatives in which the oxygen atom of the oxadiazole ring is replaced with a sulfur atom, and quinoxaline derivatives having a quinoxaline ring known as an electron-withdrawing group can also be used as electron transport materials. Furthermore, polymer materials in which these materials are introduced into the polymer chain or these materials are used as the main chain of the polymer can also be used. In addition, inorganic semiconductors such as zinc oxide can also be used as electron transport materials.

[0101] When manufacturing an organic EL element, the compound of the present invention may be used not only in the light-emitting layer but also in layers other than the light-emitting layer. In that case, the compound of the present invention used in the light-emitting layer and the compound of the present invention used in layers other than the light-emitting layer may be the same or different. For example, the compound of the present invention may also be used in the above-described injection layer, blocking layer (e.g., hole blocking layer, electron blocking layer, exciton blocking layer), hole transport layer, electron transport layer, and the like.

[0102] The film formation method for these layers is not particularly limited, and either a dry process or a wet process may be used.

[0103] Preferred materials that can be used in the organic electroluminescence element are specifically exemplified below. However, the materials that can be used in the present invention should not be construed as being limited by the following exemplified compounds. Also, even a compound exemplified as a material having a specific function can be diverted as a material having other functions. In the structural formulas of the following exemplified compounds, R, R', R1 to R 10 each independently represents a hydrogen atom or a substituent. X represents a carbon atom or a heteroatom 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.

[0104] Preferred compounds that can also be used as the host material of the light-emitting layer are listed. In order to match the HOMO / LUMO levels of the light-emitting material to be used, the HOMO / LUMO levels of the host material can be adjusted by appropriately introducing substituents into the basic skeleton of the following exemplified compounds. For example, by introducing a cyano group or a perfluoroalkyl group into the basic skeleton of the following exemplified compounds, a compound with deeper HOMO / LUMO levels can be obtained, and this can be used as the host material and peripheral compounds. The host material may be bipolar (good at flowing both holes and electrons) or unipolar, and preferably has an excited triplet energy level E T1 higher than that of the light-emitting material. A more preferred host material has bipolarity and an excited triplet energy level E T1is high.

Chem.

[0105] Next, preferred compound examples that can be used as a hole injection material are given.

Chem.

[0106] Next, preferred compound examples that can be used as an electron injection material are given.

Chem.

[0107] Next, preferred compound examples that can be used as a hole blocking material are given.

Chem.

[0108] Next, preferred compound examples that can be used as an electron blocking material are given.

Chem.

[0109] Next, preferred compound examples that can be used as a hole transport material are given.

Chem.

[0110] Next, preferred compound examples that can be used as an electron transport material are given. [Chemistry] TIFF0007694004000045.tif234170

[0111] Examples of preferable compounds as further addable materials are given. For example, they can be added as a stabilizing material. [Chemistry]

[0112] 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 X - Y matrix. Organic light - emitting elements such as the organic EL element of the present invention can be further applied to various uses. For example, it is possible to manufacture an organic electroluminescence display device using the organic EL element of the present invention. For details, reference can be made to "Organic EL Display" (Ohmsha) co - authored by Shizuka Tokito, Chihaya Adachi, and Hideyuki Murata. In particular, the organic EL element of the present invention can also be applied to organic electroluminescence lighting and backlights with high demand. Furthermore, the organic light - emitting element of the present invention can be applied to an organic light - emitting diode. [Examples]

[0113] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

[0114] (Synthesis of Intermediate D1) [Chemistry]

[0115] Under 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). While stirring at room temperature, N-bromosuccinimide (10.8 g) was added in two portions. After stirring at room temperature for 23 hours, a saturated aqueous sodium bisulfite solution (40 mL) and 1N aqueous sodium hydroxide solution (50 mL) were added to the reaction solution. The precipitate was collected by filtration and purified by sublimation to obtain 3,6-dibromo-2,7-bis(trifluoromethyl)-9H-carbazole (5.8 g, yield 84%). The 1 1H NMR spectrum and 19 19F NMR spectrum are shown in Figures 1 and 2, respectively.

[0116] [Chemical formula]

[0117] Under a nitrogen atmosphere, 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 placed in a 50 mL eggplant flask 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 layers were separated. The aqueous layer was extracted with ethyl acetate, and the organic layers were combined and concentrated under reduced pressure. The resulting crude product was subjected to a silica gel column (hexane:chloroform = 1:1) to obtain intermediate D1 (1.05 g, yield 77%). The 1 1H NMR spectrum and 19 19F NMR spectrum are shown in Figures 3 and 4, respectively.

[0118] (Synthesis of intermediate D2) [Chemical formula]

[0119] Under a nitrogen atmosphere, 3,6-dibromo-2,7-bis(trifluoromethyl)-9H-carbazole (461 mg), methylboronic acid (239 mg), potassium phosphate (10.6 g), and dichloro(1,1'-bis(diphenylphosphino)ferrocene)palladium (73 mg) were placed in a 30 mL eggplant flask, and 1,4-dioxane (10 mL) and water (3 mL) were added and dissolved. After degassing the reaction solvent, the mixture was stirred for 13 hours while heating under reflux. The reaction solution was allowed to cool, ethyl acetate and a saturated aqueous sodium chloride solution were added, and liquid separation was performed. 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%). The 1 1H NMR spectrum and 19 19F NMR spectrum are shown in FIGS. 5 and 6, respectively.

[0120] (Synthesis of Intermediate D3) [Chemical formula]

[0121] Under a nitrogen atmosphere, 3,6-dibromo-2,7-bis(trifluoromethyl)-9H-carbazole (1.73 g), dibenzofuran-4-boronic acid (1.79 g), potassium carbonate (1.99 g), and tetrakis(triphenylphosphine)palladium (266 mg) were placed in a 50 mL eggplant flask, and toluene (26.5 mL) and water (10 mL) were added and dissolved. After degassing the reaction solvent, the mixture was stirred for 16 hours while heating under reflux. The reaction solution was allowed to cool, ethyl acetate and water were added, and liquid separation was performed. 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 column (hexane / ethyl acetate = 4 / 1) to obtain Intermediate D3 (1.84 g, yield 77%). The 1 1H NMR spectrum and 19 19F NMR spectrum are shown in FIGS. 7 and 8, respectively.

[0122] (Synthesis of Intermediate D4) [Chemical formula]

[0123] Under a nitrogen atmosphere, into a 50 mL eggplant-shaped flask, 3,6-dibromo-2,7-bis(trifluoromethyl)-9H-carbazole (461 mg), 9-phenylcarbazole-3-boronic acid (860 mg), potassium phosphate (1.06 g), and dichloro(1,1'-bis(diphenylphosphino)ferrocene)palladium (70 mg) were added, and 1,4-dioxane (9 mL) and water (3 mL) were added and dissolved. After degassing the reaction solvent, it was stirred for 17 hours while heating under reflux. The reaction solution was allowed to cool, ethyl acetate and water were added, and liquid separation was performed. 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 column (hexane:chloroform = 1:1) to obtain intermediate D4 (650 mg, yield 75%). The m / z of the target product was observed by mass spectrometry (ASAP, positive).

[0124] (Synthesis of Intermediate D5) [Chemical formula]

[0125] Under a nitrogen atmosphere, into a 10 mL Schlenk tube, 4-methyl-3-trifluoromethylaniline (96 mg), 4-bromo-2-trifluoromethyltoluene (120 mg), sodium tert-butoxide (96 mg), tris(dibenzylideneacetone)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, it was stirred at 80 °C for 15 hours. The reaction solution was allowed to cool, ethyl acetate and a saturated aqueous sodium chloride solution were added, and liquid separation was performed. 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 column (hexane:chloroform = 1:1) to obtain intermediate D5 (218 mg, yield 65%). The 1H NMR spectrum and 19F NMR spectrum of intermediate D5 are shown in Figures 9 and 10, respectively. 1 1H NMR spectrum and 19 19F NMR spectrum are shown in Figures 9 and 10, respectively.

[0126] (Synthesis of Intermediate A1)

Chemical formula

[0127] Under a nitrogen atmosphere, 2-chloro-4,6-diphenyl-1,3,5-triazine (803 mg), 3,4,5-trifluorophenylboronic acid (528 mg), potassium carbonate (1.24 g), and tetrakis(triphenylphosphine)palladium (174 mg) were placed in a 50 mL eggplant flask, and THF (22 mL) and water (7 mL) were added and dissolved. The reaction solution was degassed and heated under reflux for 24 hours. The reaction solution was allowed to cool, and ethyl acetate (15 mL) and water (15 mL) were added. The insoluble matter was collected by filtration and washed with ethyl acetate and acetone to obtain Intermediate A1 (902 mg, yield 83%).

[0128] (Synthesis of Intermediate A2)

Chemical formula

[0129] Under a nitrogen atmosphere, 1,4-dibromo-2,5-difluorobenzene (1.00 g), bis(pinacolato)diboron (2.02 g), potassium acetate (1.81 g), and dichloro(1,1'-bis(diphenylphosphino)ferrocene)palladium (150 mg) were placed in a 50 mL eggplant flask 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 solution was concentrated and then subjected to a silica gel filtration column (ethyl acetate). The filtrate was concentrated and washed with hexane to obtain 2,2'-(2,5-difluoro-1,4-phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (806 mg, yield 60%). Under a nitrogen atmosphere, 2,2'-(2,5-difluoro-1,4-phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (366 mg), 2-chloro-4,6-diphenyl-1,3,5-triazine (615 mg), potassium carbonate (690 mg), and tetrakis(triphenylphosphine)palladium (57 mg) were placed in a 50 mL eggplant-shaped flask and dissolved in THF (20 mL) and water (6 mL). After degassing the reaction solvent, the mixture was stirred under heating and 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 1H NMR spectrum and 19 19F NMR spectrum are shown in Figure 11.

[0130] (Synthesis of Intermediate A3) [Chemical formula]

[0131] Under a nitrogen atmosphere, 1,5-dibromo-2,4-difluorobenzene (1.00 g), bis(pinacolato)diboron (2.02 g), potassium acetate (1.81 g), and dichloro(1,1'-bis(diphenylphosphino)ferrocene)palladium (150 mg) were placed in a 50 mL eggplant-shaped flask 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 solution was concentrated and then subjected to a silica gel filtration column (ethyl acetate). The filtrate was concentrated to obtain a crude product of 2,2'-(4,6-difluoro-1,3-phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (1.93 g, crude yield 143%). Purification was carried out after the next reaction. Under a nitrogen atmosphere, in a 50 mL eggplant flask, crude product of 2,2'-(4,6-difluoro-1,3-phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (523 mg), 2-chloro-4,6-diphenyl-1,3,5-triazine (615 mg), potassium carbonate (690 mg), and tetrakis(triphenylphosphine)palladium (57 mg) were added and dissolved in THF (20 mL) and water (6 mL). After degassing the reaction solvent, the mixture was stirred under heating and 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, two-step yield 52%). The 1 1H NMR spectrum and 19 19F NMR spectrum are shown in Figures 12 and 13, respectively.

[0132] (Synthesis of Intermediate A4)

Chemical formula

[0133] Under a nitrogen atmosphere, in a 50 mL eggplant flask, 2-bromo-4,6-diphenyl-1,3,5-triazine (623 mg), 2,4,6-trifluorophenylboronic acid (387 mg), potassium carbonate (982 mg), 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 for 20 hours while heating under reflux. The reaction solution was allowed to cool and subjected to 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 1H NMR spectrum and 19 19F NMR spectrum are shown in Figures 14 and 15, respectively.

[0134] (Synthesis of Intermediate A5)

Chemical formula

[0135] Under a nitrogen atmosphere, 2-bromo-4,6-diphenylpyrimidine (611 mg), 2,4,6-trifluorophenylboronic acid (482 mg), potassium carbonate (1.33 g), tris(dibenzylideneacetone)dipalladium(0) chloroform adduct (124 mg), and tri-tert-butylphosphonium tetrafluoroborate (156 mg) were placed in a 20 mL eggplant flask, and DMF (10 mL) was added and dissolved. After degassing the reaction solvent, the mixture was stirred for 20 hours while heating under reflux. The reaction solution was allowed to cool, toluene and water were added, and liquid separation was performed. The aqueous layer was extracted with toluene, the organic layers were combined and concentrated under reduced pressure. The obtained crude product was subjected to a silica gel column (hexane / ethyl acetate = 95 / 5) to obtain Intermediate A5 (522 mg, yield 73%). The 1 1H NMR spectrum and 19 19F NMR spectrum are shown in Figures 16 and 17, respectively.

[0136] (Synthesis of Intermediate A6)

Chemical formula

[0137] Under a nitrogen atmosphere, 6-iodoquinoline (509 mg), 3,5-difluorophenylboronic acid (471 mg), potassium carbonate (1.08 g), and tetrakis(triphenylphosphine)palladium (132 mg) were placed in a 20 mL eggplant flask, and toluene (8 mL) and water (3 mL) were added and dissolved. After degassing the reaction solvent, the mixture was stirred for 21 hours while heating under reflux. The reaction solution was allowed to cool, ethyl acetate and water were added, and liquid separation was performed. 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 column (hexane / ethyl acetate = 3 / 2) to obtain Intermediate A6 (463 mg, yield 87%). The 1 1H NMR spectrum and 19 19F NMR spectrum are shown in Figures 18 and 19, respectively.

[0138] (Synthesis of Intermediate A7)

Chemical formula

[0139] Under 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, and toluene (10 mL) and water (4 mL) were added and dissolved. After degassing the reaction solvent, the mixture was stirred for 17 hours while heating under reflux. The reaction solution was allowed to cool, ethyl acetate and water were added, and liquid separation was performed. 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 1H NMR spectrum and 19 19F NMR spectrum are shown in FIGS. 20 and 21, respectively.

[0140] (Synthesis of Intermediate A8)

Chemical formula

[0141] Under a nitrogen atmosphere, 2,2'-(2,5-difluoro-1,4-phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (183 mg), 2-chloro-4,6-diphenyl-pyrimidine (307 mg), potassium carbonate (207 mg), and tetrakistriphenylphosphine palladium (29 mg) were placed in a 20 mL Schlenk tube and dissolved in THF (10 mL) and water (3 mL). After degassing the reaction solvent, the mixture was stirred for 23 hours under heating under reflux. 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 1H NMR spectrum of Intermediate A8 is shown in FIG. 22.

[0142] (Synthesis of Intermediate A9)

Chemical formula

[0143] Under a nitrogen atmosphere, 1,4-dibromo-2-fluorobenzene (1.80 g), bis(pinacolato)diboron (3.88 g), potassium acetate (3.53 g), and [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (291 mg) were placed in a 100 mL four-necked flask, and 1,4-dioxane (36 mL) was added and dissolved. After degassing the reaction solvent, the mixture was stirred for 17 hours while heating under reflux. The reaction solution was allowed to cool and then subjected to 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%).

Chemical formula

[0144] Under a nitrogen atmosphere, 2,2′-(2-fluoro-1,4-phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (200 mg), 2-bromo-4,6-diphenyl-1,3,5-triazine (565 mg), potassium carbonate (557 mg), and tetrakis(triphenylphosphine)palladium (45 mg) were placed in a 10 mL Schlenk tube, and THF (4 mL) and water (1.3 mL) were added and dissolved. After degassing the reaction solvent, the mixture was stirred for 17 hours while heating under reflux. After allowing the reaction solution to cool, water was added and a white solid precipitated. The precipitate was collected by filtration and washed with ethyl acetate to obtain intermediate A9 (321 mg, yield 100%). The 1 1H NMR spectrum and 19 19F NMR spectrum are shown in FIGS. 23 and 24, respectively.

[0145] (Synthesis of Example 1)

Chemical formula

[0146] (Synthesis of Example 2)

Chemical formula

[0147] Under a nitrogen atmosphere, intermediate D1 (285 mg), intermediate A2 (144 mg), and cesium carbonate (305 mg) were placed in a 10 mL Schlenk tube and suspended in NMP (15 mL). After reacting at 130 °C for 21 hours, it was allowed to cool. Water (5 mL) was added to the reaction solution, and the precipitate was collected by filtration. The filtered product was purified by sublimation to obtain Example 2 (346 mg, yield 96%). The 1 1H NMR spectrum and 19 19F NMR spectrum are shown in Figures 27 and 28, respectively.

[0148] (Synthesis of Examples 3 and 4)

Chemical formula

[0149] Under a nitrogen atmosphere, intermediate D1 (285 mg), intermediate A3 (144 mg), and cesium carbonate (305 mg) were placed in a 10 mL Schlenk tube and suspended in NMP (15 mL). After reacting at 130 °C for 21 hours, it was allowed to cool. Water (5 mL) was added to the reaction solution, and the precipitate was collected by filtration. The filtered product was purified by sublimation to obtain Example 3 (355 mg, yield 98%). The 1 1H NMR spectrum and 19The \(^{19}\)F NMR spectra are shown in FIGS. 29 and 30, respectively. Under a nitrogen atmosphere, intermediate D2 (125 mg), intermediate A3 (87 mg), and cesium carbonate (184 mg) were placed in a 10 mL Schlenk tube and suspended in NMP (5 mL). After reacting at 130 °C for 2 hours, the reaction 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 sublimation purification. The 1 \(^{1}\)H NMR spectrum and 19 the \(^{19}\)F NMR spectrum are shown in FIGS. 31 and 32, respectively.

[0150] (Synthesis of Example 5) [Chemical formula]

[0151] 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 mixture was reacted at 150 °C for 22 hours. After the reaction solution was allowed to cool and water was added, a flesh-colored solid precipitated. After the precipitate was collected by filtration, Example 5 (89 mg, yield 50%) was obtained by sublimation purification. It was identified by mass spectrometry (ASAP, positive).

[0152] (Synthesis of Example 6) [Chemical formula]

[0153] 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 mixture was reacted at 130 °C for 22 hours. After the reaction solution was allowed to cool and water was added, a flesh-colored solid precipitated. After the precipitate was collected by filtration, Example 6 (417 mg, yield 70%) was obtained by sublimation purification. It was identified by mass spectrometry (ASAP, positive).

[0154] (Comparative Example 1) Comparative Example 1 is the following formula: [Chemical formula] It is a compound represented by, and the product of Lumtec Co., Ltd. (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=&search_word=&search_field2=&search_word2=&search_field3=&search_word3=&bool1=&bool2=&search_type=1&up_page=3) was used.

[0155] (Comparative Examples 2 - 4) Comparative Examples 2 - 4 are respectively the following formulas: [Chemical formula] They are compounds represented by, and were synthesized by the method described in International Publication No. 2018047948.

[0156] (Synthesis of Comparative Example 5) [Chemical formula]

[0157] As the first stage of the reaction, under a nitrogen atmosphere, into a 30 mL eggplant flask were placed intermediate A1 (500 mg), 2,7 - bis(trifluoromethyl)carbazole (444 mg), and cesium carbonate (961 mg), and they were dissolved in DMSO (20 mL). After stirring at 85 °C for 3 hours, it was allowed to cool to room temperature. To the reaction solution were added water (12 mL) and chloroform (10 mL), and it 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 obtain 9-(4-(4,6 - diphenyl - 1,3,5 - triazin - 2 - yl)-2,6 - difluorophenyl)-2,7 - bis(trifluoromethyl)-9H - carbazole (766 mg, yield 86%). As the second step of the reaction, in a 30 mL eggplant flask under a nitrogen atmosphere, 9-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)-2,6-difluorophenyl)-2,7-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, it was allowed to cool to room temperature. Next, water (15 mL) was added to the reaction solution and left standing 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 1H NMR spectrum of Comparative Example 5 is shown in Figure 33.

[0158] (Synthesis of Comparative Example 6)

Chemical formula

[0159] Under a nitrogen atmosphere, 9-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)-2,6-difluorophenyl)-2,7-bis(trifluoromethyl)-9H-carbazole (65 mg), 3,6-diphenylcarbazole (80 mg), and cesium carbonate (82 mg) were added to a 30 mL eggplant flask and dissolved in DMSO (3 mL). After stirring at 100 °C for 18 hours, it was allowed to cool to room temperature. Next, water (15 mL) was added to the reaction solution and left standing for 40 minutes. The precipitated gray crystals were collected by filtration, washed with IPA (2 mL), and sublimated to obtain Comparative Example 6 (85 mg, yield 68%). The 1 1H NMR spectrum and 19 19F NMR spectrum of Comparative Example 6 are shown in Figures 34 and 35, respectively.

[0160] (Synthesis of Comparative Examples 7 - 9) Comparative Examples 7 - 9 are respectively represented by the following formula:

Chemical formula

[0161] (Synthesis of Comparative Example 10) Comparative Example 10 is a compound represented by the following formula:

Chemical formula

[0162] (Synthesis of Comparative Example 11) Comparative Example 11 is a compound represented by the following formula:

Chemical formula

[0163] (Synthesis of Comparative Example 12) Comparative Example 12 is a compound represented by the following formula:

Chemical formula

[0164] (Synthesis of Comparative Example 13)

Chemical formula

[0165] Under a nitrogen atmosphere, the intermediate D1 (170 mg), 4,5-difluorophthalonitrile (24 mg), and cesium carbonate (182 mg) were placed in a 10 mL Schlenk tube 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. The filtered product was subjected to a silica gel column (hexane:chloroform = 1:1) to obtain Comparative Example 13 (20 mg, yield 13%). For Comparative Example 13 1 The 1H NMR spectrum and 19 the 19F NMR spectrum are shown in Figures 40 and 41, respectively.

[0166] (Emission peak wavelength (λmax), full width at half maximum) For the λmax, full width at half maximum, and CIE of the comparative examples and examples, the emission spectrum when the toluene solution of the luminescent material (luminescent material concentration: 1 × 10 -5 M) was irradiated with excitation light at 340 nm at room temperature was measured using Fluoromax 4 manufactured by HORIBA, and the measurement was performed 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 the value half of the peak top intensity.

[0167] (Luminescence efficiency (PLQY)) For the PLQY of the comparative examples and examples, it is the value when the toluene solution of the luminescent material (luminescent material concentration: 1 × 10 -5 M) was irradiated with excitation light at 340 nm at room temperature, and it was measured using an absolute PL quantum yield measurement device (Quantaurus-QY C11347-01 manufactured by Hamamatsu Photonics).

[0168] (HOMO level) For the HOMO levels of the comparative examples and examples, they were measured using an atmospheric photoelectron spectrometer (AC-3 manufactured by Riken Keiki Co., Ltd.). The measurement sample used was one obtained by vacuum depositing the luminescent material on an ITO substrate to a film thickness of 50 nm. The measurement was performed at an ultraviolet light intensity of 10 nW and a measurement range from -4.00 eV to -7.00 eV (in 0.05 eV increments), and the energy threshold of photoelectron emission during ultraviolet irradiation was taken as the HOMO level.

[0169] (Orientation parameter S) The orientation parameter S of the comparative examples and the examples was calculated by performing spectral measurement in the range of 45 to 75 degrees (in 5-degree increments) using a spectroscopic ellipsometer (product of J.A. Woollam Japan) on a single film (film thickness: about 30 nm) of the light-emitting material formed on a bare silicon substrate and performing fitting analysis of the obtained spectrum.

[0170] (Redox property ΔE) The redox properties of the comparative examples and the 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 / AgNO3 acetonitrile solution Solvent: THF Electrolyte: Bu4NPF6 Sweeping rate: 50 meV / s Concentration of light-emitting material: 1 mM Concentration of electrolyte: 100 mM

[0171] The results are shown in Table 1.

Table 1

Claims

1. A compound represented by the following formula (5): 【Chemical Formula 1】 [In the formula, X51 to X53 are each -N= or -C(R58)=, R51, R52, and R58 are each 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 a heteroaryl group which may have a substituent, R53 to R57 are each a hydrogen atom or the following formula (2): 【Chemical Formula 2】 (In the formula, Z is a single bond, R ２２ and R ２７ are each an alkylcarbonyl group, an alkylsulfonyl group, a perfluoroalkyl group, a cyano group, or a nitro group, R ２３ and R ２６ are each an electron-donating group, R ２１ 、R ２４ 、R ２５ 、and R ２８ are hydrogen atoms, The electron-donating group is an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an alkylsulfanyl group, a trialkylsilyl group, a heteroaryl group, or an N,N-diarylamino group, The wavy line indicates the bonding site with L) and is a group represented by the formula (2) (provided that at least one of R53 to R57 is a group represented by the formula (2)); A compound represented by the following formula (7): 【Chemical Formula 3】 [In the formula, X71 to X76 are each -N= or -C(R79)=, R71 to R74 and R79 are each 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 a heteroaryl group which may have a substituent. R75 to R78 are a hydrogen atom or a group represented by the above formula (2) (provided that at least one of R75 to R78 is a group represented by the above formula (2)); and A compound represented by the following formula (8): 【Chemical Formula 4】 [In the formula, X81 to X86 are each -N= or -C(R89)=, R81 to R84 and R89 are each 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 a heteroaryl group which may have a substituent, R85 to R88 are a hydrogen atom or a group represented by the above formula (2) (provided that at least one of R85 to R88 is a group represented by the above formula (2))] A compound selected from the group consisting of.

2. R ２２ and R ２７ The compound according to claim 1, wherein each is a perfluoroalkyl group or a cyano group.

3. A delayed fluorescence material containing the compound according to claim 1 or 2.

4. An organic light-emitting device containing the compound according to claim 1 or 2.

5. The organic light-emitting device according to claim 4, which is an organic EL device.

6. The following formula (9): 【Chemical Formula 5】 (In the formula, R ９１ and R ９４ each is a perfluoroalkyl group or a cyano group, R ９２ and R ９３ each is 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, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent, Z ９ is a single bond), a compound represented by

7. A method for producing the compound according to claim 1, comprising a step of reacting the compound according to claim 6 with a compound having a halogen atom instead of the group represented by the formula (2) in the formula (5), (7), or (8).

Images