JP7318178B2 - Cyclic azine compounds, materials for organic electroluminescence devices, electron transport materials for organic electroluminescence devices - Google Patents

Description

The present disclosure relates to a cyclic azine compound, a material for organic electroluminescence devices, and an electron transport material for organic electroluminescence devices.

An organic electroluminescence device has a basic structure in which a light-emitting layer containing a light-emitting material is sandwiched between a hole-transporting layer and an electron-transporting layer, and an anode and a cathode are attached to the outside thereof. It is a light-emitting element that utilizes light emission (fluorescence or phosphorescence) when excitons generated by recombination of electrons are deactivated, and is already used not only for small displays but also for large-sized televisions and lighting applications. . The hole-transporting layer is the hole-transporting layer and the hole-injecting layer, the light-emitting layer is the electron-blocking layer, the light-emitting layer, and the hole-blocking layer, and the electron-transporting layer is the electron-transporting layer and the electron-injecting layer. It may be divided and configured. A co-deposited film doped with a metal, an organometallic compound, or other organic compound may be used as a carrier transport layer (electron transport layer or hole transport layer) of an organic electroluminescence device.
Cyclic azine compounds disclosed in Patent Documents 1 and 2 have been reported as materials for organic electroluminescence devices.

JP 2011-063584 A Japanese Patent Publication No. 2007-520875

Conventional organic electroluminescent devices have a higher driving voltage than inorganic light emitting diodes, have lower luminance and luminous efficiency, and have a significantly shorter device life, and have not been put to practical use. Although recent organic electroluminescence devices have been gradually improved, materials with even better luminous efficiency characteristics, driving voltage characteristics, and long life characteristics are in demand. In some applications, such as in-vehicle applications, extremely high heat resistance is required, and materials are required to have a high glass transition temperature (Tg). Furthermore, in recent years, active research has been conducted on organic electroluminescence devices using thermally activated delayed fluorescence (TADF) and blue electroluminescence devices using phosphorescence by Adachi et al. Materials in these organic electroluminescent devices are required to have a high triplet excitation level for energy confinement.

Regarding the cyclic azine compound disclosed in Patent Document 1, further improvements are required in terms of the glass transition temperature and the triplet excitation level, and the device life and luminous efficiency when used in an organic electroluminescent device are improved. improvement is required.

Regarding the cyclic azine compound having a non-planar structure disclosed in Patent Document 2, there is a demand for further improvement in terms of extending the life of the device and increasing the luminous efficiency when used in an organic electroluminescent device. Further, with respect to the compound containing triptycene, specific synthesis examples, characteristics as an electron transport material for organic electroluminescence devices, glass transition temperature, and triplet excitation level are not described, and their physical properties are unknown. is.

An object of each aspect of the present invention is to provide a cyclic azine compound having a higher glass transition temperature and a higher triplet excitation level than conventionally known compounds, a material for organic electroluminescent devices, and an electron transport material for organic electroluminescent devices. is to provide

The present inventors have made intensive studies to solve the above problems, and found that the glass transition temperature of a cyclic azine compound to which a group having a triptycene structure is bonded (hereinafter also referred to as "cyclic azine compound (1)") is An organic electroluminescence device that has an extremely high triplet excitation level and uses the compound as an electron transport material has a lower driving voltage, a higher luminous efficiency, and a higher luminous efficiency compared to the case of using a conventionally known material. The inventors have found that heat resistance can be improved or life can be extended, and have completed each aspect of the present invention.

The cyclic azine compound according to the first aspect of the present invention is a cyclic azine compound represented by formula (1):

In formula (1),
Ar ¹ each independently represents a substituted or unsubstituted phenyl group, naphthyl group, or pyridyl group;
^Ar2 is
a substituted or unsubstituted monocyclic or condensed aromatic hydrocarbon group having 6 to 24 carbon atoms,
a monocyclic or condensed nitrogen-containing heteroaromatic group having 4 to 25 carbon atoms consisting only of a substituted or unsubstituted 6-membered ring;
represents a monocyclic or condensed heteroaromatic group having 3 to 25 carbon atoms composed of atoms selected from the group of atoms consisting of substituted or unsubstituted H, C, O, and S, or a hydrogen atom;
Ar ³ and Ar ⁴ are each independently
substituted or unsubstituted phenyl group, naphthyl group, pyridyl group,
hydrogen atom,
an unsubstituted alkyl group having 1 to 4 carbon atoms, or
represents a single bond attached to ^X2 ;
Ar ⁵ and Ar ⁶ are each independently
substituted or unsubstituted phenyl group, naphthyl group, pyridyl group,
hydrogen atom,
an unsubstituted alkyl group having 1 to 4 carbon atoms, or
represents a single bond attached to ^X2 ;
W ¹ , W ² , and W ³ are
each independently represents C—H or a nitrogen atom,
at least two represent C—H;
X ¹ and X ² are each independently
a substituted or unsubstituted phenylene group, naphthylene group, biphenylene group, pyridylene group, or
represents a single bond;
Y ¹ , Y ² , Y ³ and Y ⁴ are each independently
a group represented by C—R, or
represents a nitrogen atom;
R are each independently
substituted or unsubstituted phenyl group, naphthyl group, pyridyl group,
hydrogen atom,
an unsubstituted alkyl group having 1 to 4 carbon atoms, or
represents an unsubstituted alkenyl group having 1 to 4 carbon atoms;
R may be bonded to each other to form an aromatic ring;
Z represents a nitrogen atom or C—H;
When Ar ¹ , Ar ³ to Ar ⁶ , X ¹ to X ² and R have a substituent, the substituent is a fluorine atom, a methyl group, or a phenyl group;
When Ar ² has a substituent, the substituent is a phenyl group, a tolyl group, a pyridyl group, a methylpyridyl group, a dimethylpyridyl group, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. It is an alkoxy group.

The cyclic azine compound according to the second aspect of the present invention is
The cyclic azine compound according to the first aspect, wherein Z is a nitrogen atom.

The cyclic azine compound according to the third aspect of the present invention is
two Ar ¹ 's represent the same group and are a substituted or unsubstituted phenyl group, naphthyl group, or pyridyl group;
The cyclic azine compound according to the first or second aspect, wherein when Ar ¹ has a substituent, the substituent is a fluorine atom, a methyl group, or a phenyl group.

The cyclic azine compound according to the fourth aspect of the present invention is
The cyclic azine compound according to any one of the first to third aspects above, wherein both Ar ¹ are phenyl groups.

The cyclic azine compound according to the fifth aspect of the present invention is
^Ar2 is
a hydrogen atom, or
substituted or unsubstituted phenyl group, naphthyl group, fluorenyl group, anthryl group, phenanthryl group, benzofluorenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, pyrimidyl group, pyridyl group, pyrazyl group, a quinolyl group, an isoquinolyl group, a benzofuranyl group, a benzothienyl group, a dibenzofuranyl group, and a dibenzothienyl group;
When Ar ² has a substituent, the substituent is a phenyl group, a tolyl group, a pyridyl group, a methylpyridyl group, a dimethylpyridyl group, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. The cyclic azine compound according to any one of the first to fourth aspects above, which is an alkoxy group.

The cyclic azine compound according to the sixth aspect of the present invention is
Ar ² is a substituted or unsubstituted fluorenyl group, benzofluorenyl group, pyridyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, dibenzofuranyl group, or dibenzothienyl group;
When Ar ² has a substituent, the substituent is a phenyl group, a tolyl group, a pyridyl group, a methylpyridyl group, a dimethylpyridyl group, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. The cyclic azine compound according to any one of the first to fifth aspects above, which is an alkoxy group.

The cyclic azine compound according to the seventh aspect of the present invention is
Ar ³ and Ar ⁴ are each independently
hydrogen atom;
unsubstituted phenyl group, naphthyl group, pyridyl group; or
The cyclic azine compound according to any one of the first to sixth aspects above, wherein X is a single bond that bonds to ² ;

The cyclic azine compound according to the eighth aspect of the present invention is
X ¹ and X ² are each independently
single bond;
The cyclic azine compound according to any one of the first to seventh aspects above, which is an unsubstituted phenylene group, naphthylene group, biphenylene group, or pyridylene group.

The cyclic azine compound according to the ninth aspect of the present invention is
Y ¹ , Y ² , Y ³ and Y ⁴ are all groups represented by C—R,
The R are each independently
hydrogen atom;
unsubstituted alkyl group having 1 to 4 carbon atoms, alkenyl group having 1 to 4 carbon atoms, phenyl group, naphthyl group, or pyridyl group; It is a cyclic azine compound.

The cyclic azine compound according to the tenth aspect of the present invention is
The cyclic azine compound according to any one of the first to ninth aspects above, wherein W ¹ , W ² and W ³ are all CH.

The cyclic azine compound according to the eleventh aspect of the present invention is
A material for an organic electroluminescence device comprising the cyclic azine compound represented by formula (1) according to any one of the first to tenth aspects.

The cyclic azine compound according to the twelfth aspect of the present invention is
An electron-transporting material for an organic electroluminescence device, comprising the cyclic azine compound represented by formula (1) according to any one of the first to tenth aspects.

According to each aspect of the present invention, there are provided a cyclic azine compound having extremely excellent film heat resistance and a high triplet excitation level, a material for an organic electroluminescence device, and an electron transport material for an organic electroluminescence device containing the same. It contributes to the provision of an organic electroluminescence device that is excellent in low driving voltage, high luminous efficiency, high heat resistance, or long life.

FIG. 2 is a cross-sectional view of a single-layer device produced in Examples.

Exemplary aspects for carrying out the invention are described in detail below.

Each aspect of the present invention relates to a cyclic azine compound represented by formula (1) (cyclic azine compound (1)), a method for producing the same, and a material for an organic electroluminescence device containing the material.
A cyclic azine compound according to one aspect of the present invention is a cyclic azine compound represented by formula (1):

In formula (1),
Ar ¹ each independently represents a substituted or unsubstituted phenyl group, naphthyl group, or pyridyl group;
^Ar2 is
a substituted or unsubstituted monocyclic or condensed aromatic hydrocarbon group having 6 to 24 carbon atoms,
a monocyclic or condensed nitrogen-containing heteroaromatic group having 4 to 25 carbon atoms consisting only of a substituted or unsubstituted 6-membered ring;
represents a monocyclic or condensed heteroaromatic group having 3 to 25 carbon atoms composed of atoms selected from the group of atoms consisting of substituted or unsubstituted H, C, O, and S, or a hydrogen atom;
Ar ³ and Ar ⁴ are each independently
substituted or unsubstituted phenyl group, naphthyl group, pyridyl group,
hydrogen atom,
an unsubstituted alkyl group having 1 to 4 carbon atoms, or
represents a single bond attached to ^X2 ;
Ar ⁵ and Ar ⁶ are each independently
substituted or unsubstituted phenyl group, naphthyl group, pyridyl group,
hydrogen atom,
an unsubstituted alkyl group having 1 to 4 carbon atoms, or
represents a single bond attached to ^X2 ;
W ¹ , W ² , and W ³ are
each independently represents C—H or a nitrogen atom,
at least two represent C—H;
X ¹ and X ² are each independently
a substituted or unsubstituted phenylene group, naphthylene group, biphenylene group, pyridylene group, or
represents a single bond;
Y ¹ , Y ² , Y ³ and Y ⁴ are each independently
a group represented by C—R, or
represents a nitrogen atom;
R are each independently
substituted or unsubstituted phenyl group, naphthyl group, pyridyl group,
hydrogen atom,
an unsubstituted alkyl group having 1 to 4 carbon atoms, or
represents an unsubstituted alkenyl group having 1 to 4 carbon atoms;
R may be bonded to each other to form an aromatic ring;
Z represents a nitrogen atom or C—H;
When Ar ¹ , Ar ³ to Ar ⁶ , X ¹ to X ² and R have a substituent, the substituent is a fluorine atom, a methyl group, or a phenyl group;
When Ar ² has a substituent, the substituent is a phenyl group, a tolyl group, a pyridyl group, a methylpyridyl group, a dimethylpyridyl group, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. It is an alkoxy group.

The substituents in the cyclic azine compound (1) according to one aspect of the present invention are defined as follows.

In formula (1), each Ar ¹ independently represents a phenyl group, a naphthyl group, or a pyridyl group (these groups may be substituted with a fluorine atom, a methyl group, or a phenyl group).
The fluorine-substituted phenyl group, naphthyl group, or pyridyl group for Ar ¹ is not particularly limited, but examples thereof include a fluorophenyl group, a pentafluorophenyl group, a difluorophenyl group, a fluoronaphthyl group, a difluoro Preferred examples include a naphthyl group, a fluoropyridyl group, a difluoropyridyl group, and the like.
The methyl-substituted phenyl group, naphthyl group, or pyridyl group for Ar ¹ is not particularly limited, but examples include tolyl group, methylnaphthyl group, dimethylphenyl group, dimethylnaphthyl group, and methylpyridyl group. , or a dimethylpyridyl group and the like are preferred examples.
The phenyl group, naphthyl group, or pyridyl group substituted with a phenyl group for Ar ¹ is not particularly limited, and examples thereof include a biphenyl group, a phenylnaphthyl group, a terphenyl group, a diphenylnaphthyl group, or a phenylpyridyl group. Preferred examples include groups and the like.

When two Ar ¹ 's represent the same group and are a substituted or unsubstituted phenyl group, naphthyl group, or pyridyl group, and Ar ¹ has a substituent, the substituent is a fluorine atom or a methyl group. , or a phenyl group.

Ar ¹ is more preferably each independently a phenyl group, a tolyl group, ^a naphthyl group, or a biphenyl group in terms of excellent electron-transporting material properties. A tolyl group, a naphthyl group, or a biphenyl group is more preferable, and from the viewpoint of ease of synthesis, it is even more preferable that both Ar ¹ are phenyl groups.

Ar ¹ preferably represents the same group for ease of synthesis.

Specific examples of Ar ¹ are not particularly limited. 5-dimethylphenyl group, mesityl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,4-difluorophenyl group, 3,5-difluorophenyl group, biphenyl-2-yl group, biphenyl-3-yl group, biphenyl-4-yl group, 1-naphthyl group, 2-naphthyl group, 1-phenylnaphthalene-2-yl group, 1-phenylnaphthalene-3-yl group, 1-phenylnaphthalene-4 -yl group, 1-phenylnaphthalene-5-yl group, 1-phenylnaphthalene-6-yl group, 1-phenylnaphthalene-7-yl group, 1-phenylnaphthalene-8-yl group, 2-phenylnaphthalene-1 -yl group, 2-phenylnaphthalene-3-yl group, 2-phenylnaphthalene-4-yl group, 2-phenylnaphthalene-5-yl group, 2-phenylnaphthalene-6-yl group, 2-phenylnaphthalene-7 -yl group, 2-phenylnaphthalene-8-yl group, 1-methylnaphthalene-4-yl group, 1-methylnaphthalene-5-yl group, 1-methylnaphthalene-6-yl group, 1-methylnaphthalene-7 -yl group, 1-methylnaphthalene-8-yl group, 2-methylnaphthalene-1-yl group, 2-methylnaphthalene-3-yl group, 2-methylnaphthalene-4-yl group, 2-methylnaphthalene-5 -yl group, 2-methylnaphthalene-6-yl group, 2-methylnaphthalene-7-yl group, 2-methylnaphthalene-8-yl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2 -methylpyridin-3-yl group, 2-methylpyridin-4-yl group, 2-methylpyridin-5-yl group, 2-methylpyridin-6-yl group, 3-methylpyridin-2-yl group, 3 -methylpyridin-4-yl group, 3-methylpyridin-5-yl group, 3-methylpyridin-6-yl group, 4-methylpyridin-2-yl group, 4-methylpyridin-3-yl group, 2 ,6-dimethylpyridin-3-yl group, 2,6-dimethylpyridin-4-yl group, 3,6-dimethylpyridin-2-yl group, 3,6-dimethylpyridin-4-yl group, 3,6 -dimethylpyridin-5-yl group, 2-phenylpyridin-6-yl group, 3-phenylpyridin-6-yl group, 4-phenylpyridin-6-yl group, 5-phenylpyridin-6-yl group, 2 -phenylpyridin-3-yl group, 2-phenylpyridin-5-yl group, 3-phenylpyridin-5-yl group, 4-phenylpyridin-3-yl group, 3-phenylpyridin-4-yl group, or A preferred example is a 2-phenylpyridin-4-yl group. Among these substituents, a phenyl group, p-tolyl group, biphenyl-3-yl group, biphenyl-4-yl group, 1-naphthyl group, or 2 -Naphthyl group is preferred, and each independently, a phenyl group, biphenyl-3-yl group, biphenyl-4-yl group, 1-naphthyl group, or 2-naphthyl group is more preferred. groups are particularly preferred.

Ar ² is a monocyclic or condensed ring aromatic hydrocarbon group having 6 to 24 carbon atoms, a monocyclic or condensed nitrogen-containing heteroaromatic group having 4 to 25 carbon atoms consisting only of a 6-membered ring, or H, C, A monocyclic or condensed heteroaromatic group having 3 to 25 carbon atoms composed of atoms selected from the atomic group consisting of O and S (these groups include a phenyl group, a tolyl group, a pyridyl group, a methylpyridyl group, may have a dimethylpyridyl group, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms), or a hydrogen atom.

The monocyclic or condensed aromatic hydrocarbon group having 6 to 24 carbon atoms for Ar ² is not particularly limited, but examples include phenyl group, naphthyl group, phenanthryl group, anthryl group, pyrenyl group and triphenylenyl group. , a chrysenyl group, a fluoranthenyl group, an acenaphthyl group, a fluorenyl group, a benzofluorenyl group and the like are preferable examples. In addition, as described above, these substituents include a phenyl group, a tolyl group, a pyridyl group, a methylpyridyl group, a dimethylpyridyl group, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. may be substituted with

The monocyclic or condensed nitrogen-containing heteroaromatic group having 4 to 25 carbon atoms consisting only of a 6-membered ring for Ar ² is not particularly limited, but examples thereof include pyridyl group, pyrazyl group, pyrimidyl group and pyridazyl. Preferable examples include a group, a quinolyl group, an isoquinolyl group, a phenanthridyl group, a benzoquinolyl group, an acridinyl group, and the like. The carbazolyl group is a heteroaromatic group containing a 5-membered ring, and the monocyclic or condensed nitrogen-containing heteroaromatic group having 4 to 25 carbon atoms consisting only of a 6-membered ring according to one embodiment of the present invention is Not included. Further, as described above, these substituents are phenyl, tolyl, pyridyl, methylpyridyl, dimethylpyridyl, fluorine, alkyl having 1 to 4 carbon atoms, or alkoxy having 1 to 4 carbon atoms. may be substituted with

The monocyclic or condensed heteroaromatic group having 3 to 25 carbon atoms composed of atoms selected from the atomic group consisting of H, C, O and S in Ar ² is not particularly limited, Preferred examples include thienyl, furyl, bithienyl, bifuryl, benzothienyl, benzofuryl, dibenzothienyl, and dibenzofuryl groups. In addition, as described above, these substituents include a phenyl group, a tolyl group, a pyridyl group, a methylpyridyl group, a dimethylpyridyl group, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. may be substituted with

The alkyl group having 1 to 4 carbon atoms in Ar ² is not particularly limited, but is preferably, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, or the like. Examples include:

The alkoxy group having 1 to 4 carbon atoms in Ar ² is not particularly limited, but may be a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a t-butoxy group, or the like. Preferred examples include:

Ar ² is a hydrogen atom, a monocyclic or condensed ring aromatic hydrocarbon group having 6 to 24 carbon atoms, a monocyclic or condensed nitrogen-containing heteroaromatic group having 4 to 25 carbon atoms consisting only of a 6-membered ring, or H , C, O, and S, and preferably a monocyclic or condensed heteroaromatic group having 3 to 25 carbon atoms. In terms of the high glass transition temperature, Ar ² is a monocyclic or condensed aromatic hydrocarbon group having 6 to 24 carbon atoms, a monocyclic or condensed nitrogen-containing group having 4 to 25 carbon atoms consisting only of a 6-membered ring. A heteroaromatic group or a monocyclic or condensed heteroaromatic group having 3 to 25 carbon atoms composed of atoms selected from the atomic group consisting of H, C, O and S is preferred.

Specifically, Ar ² is a hydrogen atom; pyrimidyl group, pyrazyl group, pyridyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, dibenzofuranyl group, or dibenzothienyl group (these groups are phenyl, tolyl, pyridyl, methylpyridyl, may have a dimethylpyridyl group, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms); Ar ² is a phenyl group, naphthyl group, biphenyl group, fluorenyl group, anthryl group, phenanthryl group, benzofluorenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, pyrimidyl group, pyrazyl group, pyridyl group , quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, dibenzofuranyl group, or dibenzothienyl group (these groups are phenyl, tolyl, pyridyl, methylpyridyl, dimethylpyridyl, fluorine, carbon may have an alkyl group of 1 to 4 carbon atoms or an alkoxy group of 1 to 4 carbon atoms). Ar ² is a phenyl group, naphthyl group, fluorenyl group, anthryl group, phenanthryl group, benzofluorenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, pyrimidyl group, pyrazyl group, pyridyl group, quinolyl group , an isoquinolyl group, a benzofuranyl group, a benzothienyl group, a dibenzofuranyl group, a dibenzothienyl group, a biphenyl group, a pyridylphenyl group, or a terphenyl group.

Ar ² is a fluorenyl group, a benzofluorenyl group, a pyridyl group, a quinolyl group, an isoquinolyl group, a benzofuranyl group, a benzothienyl group, a dibenzofuranyl group, or a dibenzothienyl group in terms of excellent electron transport material properties. group (these groups may have a phenyl group, a tolyl group, a pyridyl group, a methylpyridyl group, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms); Preferably. More preferably Ar ² is a pyridyl group.

Specific examples of Ar ² include, but are not limited to, hydrogen atom, phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, 2,4-dimethylphenyl group, 3,5-dimethyl phenyl group, mesityl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,4-diethylphenyl group, 3,5-diethylphenyl group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 2,4-dipropylphenyl group, 3,5-dipropylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2,4-diisopropylphenyl group, 3,5-diisopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 2,4-dibutylphenyl group, 3,5-dibutylphenyl group, 2-tert-butylphenyl group, 3-tert-butylphenyl group, 4-tert-butylphenyl group, 2,4-di-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, biphenyl-2-yl group, biphenyl -3-yl group, biphenyl-4-yl group, 3-methylbiphenyl-4-yl group, 2'-methylbiphenyl-4-yl group, 4'-methylbiphenyl-4-yl group, 2,2'- dimethylbiphenyl-4-yl group, 6-methylbiphenyl-3-yl group, 5-methylbiphenyl-3-yl group, 2'-methylbiphenyl-3-yl group, 4'-methylbiphenyl-3-yl group, 6,2'-dimethylbiphenyl-3-yl group, 5-methylbiphenyl-2-yl group, 6-methylbiphenyl-2-yl group, 2'-methylbiphenyl-2-yl group, 4'-methylbiphenyl- 2-yl group, 6,2'-dimethylbiphenyl-2-yl group, 3-ethylbiphenyl-4-yl group, 6-ethylbiphenyl-3-yl group, 5-ethylbiphenyl-2-yl group, 3- propylbiphenyl-4-yl group, 6-propylbiphenyl-3-yl group, 5-propylbiphenyl-2-yl group, 3-isopropylbiphenyl-4-yl group, 6-isopropylbiphenyl-3-yl group, 5- isopropylbiphenyl-2-yl group, 3-butylbiphenyl-4-yl group, 6-butylbiphenyl-3-yl group, 5-butylbiphenyl-2-yl group, 3-tert-butylbiphenyl-4-yl group, 4'-tert-butylbiphenyl-4-yl group, 6-tert-butylbiphenyl-3-yl group, 5-tert-butylbiphenyl-2-yl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-methylpyridin-3-yl group, 2-methylpyridin-4-yl group, 2-methylpyridin-5-yl group, 2-methylpyridin-6-yl group, 3-methylpyridin-2-yl group, 3-methylpyridin-4-yl group, 3-methylpyridin-5-yl group, 3-methylpyridin-6-yl group, 4-methylpyridin-2-yl group, 4-methylpyridin-3-yl 2,6-dimethylpyridin-3-yl group, 2,6-dimethylpyridin-4-yl group, 3,6-dimethylpyridin-2-yl group, 3,6-dimethylpyridin-4-yl group, 3,6-dimethylpyridin-5-yl group, 2-phenylpyridin-6-yl group, 3-phenylpyridin-6-yl group, 4-phenylpyridin-6-yl group, 5-phenylpyridin-6-yl group, 2-phenylpyridin-3-yl group, 2-phenylpyridin-5-yl group, 3-phenylpyridin-5-yl group, 4-phenylpyridin-3-yl group, 3-phenylpyridin-4-yl group, 2-phenylpyridin-4-yl group, 2-(2-pyridyl)phenyl group, 3-(2-pyridyl)phenyl group,
4-(2-pyridyl)phenyl group, 2-(3-pyridyl)phenyl group, 3-(3-pyridyl)phenyl group, 4-(3-pyridyl)phenyl group, 2-(4-pyridyl)phenyl group, 3-(4-pyridyl)phenyl group, 4-(4-pyridyl)phenyl group, 2-(3-methyl-2-pyridyl)phenyl group, 3-(3-methyl-2-pyridyl)phenyl group, 4- (3-methyl-2-pyridyl)phenyl group, 2-(4-methyl-2-pyridyl)phenyl group, 3-(4-methyl-2-pyridyl)phenyl group, 4-(4-methyl-2-pyridyl) ) phenyl group, 2-(5-methyl-2-pyridyl)phenyl group, 3-(5-methyl-2-pyridyl)phenyl group, 4-(5-methyl-2-pyridyl)phenyl group, 2-(6 -methyl-2-pyridyl)phenyl group, 3-(6-methyl-2-pyridyl)phenyl group, 4-(6-methyl-2-pyridyl)phenyl group, 2-(2-methyl-3-pyridyl)phenyl group, 3-(2-methyl-3-pyridyl)phenyl group, 4-(2-methyl-3-pyridyl)phenyl group, 2-(4-methyl-3-pyridyl)phenyl group, 3-(4-methyl -3-pyridyl)phenyl group, 4-(4-methyl-3-pyridyl)phenyl group, 2-(5-methyl-3-pyridyl)phenyl group, 3-(5-methyl-3-pyridyl)phenyl group, 4-(5-methyl-3-pyridyl)phenyl group, 2-(6-methyl-3-pyridyl)phenyl group, 3-(6-methyl-3-pyridyl)phenyl group, 4-(6-methyl-3 -pyridyl)phenyl group, 2-(2-methyl-4-pyridyl)phenyl group, 3-(2-methyl-4-pyridyl)phenyl group, 4-(2-methyl-4-pyridyl)phenyl group, 2- (3-methyl-4-pyridyl)phenyl group, 3-(3-methyl-4-pyridyl)phenyl group, 4-(3-methyl-4-pyridyl)phenyl group, 2,6-diphenylpyridin-3-yl 2,6-diphenylpyridin-4-yl group, 4,6-diphenylpyridin-2-yl group, 3,6-diphenylpyridin-4-yl group, 3,6-diphenylpyridin-5-yl group, 1-naphthyl group, 2-naphthyl group, 1-phenylnaphthalen-2-yl group, 1-phenylnaphthalen-3-yl group, 1-phenylnaphthalen-4-yl group, 1-phenylnaphthalen-5-yl group, 1-phenylnaphthalene-6-yl group, 1-phenylnaphthalene-7-yl group, 1-phenylnaphthalene-8-yl group, 2-phenylnaphthalene-1-yl group, 2-phenylnaphthalene-3-yl group, 2-phenylnaphthalene-4-yl group, 2-phenylnaphthalene-5-yl group, 2-phenylnaphthalene-6-yl group, 2-phenylnaphthalene-7-yl group, 2-phenylnaphthalene-8-yl group, 1-methylnaphthalene-4-yl group, 1-methylnaphthalene-5-yl group, 1-methylnaphthalene-6-yl group, 1-methylnaphthalene-7-yl group, 1-methylnaphthalene-8-yl group, 2-methylnaphthalene-1-yl group, 2-methylnaphthalene-3-yl group, 2-methylnaphthalene-4-yl group, 2-methylnaphthalene-5-yl group, 2-methylnaphthalene-6-yl group, 2-methylnaphthalene-7-yl group, 2-methylnaphthalene-8-yl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group,
1-phenylphenanthren-2-yl group, 1-phenylphenanthren-3-yl group, 1-phenylphenanthren-4-yl group, 1-phenylphenanthren-5-yl group, 1-phenylphenanthren-6-yl group, 1-phenylphenanthren-7-yl group, 1-phenylphenanthren-8-yl group, 1-phenylphenanthren-9-yl group, 1-phenylphenanthren-10-yl group, 2-phenylphenanthren-1-yl group, 2-phenylphenanthren-3-yl group, 2-phenylphenanthren-4-yl group, 2-phenylphenanthren-5-yl group, 2-phenylphenanthren-6-yl group, 2-phenylphenanthren-7-yl group, 2-phenylphenanthren-8-yl group, 2-phenylphenanthren-9-yl group, 2-phenylphenanthren-10-yl group, 3-phenylphenanthren-1-yl group, 3-phenylphenanthren-2-yl group, 3-phenylphenanthren-4-yl group, 3-phenylphenanthren-5-yl group, 3-phenylphenanthren-6-yl group, 3-phenylphenanthren-7-yl group, 3-phenylphenanthren-8-yl group, 3-phenylphenanthren-9-yl group, 3-phenylphenanthren-10-yl group, 4-phenylphenanthren-1-yl group, 4-phenylphenanthren-2-yl group, 4-phenylphenanthren-3-yl group, 4-phenylphenanthren-5-yl group, 4-phenylphenanthren-6-yl group, 4-phenylphenanthren-7-yl group, 4-phenylphenanthren-8-yl group, 4-phenylphenanthren-9-yl group, 4-phenylphenanthren-10-yl group, 1-methylphenanthren-2-yl group, 1-methylphenanthren-3-yl group, 1-methylphenanthren-4-yl group, 1-methylphenanthren-5-yl group, 1-methylphenanthren-6-yl group, 1-methylphenanthren-7-yl group, 1-methylphenanthren-8-yl group, 1-methylphenanthren-9-yl group, 1-methylphenanthren-10-yl group, 2-methylphenanthren-1-yl group, 2-methylphenanthren-3-yl group, 2-methylphenanthren-4-yl group, 2-methylphenanthren-5-yl group, 2-methylphenanthren-6-yl group, 2-methylphenanthren-7-yl group, 2-methylphenanthren-8-yl group, 2-methylphenanthren-9-yl group, 2-methylphenanthren-10-yl group, 3-methylphenanthren-1-yl group, 3-methylphenanthren-2-yl group, 3-methylphenanthren-4-yl group, 3-methylphenanthren-5-yl group, 3-methylphenanthren-6-yl group, 3-methylphenanthren-7-yl group, 3-methylphenanthren-8-yl group, 3-methylphenanthren-9-yl group, 3-methylphenanthren-10-yl group, 4-methylphenanthren-1-yl group, 4-methylphenanthren-2-yl group, 4-methylphenanthren-3-yl group, 4-methylphenanthren-5-yl group, 4-methylphenanthren-6-yl group, 4-methylphenanthren-7-yl group, 4-methylphenanthren-8-yl group, 4-methylphenanthren-9-yl group, 4-methylphenanthren-10-yl group, 1-anthryl group, 2-anthryl group, 9-anthryl group,
1-phenylanthracen-2-yl group, 1-phenylanthracen-3-yl group, 1-phenylanthracen-4-yl group, 1-phenylanthracen-5-yl group, 1-phenylanthracen-6-yl group, 1-phenylanthracen-7-yl group, 1-phenylanthracen-8-yl group, 1-phenylanthracen-9-yl group, 1-phenylanthracen-10-yl group, 2-phenylanthracen-1-yl group, 2-phenylanthracen-3-yl group, 2-phenylanthracen-4-yl group, 2-phenylanthracen-5-yl group, 2-phenylanthracen-6-yl group, 2-phenylanthracen-7-yl group, 2-phenylanthracen-8-yl group, 2-phenylanthracen-9-yl group, 2-phenylanthracen-10-yl group, 9-phenylanthracen-1-yl group, 9-phenylanthracen-2-yl group, 9-phenylanthracen-3-yl group, 9-phenylanthracen-4-yl group, 9-phenylanthracen-5-yl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 1-phenylpyrene- 2-yl group, 1-phenylpyren-3-yl group, 1-phenylpyren-4-yl group, 1-phenylpyren-5-yl group, 1-phenylpyren-6-yl group, 1-phenylpyrene- 7-yl group, 1-phenylpyren-8-yl group, 1-phenylpyren-9-yl group, 1-phenylpyren-10-yl group, 2-phenylpyren-1-yl group, 2-phenylpyrene- 3-yl group, 2-phenylpyren-4-yl group, 2-phenylpyren-5-yl group, 2-phenylpyren-6-yl group, 2-phenylpyren-7-yl group, 2-phenylpyrene- 8-yl group, 2-phenylpyren-9-yl group, 2-phenylpyren-10-yl group, 9-phenylpyren-1-yl group, 9-phenylpyren-2-yl group, 9-phenylpyrene- 3-yl group, 9-phenylpyren-4-yl group, 9-phenylpyren-5-yl group, 9-phenylpyren-6-yl group, 9-phenylpyren-7-yl group, 9-phenylpyrene- 8-yl group, 9-phenylpyren-10-yl group, 1-methylpyren-2-yl group, 1-methylpyren-3-yl group, 1-methylpyren-4-yl group, 1-methylpyren-5-yl group , 1-methylpyren-6-yl group, 1-methylpyren-7-yl group, 1-methylpyren-8-yl group, 1-methylpyren-9-yl group, 1-methylpyren-10-yl group, 2-methylpyren- 1-yl group, 2-methylpyren-3-yl group, 2-methylpyren-4-yl group, 2-methylpyren-5-yl group, 2-methylpyren-6-yl group, 2-methylpyren-7-yl group, 2-methylpyren-8-yl group, 2-methylpyren-9-yl group, 2-methylpyren-10-yl group, 9-methylpyren-1-yl group, 9-methylpyren-2-yl group, 9-methylpyren-3 -yl group, 9-methylpyren-4-yl group, 9-methylpyren-5-yl group, 9-methylpyren-6-yl group, 9-methylpyren-7-yl group, 9-methylpyren-8-yl group, 9 - methylpyren-10-yl group, fluoranthene-1-yl group, fluoranthene-1-yl group, fluoranthene-2-yl group, fluoranthene-3-yl group, fluoranthene-4-yl group, fluoranthene-5-yl group, fluoranthene-6-yl group, fluoranthene-7-yl group, fluoranthene-8-yl group, fluoranthene-9-yl group, fluoranthene-10-yl group, triphenylene-1-yl group, triphenylene-2-yl group, acenaphthylene -1-yl group, acenaphthylene-3-yl group, acenaphthylene-4-yl group, acenaphthylene-5-yl group, chrysen-1-yl group, chrysen-2-yl group, chrysen-5-yl group, chrysen- 6-yl group,
2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, quinoxalin-2-yl group, quinoxalin-5-yl group, quinoxalin-6-yl group, quinazolin-2-yl group, quinazoline- 4-yl group, quinazolin-5-yl group, quinazolin-6-yl group, quinazolin-7-yl group, quinazolin-8-yl group, pyrazin-2-yl group, 5-methylpyrazin-2-yl group, 5,6-diphenylpyrazin-2-yl group, pyrimidin-2-yl group, pyrimidin-4-yl group, pyrimidin-5-yl group, 2,4-diphenylpyrimidin-6-yl group, 4,6-diphenyl pyrimidin-2-yl group, acridin-1-yl group, acridin-1-yl group, acridin-2-yl group, acridin-3-yl group, acridin-4-yl group, acridin-9-yl group, phenyl Nanthridin-1-yl group, phenanthridin-1-yl group, phenanthridin-2-yl group, phenanthridin-3-yl group, phenanthridin-4-yl group, phenanthridin-6- yl group, phenanthridin-7-yl group, phenanthridin-8-yl group, phenanthridin-9-yl group, phenanthridin-10-yl group, phenazin-1-yl group, phenazin-2- yl group, benzo[h]quinolin-2-yl group, benzo[h]quinolin-3-yl group, benzo[h]quinolin-4-yl group, benzo[h]quinolin-5-yl group, benzo[h ] quinolin-6-yl group, benzo[h]quinolin-7-yl group, benzo[h]quinolin-8-yl group, benzo[h]quinolin-9-yl group, benzo[h]quinolin-10-yl group, 2-thienyl group, 3-thienyl group, 2-furyl group, 3-furyl group, benzothiophen-2-yl group, benzothiophen-3-yl group, benzothiophen-4-yl group, benzothiophene-5 -yl group, benzothiophen-6-yl group, benzothiophen-7-yl group, benzofuran-2-yl group, benzofuran-3-yl group, benzofuran-4-yl group, benzofuran-5-yl group, benzofuran- 6-yl group, benzofuran-7-yl group, dibenzothiophen-1-yl group, dibenzothiophen-2-yl group, dibenzothiophen-3-yl group, dibenzofuran-1-yl group, dibenzofuran-2-yl group, dibenzofuran-3-yl group, 3-methylthiophen-2-yl group, 4-methylthiophen-2-yl group, 5-methylthiophen-2-yl group, 2-methylthiophen-3-yl group, 4-methyl thiophen-3-yl group, 5-methylthiophen-3-yl group, 3-methylfuran-2-yl group, 4-methylfuran-2-yl group, 5-methylfuran-2-yl group, 2-methyl furan-3-yl group, 4-methylfuran-3-yl group, 5-methylfuran-3-yl group,
3-methylbenzothiophen-2-yl group, 4-methylbenzothiophen-2-yl group, 5-methylbenzothiophen-2-yl group, 6-methylbenzothiophen-2-yl group, 7-methylbenzothiophene- 2-yl group, 2-methylbenzothiophen-3-yl group, 4-methylbenzothiophen-3-yl group, 5-methylbenzothiophen-3-yl group, 6-methylbenzothiophen-3-yl group, 7 -methylbenzothiophen-3-yl group, 2-methylbenzothiophen-4-yl group, 3-methylbenzothiophen-4-yl group, 5-methylbenzothiophen-4-yl group, 6-methylbenzothiophene-4 -yl group, 7-methylbenzothiophen-4-yl group, 2-methylbenzothiophen-5-yl group, 3-methylbenzothiophen-5-yl group, 4-methylbenzothiophen-5-yl group, 6- methylbenzothiophen-5-yl group, 7-methylbenzothiophen-5-yl group, 2-methylbenzothiophen-6-yl group, 3-methylbenzothiophen-6-yl group, 4-methylbenzothiophene-6- yl group, 5-methylbenzothiophen-6-yl group, 7-methylbenzothiophen-6-yl group, 2-methylbenzothiophen-7-yl group, 3-methylbenzothiophen-7-yl group, 4-methyl benzothiophen-7-yl group, 5-methylbenzothiophen-7-yl group, 6-methylbenzothiophen-7-yl group, 3-methylbenzofuran-2-yl group, 4-methylbenzofuran-2-yl group, 5-methylbenzofuran-2-yl group, 6-methylbenzofuran-2-yl group, 7-methylbenzofuran-2-yl group, 2-methylbenzofuran-3-yl group, 4-methylbenzofuran-3-yl group, 5-methylbenzofuran-3-yl group, 6-methylbenzofuran-3-yl group, 7-methylbenzofuran-3-yl group, 2-methylbenzofuran-4-yl group, 3-methylbenzofuran-4-yl group, 5-methylbenzofuran-4-yl group, 6-methylbenzofuran-4-yl group, 7-methylbenzofuran-4-yl group, 2-methylbenzofuran-5-yl group, 3-methylbenzofuran-5-yl group, 4-methylbenzofuran-5-yl group, 6-methylbenzofuran-5-yl group, 7-methylbenzofuran-5-yl group, 2-methylbenzofuran-6-yl group, 3-methylbenzofuran-6-yl group, 4-methylbenzofuran-6-yl group, 5-methylbenzofuran-6-yl group, 7-methylbenzofuran-6-yl group, 2-methylbenzofuran-7-yl group, 3-methylbenzofuran-7-yl group, 4-methylbenzofuran-7-yl group, 5-methylbenzofuran-7-yl group, 6-methylbenzofuran-7-yl group, 2-methyldibenzothiophen-1-yl group, 3-methyldibenzothiophen-1-yl group, 4-methyldibenzothiophen-1-yl group, 6-methyldibenzothiophen-1-yl group, 7-methyldibenzothiophen-1-yl group, 8-methyldibenzothiophen-1-yl group, 9-methyldibenzo thiophen-1-yl group, 1-methyldibenzothiophen-2-yl group, 3-methyldibenzothiophen-2-yl group, 4-methyldibenzothiophen-2-yl group, 6-methyldibenzothiophen-2-yl group , 7-methyldibenzothiophen-2-yl group, 8-methyldibenzothiophen-2-yl group, 9-methyldibenzothiophen-2-yl group, 1-methyldibenzothiophen-3-yl group, 2-methyldibenzothiophene -3-yl group, 4-methyldibenzothiophen-3-yl group, 6-methyldibenzothiophen-3-yl group, 7-methyldibenzothiophen-3-yl group, 8-methyldibenzothiophen-3-yl group,
9-methyldibenzothiophen-3-yl group, 2-methyldibenzofuran-1-yl group, 3-methyldibenzofuran-1-yl group, 4-methyldibenzofuran-1-yl group, 6-methyldibenzofuran-1-yl group , 7-methyldibenzofuran-1-yl group, 8-methyldibenzofuran-1-yl group, 9-methyldibenzofuran-1-yl group, 1-methyldibenzofuran-2-yl group, 3-methyldibenzofuran-2-yl group , 4-methyldibenzofuran-2-yl group, 6-methyldibenzofuran-2-yl group, 7-methyldibenzofuran-2-yl group, 8-methyldibenzofuran-2-yl group, 9-methyldibenzofuran-2-yl group , 1-methyldibenzofuran-3-yl group, 2-methyldibenzofuran-3-yl group, 4-methyldibenzofuran-3-yl group, 6-methyldibenzofuran-3-yl group, 7-methyldibenzofuran-3-yl group , 8-methyldibenzofuran-3-yl group, 9-methyldibenzofuran-3-yl group, 3-phenylthiophen-2-yl group, 4-phenylthiophen-2-yl group, 5-phenylthiophen-2-yl group , 2-phenylthiophen-3-yl group, 4-phenylthiophen-3-yl group, 5-phenylthiophen-3-yl group, 3-phenylfuran-2-yl group, 4-phenylfuran-2-yl group , 5-phenylfuran-2-yl group, 2-phenylfuran-3-yl group, 4-phenylfuran-3-yl group, 5-phenylfuran-3-yl group, 3-phenylbenzothiophen-2-yl group, 4-phenylbenzothiophen-2-yl group, 5-phenylbenzothiophen-2-yl group, 6-phenylbenzothiophen-2-yl group, 7-phenylbenzothiophen-2-yl group, 2-phenylbenzo thiophen-3-yl group, 4-phenylbenzothiophen-3-yl group, 5-phenylbenzothiophen-3-yl group, 6-phenylbenzothiophen-3-yl group, 7-phenylbenzothiophen-3-yl group , 2-phenylbenzothiophen-4-yl group, 3-phenylbenzothiophen-4-yl group, 5-phenylbenzothiophen-4-yl group, 6-phenylbenzothiophen-4-yl group, 7-phenylbenzothiophene -4-yl group, 2-phenylbenzothiophen-5-yl group, 3-phenylbenzothiophen-5-yl group, 4-phenylbenzothiophen-5-yl group, 6-phenylbenzothiophen-5-yl group, 7-phenylbenzothiophen-5-yl group, 2-phenylbenzothiophen-6-yl group, 3-phenylbenzothiophen-6-yl group, 4-phenylbenzothiophen-6-yl group, 5-phenylbenzothiophene- 6-yl group, 7-phenylbenzothiophen-6-yl group, 2-phenylbenzothiophen-7-yl group, 3-phenylbenzothiophen-7-yl group, 4-phenylbenzothiophen-7-yl group, 5 -phenylbenzothiophen-7-yl group, 6-phenylbenzothiophen-7-yl group, 3-phenylbenzofuran-2-yl group, 4-phenylbenzofuran-2-yl group, 5-phenylbenzofuran-2-yl group , 6-phenylbenzofuran-2-yl group, 7-phenylbenzofuran-2-yl group, 2-phenylbenzofuran-3-yl group, 4-phenylbenzofuran-3-yl group, 5-phenylbenzofuran-3-yl group , 6-phenylbenzofuran-3-yl group, 7-phenylbenzofuran-3-yl group, 2-phenylbenzofuran-4-yl group, 3-phenylbenzofuran-4-yl group,
5-phenylbenzofuran-4-yl group, 6-phenylbenzofuran-4-yl group, 7-phenylbenzofuran-4-yl group, 2-phenylbenzofuran-5-yl group, 3-phenylbenzofuran-5-yl group, 4-phenylbenzofuran-5-yl group, 6-phenylbenzofuran-5-yl group, 7-phenylbenzofuran-5-yl group, 2-phenylbenzofuran-6-yl group, 3-phenylbenzofuran-6-yl group, 4-phenylbenzofuran-6-yl group, 5-phenylbenzofuran-6-yl group, 7-phenylbenzofuran-6-yl group, 2-phenylbenzofuran-7-yl group, 3-phenylbenzofuran-7-yl group, 4-phenylbenzofuran-7-yl group, 5-phenylbenzofuran-7-yl group, 6-phenylbenzofuran-7-yl group, 2-phenyldibenzothiophen-1-yl group, 3-phenyldibenzothiophen-1-yl group, 4-phenyldibenzothiophen-1-yl group, 6-phenyldibenzothiophen-1-yl group, 7-phenyldibenzothiophen-1-yl group, 8-phenyldibenzothiophen-1-yl group, 9-phenyldibenzo thiophen-1-yl group, 1-phenyldibenzothiophen-2-yl group, 3-phenyldibenzothiophen-2-yl group, 4-phenyldibenzothiophen-2-yl group, 6-phenyldibenzothiophen-2-yl group , 7-phenyldibenzothiophen-2-yl group, 8-phenyldibenzothiophen-2-yl group, 9-phenyldibenzothiophen-2-yl group, 1-phenyldibenzothiophen-3-yl group, 2-phenyldibenzothiophene -3-yl group, 4-phenyldibenzothiophen-3-yl group, 6-phenyldibenzothiophen-3-yl group, 7-phenyldibenzothiophen-3-yl group, 8-phenyldibenzothiophen-3-yl group, 9-phenyldibenzothiophen-3-yl group, 2-phenyldibenzofuran-1-yl group, 3-phenyldibenzofuran-1-yl group, 4-phenyldibenzofuran-1-yl group, 6-phenyldibenzofuran-1-yl group , 7-phenyldibenzofuran-1-yl group, 8-phenyldibenzofuran-1-yl group, 9-phenyldibenzofuran-1-yl group, 1-phenyldibenzofuran-2-yl group, 3-phenyldibenzofuran-2-yl group , 4-phenyldibenzofuran-2-yl group, 6-phenyldibenzofuran-2-yl group, 7-phenyldibenzofuran-2-yl group, 8-phenyldibenzofuran-2-yl group, 9-phenyldibenzofuran-2-yl group , 1-phenyldibenzofuran-3-yl group, 2-phenyldibenzofuran-3-yl group, 4-phenyldibenzofuran-3-yl group, 6-phenyldibenzofuran-3-yl group, 7-phenyldibenzofuran-3-yl group , 8-phenyldibenzofuran-3-yl group, 9-phenyldibenzofuran-3-yl group,
3-(2-pyridyl)thiophen-2-yl group, 4-(2-pyridyl)thiophen-2-yl group, 5-(2-pyridyl)thiophen-2-yl group, 2-(2-pyridyl)thiophene -3-yl group, 4-(2-pyridyl)thiophen-3-yl group, 5-(2-pyridyl)thiophen-3-yl group, 3-(2-pyridyl)furan-2-yl group, 4- (2-pyridyl)furan-2-yl group, 5-(2-pyridyl)furan-2-yl group, 2-(2-pyridyl)furan-3-yl group, 4-(2-pyridyl)furan-3 -yl group, 5-(2-pyridyl)furan-3-yl group, 3-(2-pyridyl)benzothiophen-2-yl group, 4-(2-pyridyl)benzothiophen-2-yl group, 5- (2-pyridyl)benzothiophen-2-yl group, 6-(2-pyridyl)benzothiophen-2-yl group, 7-(2-pyridyl)benzothiophen-2-yl group, 2-(2-pyridyl) benzothiophen-3-yl group, 4-(2-pyridyl)benzothiophen-3-yl group, 5-(2-pyridyl)benzothiophen-3-yl group, 6-(2-pyridyl)benzothiophene-3- yl group, 7-(2-pyridyl)benzothiophen-3-yl group, 2-(2-pyridyl)benzothiophen-4-yl group, 3-(2-pyridyl)benzothiophen-4-yl group, 5- (2-pyridyl)benzothiophen-4-yl group, 6-(2-pyridyl)benzothiophen-4-yl group, 7-(2-pyridyl)benzothiophen-4-yl group, 2-(2-pyridyl) benzothiophen-5-yl group, 3-(2-pyridyl)benzothiophen-5-yl group, 4-(2-pyridyl)benzothiophen-5-yl group, 6-(2-pyridyl)benzothiophene-5- yl group, 7-(2-pyridyl)benzothiophen-5-yl group, 2-(2-pyridyl)benzothiophen-6-yl group, 3-(2-pyridyl)benzothiophen-6-yl group, 4- (2-pyridyl)benzothiophen-6-yl group, 5-(2-pyridyl)benzothiophen-6-yl group, 7-(2-pyridyl)benzothiophen-6-yl group, 2-(2-pyridyl) benzothiophen-7-yl group, 3-(2-pyridyl)benzothiophen-7-yl group, 4-(2-pyridyl)benzothiophen-7-yl group, 5-(2-pyridyl)benzothiophene-7- yl group, 6-(2-pyridyl)benzothiophen-7-yl group, 3-(2-pyridyl)benzofuran-2-yl group, 4-(2-pyridyl)benzofuran-2-yl group, 5-(2 -pyridyl)benzofuran-2-yl group, 6-(2-pyridyl)benzofuran-2-yl group, 7-(2-pyridyl)benzofuran-2-yl group, 2-(2-pyridyl)benzofuran-3-yl group, 4-(2-pyridyl)benzofuran-3-yl group, 5-(2-pyridyl)benzofuran-3-yl group, 6-(2-pyridyl)benzofuran-3-yl group, 7-(2-pyridyl ) benzofuran-3-yl group, 2-(2-pyridyl)benzofuran-4-yl group, 3-(2-pyridyl)benzofuran-4-yl group, 5-(2-pyridyl)benzofuran-4-yl group, 6-(2-pyridyl)benzofuran-4-yl group, 7-(2-pyridyl)benzofuran-4-yl group, 2-(2-pyridyl)benzofuran-5-yl group, 3-(2-pyridyl)benzofuran -5-yl group, 4-(2-pyridyl)benzofuran-5-yl group, 6-(2-pyridyl)benzofuran-5-yl group, 7-(2-pyridyl)benzofuran-5-yl group, 2- (2-pyridyl)benzofuran-6-yl group, 3-(2-pyridyl)benzofuran-6-yl group, 4-(2-pyridyl)benzofuran-6-yl group, 5-(2-pyridyl)benzofuran-6 -yl group, 7-(2-pyridyl)benzofuran-6-yl group, 2-(2-pyridyl)benzofuran-7-yl group,
3-(2-pyridyl)benzofuran-7-yl group, 4-(2-pyridyl)benzofuran-7-yl group, 5-(2-pyridyl)benzofuran-7-yl group, 6-(2-pyridyl)benzofuran -7-yl group, 2-(2-pyridyl)dibenzothiophen-1-yl group, 3-(2-pyridyl)dibenzothiophen-1-yl group, 4-(2-pyridyl)dibenzothiophen-1-yl group , 6-(2-pyridyl) dibenzothiophen-1-yl group, 7-(2-pyridyl) dibenzothiophen-1-yl group, 8-(2-pyridyl) dibenzothiophen-1-yl group, 9-(2 -pyridyl)dibenzothiophen-1-yl group, 1-(2-pyridyl)dibenzothiophen-2-yl group, 3-(2-pyridyl)dibenzothiophen-2-yl group, 4-(2-pyridyl)dibenzothiophene -2-yl group, 6-(2-pyridyl)dibenzothiophen-2-yl group, 7-(2-pyridyl)dibenzothiophen-2-yl group, 8-(2-pyridyl)dibenzothiophen-2-yl group , 9-(2-pyridyl) dibenzothiophen-2-yl group, 1-(2-pyridyl) dibenzothiophen-3-yl group, 2-(2-pyridyl) dibenzothiophen-3-yl group, 4-(2 -pyridyl)dibenzothiophen-3-yl group, 6-(2-pyridyl)dibenzothiophen-3-yl group, 7-(2-pyridyl)dibenzothiophen-3-yl group, 8-(2-pyridyl)dibenzothiophene -3-yl group, 9-(2-pyridyl)dibenzothiophen-3-yl group, 2-(2-pyridyl)dibenzofuran-1-yl group, 3-(2-pyridyl)dibenzofuran-1-yl group, 4 -(2-pyridyl) dibenzofuran-1-yl group, 6-(2-pyridyl) dibenzofuran-1-yl group, 7-(2-pyridyl) dibenzofuran-1-yl group, 8-(2-pyridyl) dibenzofuran- 1-yl group, 9-(2-pyridyl) dibenzofuran-1-yl group, 1-(2-pyridyl) dibenzofuran-2-yl group, 3-(2-pyridyl) dibenzofuran-2-yl group, 4-( 2-pyridyl)dibenzofuran-2-yl group, 6-(2-pyridyl)dibenzofuran-2-yl group, 7-(2-pyridyl)dibenzofuran-2-yl group, 8-(2-pyridyl)dibenzofuran-2- yl group, 9-(2-pyridyl) dibenzofuran-2-yl group, 1-(2-pyridyl) dibenzofuran-3-yl group, 2-(2-pyridyl) dibenzofuran-3-yl group, 4-(2- pyridyl)dibenzofuran-3-yl group, 6-(2-pyridyl)dibenzofuran-3-yl group, 7-(2-pyridyl)dibenzofuran-3-yl group, 8-(2-pyridyl)dibenzofuran-3-yl group , 9-(2-pyridyl) dibenzofuran-3-yl group, 3-(3-pyridyl) thiophen-2-yl group, 4-(3-pyridyl) thiophen-2-yl group, 5-(3-pyridyl) thiophen-2-yl group, 2-(3-pyridyl)thiophen-3-yl group, 4-(3-pyridyl)thiophen-3-yl group, 5-(3-pyridyl)thiophen-3-yl group, 3 -(3-pyridyl)furan-2-yl group, 4-(3-pyridyl)furan-2-yl group, 5-(3-pyridyl)furan-2-yl group, 2-(3-pyridyl)furan- 3-yl group, 4-(3-pyridyl)furan-3-yl group, 5-(3-pyridyl)furan-3-yl group,
3-(3-pyridyl)benzothiophen-2-yl group, 4-(3-pyridyl)benzothiophen-2-yl group, 5-(3-pyridyl)benzothiophen-2-yl group, 6-(3- pyridyl)benzothiophen-2-yl group, 7-(3-pyridyl)benzothiophen-2-yl group, 2-(3-pyridyl)benzothiophen-3-yl group, 4-(3-pyridyl)benzothiophene- 3-yl group, 5-(3-pyridyl)benzothiophen-3-yl group, 6-(3-pyridyl)benzothiophen-3-yl group, 7-(3-pyridyl)benzothiophen-3-yl group, 2-(3-pyridyl)benzothiophen-4-yl group, 3-(3-pyridyl)benzothiophen-4-yl group, 5-(3-pyridyl)benzothiophen-4-yl group, 6-(3- pyridyl)benzothiophen-4-yl group, 7-(3-pyridyl)benzothiophen-4-yl group, 2-(3-pyridyl)benzothiophen-5-yl group, 3-(3-pyridyl)benzothiophene- 5-yl group, 4-(3-pyridyl)benzothiophen-5-yl group, 6-(3-pyridyl)benzothiophen-5-yl group, 7-(3-pyridyl)benzothiophen-5-yl group, 2-(3-pyridyl)benzothiophen-6-yl group, 3-(3-pyridyl)benzothiophen-6-yl group, 4-(3-pyridyl)benzothiophen-6-yl group, 5-(3- pyridyl)benzothiophen-6-yl group, 7-(3-pyridyl)benzothiophen-6-yl group, 2-(3-pyridyl)benzothiophen-7-yl group, 3-(3-pyridyl)benzothiophene- 7-yl group, 4-(3-pyridyl)benzothiophen-7-yl group, 5-(3-pyridyl)benzothiophen-7-yl group, 6-(3-pyridyl)benzothiophen-7-yl group, 3-(3-pyridyl)benzofuran-2-yl group, 4-(3-pyridyl)benzofuran-2-yl group, 5-(3-pyridyl)benzofuran-2-yl group, 6-(3-pyridyl)benzofuran -2-yl group, 7-(3-pyridyl)benzofuran-2-yl group, 2-(3-pyridyl)benzofuran-3-yl group, 4-(3-pyridyl)benzofuran-3-yl group, 5- (3-pyridyl)benzofuran-3-yl group, 6-(3-pyridyl)benzofuran-3-yl group, 7-(3-pyridyl)benzofuran-3-yl group, 2-(3-pyridyl)benzofuran-4 -yl group, 3-(3-pyridyl)benzofuran-4-yl group, 5-(3-pyridyl)benzofuran-4-yl group, 6-(3-pyridyl)benzofuran-4-yl group, 7-(3 -pyridyl)benzofuran-4-yl group, 2-(3-pyridyl)benzofuran-5-yl group, 3-(3-pyridyl)benzofuran-5-yl group, 4-(3-pyridyl)benzofuran-5-yl group, 6-(3-pyridyl)benzofuran-5-yl group, 7-(3-pyridyl)benzofuran-5-yl group, 2-(3-pyridyl)benzofuran-6-yl group, 3-(3-pyridyl ) benzofuran-6-yl group, 4-(3-pyridyl)benzofuran-6-yl group, 5-(3-pyridyl)benzofuran-6-yl group, 7-(3-pyridyl)benzofuran-6-yl group, 2-(3-pyridyl)benzofuran-7-yl group, 3-(3-pyridyl)benzofuran-7-yl group, 4-(3-pyridyl)benzofuran-7-yl group, 5-(3-pyridyl)benzofuran -7-yl group, 6-(3-pyridyl)benzofuran-7-yl group,
2-(3-pyridyl) dibenzothiophen-1-yl group, 3-(3-pyridyl) dibenzothiophen-1-yl group, 4-(3-pyridyl) dibenzothiophen-1-yl group, 6-(3- pyridyl)dibenzothiophen-1-yl group, 7-(3-pyridyl)dibenzothiophen-1-yl group, 8-(3-pyridyl)dibenzothiophen-1-yl group, 9-(3-pyridyl)dibenzothiophene- 1-yl group, 1-(3-pyridyl)dibenzothiophen-2-yl group, 3-(3-pyridyl)dibenzothiophen-2-yl group, 4-(3-pyridyl)dibenzothiophen-2-yl group, 6-(3-pyridyl) dibenzothiophen-2-yl group, 7-(3-pyridyl) dibenzothiophen-2-yl group, 8-(3-pyridyl) dibenzothiophen-2-yl group, 9-(3- pyridyl)dibenzothiophen-2-yl group, 1-(3-pyridyl)dibenzothiophen-3-yl group, 2-(3-pyridyl)dibenzothiophen-3-yl group, 4-(3-pyridyl)dibenzothiophene- 3-yl group, 6-(3-pyridyl)dibenzothiophen-3-yl group, 7-(3-pyridyl)dibenzothiophen-3-yl group, 8-(3-pyridyl)dibenzothiophen-3-yl group, 9-(3-pyridyl)dibenzothiophen-3-yl group, 2-(3-pyridyl)dibenzofuran-1-yl group, 3-(3-pyridyl)dibenzofuran-1-yl group, 4-(3-pyridyl) dibenzofuran-1-yl group, 6-(3-pyridyl)dibenzofuran-1-yl group, 7-(3-pyridyl)dibenzofuran-1-yl group, 8-(3-pyridyl)dibenzofuran-1-yl group, 9 -(3-pyridyl) dibenzofuran-1-yl group, 1-(3-pyridyl) dibenzofuran-2-yl group, 3-(3-pyridyl) dibenzofuran-2-yl group, 4-(3-pyridyl) dibenzofuran- 2-yl group, 6-(3-pyridyl) dibenzofuran-2-yl group, 7-(3-pyridyl) dibenzofuran-2-yl group, 8-(3-pyridyl) dibenzofuran-2-yl group, 9-( 3-pyridyl)dibenzofuran-2-yl group, 1-(3-pyridyl)dibenzofuran-3-yl group, 2-(3-pyridyl)dibenzofuran-3-yl group, 4-(3-pyridyl)dibenzofuran-3- yl group, 6-(3-pyridyl) dibenzofuran-3-yl group, 7-(3-pyridyl) dibenzofuran-3-yl group, 8-(3-pyridyl) dibenzofuran-3-yl group, 9-(3- pyridyl)dibenzofuran-3-yl group, 3-(4-pyridyl)thiophen-2-yl group, 4-(4-pyridyl)thiophen-2-yl group, 5-(4-pyridyl)thiophen-2-yl group , 2-(4-pyridyl)thiophen-3-yl group, 4-(4-pyridyl)thiophen-3-yl group, 5-(4-pyridyl)thiophen-3-yl group, 3-(4-pyridyl) furan-2-yl group, 4-(4-pyridyl)furan-2-yl group, 5-(4-pyridyl)furan-2-yl group, 2-(4-pyridyl)furan-3-yl group, 4 -(4-pyridyl) furan-3-yl group, 5-(4-pyridyl) furan-3-yl group, 3-(4-pyridyl) benzothiophen-2-yl group, 4-(4-pyridyl) benzo thiophen-2-yl group, 5-(4-pyridyl)benzothiophen-2-yl group, 6-(4-pyridyl)benzothiophen-2-yl group, 7-(4-pyridyl)benzothiophen-2-yl group, 2-(4-pyridyl)benzothiophen-3-yl group, 4-(4-pyridyl)benzothiophen-3-yl group,
5-(4-pyridyl)benzothiophen-3-yl group, 6-(4-pyridyl)benzothiophen-3-yl group, 7-(4-pyridyl)benzothiophen-3-yl group, 2-(4- pyridyl)benzothiophen-4-yl group, 3-(4-pyridyl)benzothiophen-4-yl group, 5-(4-pyridyl)benzothiophen-4-yl group, 6-(4-pyridyl)benzothiophene- 4-yl group, 7-(4-pyridyl)benzothiophen-4-yl group, 2-(4-pyridyl)benzothiophen-5-yl group, 3-(4-pyridyl)benzothiophen-5-yl group, 4-(4-pyridyl)benzothiophen-5-yl group, 6-(4-pyridyl)benzothiophen-5-yl group, 7-(4-pyridyl)benzothiophen-5-yl group, 2-(4- pyridyl)benzothiophen-6-yl group, 3-(4-pyridyl)benzothiophen-6-yl group, 4-(4-pyridyl)benzothiophen-6-yl group, 5-(4-pyridyl)benzothiophene- 6-yl group, 7-(4-pyridyl)benzothiophen-6-yl group, 2-(4-pyridyl)benzothiophen-7-yl group, 3-(4-pyridyl)benzothiophen-7-yl group, 4-(4-pyridyl)benzothiophen-7-yl group, 5-(4-pyridyl)benzothiophen-7-yl group, 6-(4-pyridyl)benzothiophen-7-yl group, 3-(4- pyridyl)benzofuran-2-yl group, 4-(4-pyridyl)benzofuran-2-yl group, 5-(4-pyridyl)benzofuran-2-yl group, 6-(4-pyridyl)benzofuran-2-yl group , 7-(4-pyridyl)benzofuran-2-yl group, 2-(4-pyridyl)benzofuran-3-yl group, 4-(4-pyridyl)benzofuran-3-yl group, 5-(4-pyridyl) benzofuran-3-yl group, 6-(4-pyridyl)benzofuran-3-yl group, 7-(4-pyridyl)benzofuran-3-yl group, 2-(4-pyridyl)benzofuran-4-yl group, 3 -(4-pyridyl)benzofuran-4-yl group, 5-(4-pyridyl)benzofuran-4-yl group, 6-(4-pyridyl)benzofuran-4-yl group, 7-(4-pyridyl)benzofuran- 4-yl group, 2-(4-pyridyl)benzofuran-5-yl group, 3-(4-pyridyl)benzofuran-5-yl group, 4-(4-pyridyl)benzofuran-5-yl group, 6-( 4-pyridyl)benzofuran-5-yl group, 7-(4-pyridyl)benzofuran-5-yl group, 2-(4-pyridyl)benzofuran-6-yl group, 3-(4-pyridyl)benzofuran-6- yl group, 4-(4-pyridyl)benzofuran-6-yl group, 5-(4-pyridyl)benzofuran-6-yl group, 7-(4-pyridyl)benzofuran-6-yl group, 2-(4- pyridyl)benzofuran-7-yl group, 3-(4-pyridyl)benzofuran-7-yl group, 4-(4-pyridyl)benzofuran-7-yl group, 5-(4-pyridyl)benzofuran-7-yl group , 6-(4-pyridyl) benzofuran-7-yl group, 2-(4-pyridyl) dibenzothiophen-1-yl group, 3-(4-pyridyl) dibenzothiophen-1-yl group, 4-(4- pyridyl)dibenzothiophen-1-yl group, 6-(4-pyridyl)dibenzothiophen-1-yl group, 7-(4-pyridyl)dibenzothiophen-1-yl group,
8-(4-pyridyl) dibenzothiophen-1-yl group, 9-(4-pyridyl) dibenzothiophen-1-yl group, 1-(4-pyridyl) dibenzothiophen-2-yl group, 3-(4- pyridyl)dibenzothiophen-2-yl group, 4-(4-pyridyl)dibenzothiophen-2-yl group, 6-(4-pyridyl)dibenzothiophen-2-yl group, 7-(4-pyridyl)dibenzothiophene- 2-yl group, 8-(4-pyridyl)dibenzothiophen-2-yl group, 9-(4-pyridyl)dibenzothiophen-2-yl group, 1-(4-pyridyl)dibenzothiophen-3-yl group, 2-(4-pyridyl) dibenzothiophen-3-yl group, 4-(4-pyridyl) dibenzothiophen-3-yl group, 6-(4-pyridyl) dibenzothiophen-3-yl group, 7-(4- pyridyl)dibenzothiophen-3-yl group, 8-(4-pyridyl)dibenzothiophen-3-yl group, 9-(4-pyridyl)dibenzothiophen-3-yl group, 2-(4-pyridyl)dibenzofuran-1 -yl group, 3-(4-pyridyl)dibenzofuran-1-yl group, 4-(4-pyridyl)dibenzofuran-1-yl group, 6-(4-pyridyl)dibenzofuran-1-yl group, 7-(4 -pyridyl)dibenzofuran-1-yl group, 8-(4-pyridyl)dibenzofuran-1-yl group, 9-(4-pyridyl)dibenzofuran-1-yl group, 1-(4-pyridyl)dibenzofuran-2-yl group, 3-(4-pyridyl) dibenzofuran-2-yl group, 4-(4-pyridyl) dibenzofuran-2-yl group, 6-(4-pyridyl) dibenzofuran-2-yl group, 7-(4-pyridyl ) dibenzofuran-2-yl group, 8-(4-pyridyl)dibenzofuran-2-yl group, 9-(4-pyridyl)dibenzofuran-2-yl group, 1-(4-pyridyl)dibenzofuran-3-yl group, 2-(4-pyridyl)dibenzofuran-3-yl group, 4-(4-pyridyl)dibenzofuran-3-yl group, 6-(4-pyridyl)dibenzofuran-3-yl group, 7-(4-pyridyl)dibenzofuran -3-yl group, 8-(4-pyridyl)dibenzofuran-3-yl group, or 9-(4-pyridyl)dibenzofuran-3-yl group is preferred. Among these substituents, a hydrogen atom, a phenyl group, a p-tolyl group, a biphenyl-2-yl group, a biphenyl-3-yl group, a biphenyl-4-yl group, a 3 -(2-pyridyl)phenyl group, 4-(2-pyridyl)phenyl group, 3-(3-pyridyl)phenyl group, 4-(3-pyridyl)phenyl group, 2-pyridyl group, 3-pyridyl group, 4 -pyridyl group, 2-phenylpyridin-6-yl group, 2-phenylpyridin-5-yl group, 2-phenylpyridin-4-yl group, 3-phenylpyridin-5-yl group, 3-phenylpyridin-6 -yl group, 2,6-diphenylpyridin-4-yl group, 4,6-diphenylpyridin-2-yl group, 2-pyrimidyl group, 2-pyrazyl group, 1-naphthyl group, 2-naphthyl group, 3- quinolyl group, 4-quinolyl group, 3-isoquinolyl group, 2-benzothienyl group, 2-benzofuryl group, 2-fluorenyl group, 9,9-dimethylfluorene-2-yl group, 9,9-diphenylfluorene- 2-yl group, 9-anthranyl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 2-dibenzothienyl group, 2-dibenzofuryl group, 4-dibenzothienyl group, 4- A dibenzofuryl group, a 3-fluoranthenyl group, a 1-pyrenyl group, a 2-triphenylenyl group, and the like are preferred. Among these substituents, Ar ² is a phenyl group, p-tolyl group, biphenyl-2-yl group, biphenyl-3-yl group, biphenyl-4-yl group, 3-(2-pyridyl)phenyl group, 4-(2-pyridyl)phenyl group, 3-(3-pyridyl)phenyl group, 4-(3-pyridyl)phenyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-phenyl pyridin-6-yl group, 2-phenylpyridin-5-yl group, 2-phenylpyridin-4-yl group, 3-phenylpyridin-5-yl group, 3-phenylpyridin-6-yl group, 2,6 -diphenylpyridin-4-yl group, 4,6-diphenylpyridin-2-yl group, 2-pyrimidyl group, 2-pyrazyl group, 1-naphthyl group, 2-naphthyl group, 3-quinolyl group, 4-quinolyl group , 3-isoquinolyl group, 2-benzothienyl group, 2-benzofuryl group, 2-fluorenyl group, 9,9-dimethylfluoren-2-yl group, 9,9-diphenylfluoren-2-yl group, 9- anthranyl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 2-dibenzothienyl group, 2-dibenzofuryl group, 4-dibenzothienyl group, 4-dibenzofuryl group, 3-fur Olanthenyl group, 1-pyrenyl group, 2-triphenylenyl group and the like are preferred. Furthermore, 3-(2-pyridyl)phenyl group, 4-(2-pyridyl)phenyl group, 3-(3-pyridyl)phenyl group, 4-(3-pyridyl)phenyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-phenylpyridin-6-yl group, 2-phenylpyridin-5-yl group, 2-phenylpyridin-4-yl group, 3-phenylpyridin-5-yl group, 3-phenyl pyridin-6-yl group, 3-quinolyl group, 4-quinolyl group, 3-isoquinolyl group, 2-benzothienyl group, 2-benzofuryl group, 2-fluorenyl group, 9,9-dimethylfluoren-2-yl group , 9,9-diphenylfluoren-2-yl group, 2-dibenzothienyl group, 2-dibenzofuryl group, 4-dibenzothienyl group, 4-dibenzofuryl group and the like are particularly preferred.

Ar ³ and Ar ⁴ are each independently a phenyl group, a naphthyl group, a pyridyl group (these groups may be substituted with a fluorine atom, a methyl group, or a phenyl group), a hydrogen atom, and a carbon number 1 to 4 alkyl groups, or a single bond formed with ^X2 .

The alkyl group having 1 to 4 carbon atoms in Ar ³ and Ar ⁴ is not particularly limited, but may be methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, or the like. is mentioned as a preferable example.
The fluorine-substituted phenyl group, naphthyl group and pyridyl group for Ar ³ and Ar ⁴ are not particularly limited, but include the same groups as those for Ar ¹ .
The phenyl group, naphthyl group, and pyridyl group substituted with a methyl group for Ar ³ and Ar ⁴ are not particularly limited, and include the same groups as those for Ar ¹ .
The phenyl group, naphthyl group, and pyridyl group substituted with a phenyl group for Ar ³ and Ar ⁴ are not particularly limited, and include the same groups as those for Ar ¹ .

Ar ³ and Ar ⁴ are preferably each independently a hydrogen atom, a phenyl group, a naphthyl group, a biphenyl group, a pyridyl group, or a single bond formed with X ² in terms of excellent electron-transporting material properties. stomach. Ar ³ and Ar ⁴ are more preferably each independently a hydrogen atom or a single bond formed with X ² in terms of ease of synthesis.

Specific examples of the phenyl group, naphthyl group, or pyridyl group (these groups may be substituted with a fluorine atom, a methyl group, or a phenyl group) for Ar ³ and Ar ⁴ are particularly limited. However, groups similar to Ar ¹ can be mentioned. Among these substituents, phenyl group, biphenyl-3-yl group, biphenyl-4-yl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 1 A -naphthyl group or a 2-naphthyl group is preferred, and a phenyl group is particularly preferred in terms of ease of synthesis.

Ar ⁵ and Ar ⁶ are each independently a phenyl group, a naphthyl group, a pyridyl group (these groups may be substituted with a fluorine atom, a methyl group, or a phenyl group), a hydrogen atom, or a carbon represents an alkyl group of numbers 1 to 4; Ar ⁵ or Ar ⁶ may be a single bond that joins with ^X2 .

The alkyl group having 1 to 4 carbon atoms in Ar ⁵ and Ar ⁶ is not particularly limited, but may be methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, or the like. is mentioned as a preferable example.
The fluorine-substituted phenyl group, naphthyl group and pyridyl group for Ar ⁵ and Ar ⁶ are not particularly limited, but include the same groups as those for Ar ¹ .
The phenyl group, naphthyl group and pyridyl group substituted with a methyl group for Ar ⁵ and Ar ⁶ are not particularly limited, and include the same groups as those for Ar ¹ .
The phenyl group, naphthyl group, and pyridyl group substituted with a phenyl group for Ar ⁵ and Ar ⁶ are not particularly limited, and include the same groups as those for Ar ¹ .

Ar ⁵ and Ar ⁶ are each independently a hydrogen atom, a phenyl group, a tolyl group, a naphthyl group, a biphenyl group, a pyridyl group, or a single bond that bonds to X ² in terms of excellent electron-transporting material properties. is preferred, and a hydrogen atom or a single bond that bonds to ^X2 is more preferred in terms of ease of synthesis.

W ¹ , W ² and W ³ each independently represent C—H or a nitrogen atom, W ¹ , W ² and W ³ all represent C—H, or W ¹ , W ² , ^W3 represents a nitrogen atom, and the remaining two represent C—H. That is, W ¹ , W ² and W ³ each independently represent C—H or a nitrogen atom, and at least two of them represent C—H.
W ¹ , W ² and W ³ are preferably all C—H in terms of ease of synthesis.

X ¹ and X ² each independently represent a phenylene group, a naphthylene group, a biphenylene group, a pyridylene group (these groups may be substituted with a fluorine atom, a methyl group, or a phenyl group), or a single represents a bond.
X ¹ and X ² are each independently
single bond;
An unsubstituted phenylene group, naphthylene group, biphenylene group, or pyridylene group; is preferred.
Among these groups, a single bond, a phenylene group, or a pyridylene group are more preferred from the viewpoint of easy availability of raw materials.

Z represents a nitrogen atom or CH. Among these, Z is preferably a nitrogen atom from the viewpoint of excellent electron transport material properties.

Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a group represented by CR or a nitrogen atom. R is a phenyl group, a naphthyl group, or a pyridyl group (these groups may be substituted with a fluorine atom, a methyl group, or a phenyl group), a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, 1 carbon atom represents an alkenyl group of ∼4.

Further, when any one of Y ¹ , Y ² , Y ³ and Y ⁴ represents a nitrogen atom, only one of Y ¹ , Y ² , Y ³ and Y ⁴ is a nitrogen atom and the rest are C A group represented by —R (each R independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 1 to 4 carbon atoms, a phenyl group, a naphthyl group, or a pyridyl group. A phenyl group , a naphthyl group, or a pyridyl group may be substituted with a fluorine atom, a methyl group, or a phenyl group) is preferable from the viewpoint of ease of synthesis.

Of these, Y ¹ , Y ² , Y ³ and Y ⁴ are all groups represented by C—R (each R is independently a hydrogen atom, a an alkyl group, an alkenyl group having 1 to 4 carbon atoms, a phenyl group, a naphthyl group, or a pyridyl group). More preferably, all of Y ¹ , Y ² , Y ³ and Y ⁴ are groups represented by CH.

R may combine with each other to form an aromatic ring. The compound in which the R's are bonded to each other to form an aromatic ring is not particularly limited, but examples thereof include formulas (1f) and (1g), which will be described later.

The compound represented by formula (1) is not particularly limited, but for example, the following formulas (1a), (1b), (1c), (1d), (1e), (1f), or It can be embodied in a compound represented by (1g) or the like.

(In formulas (1a), (1b), (1c), (1d), (1e), (1f), and (1g), Ar ¹ , Ar ² , Ar 3 , Ar ^{4 ,} Ar ⁵ , Ar ⁶ , X ¹ , X ² , Z, Y ¹ , Y ² , Y ³ , Y ⁴ and R have the same meanings as in formula (1).)

In formula (1a), (1b), (1c), (1d), (1e), (1f), or (1g), the preferred range of each definition is the same as the preferred range shown in formula (1) is.

When the cyclic azine compound (1) according to one aspect of the present invention is used as a component of an organic electroluminescent element, effects such as high luminous efficiency, long life, and low voltage can be obtained. In particular, this effect appears remarkably when used as an electron transport layer or a hole blocking layer.

Among the compounds represented by formula (1), specific examples of particularly preferred compounds include the following (A-1) to (A-1356), but the present disclosure is not limited thereto.

Applications of the cyclic azine compound (1) are described below.
Although the cyclic azine compound (1) according to one aspect of the present invention is not particularly limited, it can be used, for example, as a material for organic electroluminescence devices.
Therefore, the material for an organic electroluminescence device according to one aspect of the present invention contains the cyclic azine compound (1).

In a broad sense, the light-emitting layer in the organic electroluminescence device refers to a layer that emits light when a current is passed through electrodes consisting of a cathode and an anode. Specifically, it refers to a layer containing a fluorescent compound that emits light when an electric current is passed through electrodes consisting of a cathode and an anode. An organic electroluminescent element usually has a structure in which a light-emitting layer is sandwiched between a pair of electrodes.

The organic electroluminescent device according to one aspect of the present invention has a hole-transporting layer, an electron-transporting layer, an anode buffer layer, a cathode buffer layer, etc., in addition to the light-emitting layer, if necessary, and is sandwiched between the cathode and the anode. take structure. Specific examples include the structures shown below.
(i) anode/emissive layer/cathode (ii) anode/hole transport layer/emissive layer/cathode (iii) anode/emissive layer/electron transport layer/cathode (iv) anode/hole transport layer/emissive layer/electron Transport layer/cathode (v) anode/anode buffer layer/hole transport layer/light emitting layer/electron transport layer/cathode buffer layer/cathode

A conventionally known light-emitting material can be used for the light-emitting layer. As a method for forming the light-emitting layer, there is a method of forming a thin film by a known method such as a vapor deposition method, a spin coating method, a casting method, or an LB method.

The light-emitting layer can be obtained by dissolving a light-emitting material together with a binder such as a resin in a solvent to form a solution, and then applying the solution by spin coating or the like to form a thin film.

The film thickness of the light-emitting layer thus formed is not particularly limited and can be appropriately selected depending on the situation, but is usually in the range of 5 nm to 5 μm.

Next, other layers such as a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, etc., which constitute an organic electroluminescence device in combination with the light emitting layer, will be described.

The hole-injecting layer and the hole-transporting layer have a function of transferring holes injected from the anode to the light-emitting layer, and the hole-injecting layer and the hole-transporting layer are interposed between the anode and the light-emitting layer. causes more holes to be injected into the light-emitting layer at a lower electric field.

In addition, electrons injected from the cathode and transported from the electron injection layer and/or the electron transport layer to the light-emitting layer are converted into holes by an electron barrier present at the interface between the light-emitting layer and the hole injection layer or the hole transport layer. It accumulates at the interface in the light-emitting layer without leaking into the injection layer or the hole-transporting layer, resulting in a device with excellent light-emitting performance such as improved light-emitting efficiency.

The hole-injecting material and the hole-transporting material have either hole injection or transport or electron blocking properties, and may be either organic or inorganic. Examples of hole injection materials and hole transport materials include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, conductive polymer oligomers, especially thiophene oligomers, and the like. As the hole-injecting material and the hole-transporting material, the above materials can be used, and porphyrin compounds, aromatic tertiary amine compounds and styrylamine compounds, particularly aromatic tertiary amine compounds can be used. preferable.

Representative examples of the aromatic tertiary amine compounds and styrylamine compounds include N,N,N',N'-tetraphenyl-4,4'-diaminophenyl, N,N'-diphenyl-N,N' -bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine (TPD), 2,2-bis(4-di-p-tolylaminophenyl)propane, 1,1- Bis(4-di-p-tolylaminophenyl)cyclohexane, N,N,N',N'-tetra-p-tolyl-4,4'-diaminobiphenyl, 1,1-bis(4-di-p- tolylaminophenyl)-4-phenylcyclohexane, bis(4-dimethylamino-2-methylphenyl)phenylmethane, bis(4-di-p-tolylaminophenyl)phenylmethane, N,N'-diphenyl-N,N '-di(4-methoxyphenyl)-4,4'-diaminobiphenyl, N,N,N',N'-tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis(diphenylamino) Oudriphenyl, N,N,N-tri(p-tolyl)amine, 4-(di-p-tolylamino)-4'-[4-(di-p-tolylamino)styryl]stilbene, 4-N,N- Diphenylamino-(2-diphenylvinyl)benzene, 3-methoxy-4'-N,N-diphenylaminostilbenzene, N-phenylcarbazole, 4,4'-bis[N-(1-naphthyl)-N-phenyl amino]biphenyl (NPD), 4,4′,4″-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine (MTDATA) and the like.

Inorganic compounds such as p-type Si and p-type SiC can also be used as hole injection materials and hole transport materials. The hole injection layer and the hole transport layer are formed by thinning the hole injection material and the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, and an LB method. can be formed. The film thickness of the hole injection layer and hole transport layer is not particularly limited, but is usually about 5 nm to 5 μm. The hole injection layer and the hole transport layer may have a single layer structure composed of one or more of the above materials, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions.

In the organic electroluminescent device according to one aspect of the present invention, the electron transport layer preferably contains the cyclic azine compound represented by formula (1) above. Therefore, the electron-transporting material for an organic electroluminescence device according to one aspect of the present invention contains the cyclic azine compound (1). Note that the cyclic azine compound (1) according to one aspect of the present invention can also be used in a layer other than the electron transport layer of an organic electroluminescence device.

The electron transport layer can be formed by forming a film from the cyclic azine compound represented by the formula (1) by a known thin film forming method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method. can. The thickness of the electron transport layer is not particularly limited, but is usually selected within the range of 5 nm to 5 μm. Further, the electron transport layer preferably contains a cyclic azine compound represented by formula (1), and may contain a conventionally known electron transport material, and has a single layer structure consisting of one or more kinds. Alternatively, it may be a laminated structure composed of a plurality of layers having the same composition or different compositions.

Moreover, the light-emitting material is not limited to the light-emitting layer, and one type of light-emitting material may be contained in the hole-transporting layer or the electron-transporting layer adjacent to the light-emitting layer, thereby further increasing the light-emitting efficiency of the organic electroluminescent device. be able to.

There are no particular restrictions on the type of the substrate, such as glass or plastic, and there is no particular restriction as long as it is transparent. Examples of substrates that are preferably used in the organic electroluminescent device according to one aspect of the present invention include glass, quartz, and light-transmitting plastic films.

Examples of light-transmitting plastic films include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, and polycarbonate (PC). , cellulose triacetate (TAC), cellulose acetate propionate (CAP), and the like.

A preferred example for producing an organic electroluminescence device will be described. As an example, a method for producing an organic electroluminescence device comprising the anode/hole injection layer/hole transport layer/luminescent layer/electron transport layer/electron injection layer/cathode will be described.

First, a thin film made of a desired electrode material, for example, an anode material is formed on a suitable substrate by a method such as vapor deposition or sputtering so as to have a thickness of 1 μm or less, preferably in the range of 10 to 200 nm. Fabricate the anode. Next, a thin film composed of a hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer/electron injection layer, which are element materials, is formed thereon.

A buffer layer (electrode interface layer) may exist between the anode and the light emitting layer or the hole injection layer and between the cathode and the light emitting layer or the electron injection layer.

Furthermore, in addition to the basic constituent layers described above, layers having other functions may be laminated as necessary, and functional layers such as a hole blocking layer and an electron blocking layer may be provided.

Next, electrodes of the organic electroluminescence device according to one aspect of the present invention will be described. As the anode in the organic electroluminescence device, an electrode material having a large work function (4 eV or more), an alloy, an electrically conductive compound, or a mixture thereof is preferably used. Specific examples of such electrode materials include metals such as Au, conductive transparent materials such as CuI, indium-tin oxide (ITO), SnO ₂ and ZnO.

The anode may be formed by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering, and forming a pattern of a desired shape by photolithography, or patterning through a mask of a desired shape during vapor deposition or sputtering. may be formed.

On the other hand, as the cathode, an electrode material having a small work function (4 eV or less) (referred to as an electron-injecting metal), an alloy, an electrically conductive compound, or a mixture thereof is preferably used. Specific examples of such electrode materials include sodium, sodium-potassium alloys, magnesium, lithium, magnesium/copper mixtures, magnesium/silver mixtures, magnesium/aluminum mixtures, magnesium/indium mixtures, aluminum/aluminum oxide (Al ₂ O ₃ ) mixtures, indium, lithium/aluminum mixtures, rare earth metals, etc.; Among these, mixtures of electron-injecting metals and second metals, which are stable metals with a larger work function value, such as magnesium/silver mixtures, magnesium /aluminum mixtures, magnesium/indium _mixtures , aluminum/aluminum oxide ( _Al2O3 ) mixtures, lithium/aluminum mixtures, etc. are suitable. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.

As described above, a thin film of a desired electrode material such as an anode material is formed on a suitable substrate by a method such as vapor deposition or sputtering so as to have a thickness of 1 μm or less, preferably in the range of 10 to 200 nm. After forming the anode, each layer thin film consisting of the hole injection layer, the hole transport layer, the light emitting layer, and the electron transport layer/electron injection layer is formed on the anode as described above. A desired organic electroluminescence device is obtained by forming a thin film made of a substance to a thickness of 1 μm or less, preferably in the range of 50 to 200 nm, by a method such as vapor deposition or sputtering to provide a cathode.

The organic electroluminescence element according to one aspect of the present invention may be used as a kind of lamp such as an illumination light source or an exposure light source, a type of projection device that projects an image, or a still image or a moving image that can be directly viewed. You may use it as a display apparatus (display) of the type to carry out. When used as a display device for reproducing moving images, the driving method may be either a simple matrix (passive matrix) method or an active matrix method. Further, by using two or more kinds of organic electroluminescent elements according to one embodiment of the present invention having different emission colors, a full-color display device can be manufactured.

Next, a manufacturing method according to one aspect of the present invention will be described.
The cyclic azine compound (1) according to one aspect of the present invention is not particularly limited, but for example, in the presence or absence of a base in the presence of a palladium catalyst, It can be produced by any of the methods shown in (4) and the like.

(In reaction formula (1), Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , X ¹ , X ² , Z, W ¹ , W ² , W ³ , Y 1 , Y ^{2 ,} Y ³ and Y ⁴ represent the same substituents as in formula (1), A ¹ and A ² represent leaving groups described later, and M ³ and M ⁴ represent substituents described later. )

(In reaction formula (2), Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , X ¹ , X ² , Z, W ¹ , W ² , W ³ , Y 1 , Y ^{2 ,} Y ³ and Y ⁴ represent the same substituents as in formula (1), ^{A 2} and A ³ represent leaving groups described later, and ^{M 1} and M ⁴ represent substituents described later. )

(In reaction formula (3), Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , X ¹ , X ² , Z, W ¹ , W ² , W ^{3 , Y 1 ,} Y ² , Y ³ and Y ⁴ represent the same substituents as in formula (1) above.A ⁴ represents a leaving group described later.M ² represents a substituent described later.)

(In reaction formula (4), Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , X ¹ , X ² , Z, W ¹ , W ² , W ³ , Y ¹ , Y ² , Y ³ and Y ⁴ represent the same substituents as in the above formula (1).A ² represents a leaving group described later.M ⁴ represents a substituent described later.)

Further, hereinafter, the compound represented by formula (2a) is referred to as compound (2a). Compound (3a), compound (4a), compound (5a), compound (3b), compound (4b), compound (5b), compound (4c), compound (1g), and the like are also synonymous. Definitions of these compounds are described below.

A ¹ , A ² , A ³ , and A ⁴ each represent a leaving group, which is not particularly limited and includes, for example, each independently chlorine atom, bromine atom, iodine atom, triflate, and the like. Of these, a bromine atom or a chlorine atom is each independently preferable in that the reaction yield is good. However, in some cases, it is preferable to use triflate from the availability of raw materials.

M ¹ , M ² , M ³ , and M ⁴ represent leaving groups, and are not particularly limited, for example, each independently ZnR ¹ , MgR ² , Sn(R ³ ) ₃ or B( OR ⁴ ) ₂ . provided that R ¹ and R ² above each independently represent a chlorine atom, a bromine atom or an iodine atom, R ³ above represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ⁴ above represents It represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and two R ⁴ in B(OR ⁴ ) ₂ may be the same or different. Also, two ^R4 's may be united to form a ring containing an oxygen atom and a boron atom.

Examples of ZnR ¹ and MgR ² include, but are not limited to, ZnCl, ZnBr, ZnI, MgCl, MgBr and MgI.

Examples of Sn(R ³ ) ₃ include, but are not limited to, Sn(Me) ₃ and Sn(Bu) ₃ .

Examples of B(OR ⁴ ) ₂ include, but are not limited to, B(OH) ₂ , B(OMe) ₂ , B(O ⁱ Pr) ₂ and B(OBu) ₂ . Examples of B(OR ⁴ ) ₂ in the case where two R ⁴ are combined to form a ring containing an oxygen atom and a boron atom include the following (C-1) to (C-6). The groups shown can be exemplified, and the group shown by (C-2) is preferable in that the yield is good.

Compound (5a) used in reaction formula (1) can be prepared according to, for example, J. Am. Am. Chem. Soc. , 1963, 85 (10), 1549, paragraph numbers [0091] to [0103] of WO2010/082621, or paragraph numbers [0045] to [0067] of JP 2013-223458. can be manufactured in combination.

Next, the reaction formula (1) will be explained. Reaction formula (1) is a method for obtaining a cyclic azine compound (1) according to one embodiment of the present invention by performing "Step 1" followed by "Step 2". "Step 1" is a method of reacting compound (2a) with compound (3a) in the presence or absence of a base and in the presence of a palladium catalyst to obtain compound (4a), which is a Suzuki-Miyaura reaction. , Negishi reaction, Tamao-Kumada reaction, Stille reaction, etc., the desired product can be obtained in good yield by applying reaction conditions for general coupling reactions.

The palladium catalyst that can be used in "step 1" is not particularly limited, but examples thereof include salts such as palladium chloride, palladium acetate, palladium trifluoroacetate, and palladium nitrate. In addition, π-allylpalladium chloride dimer, palladium acetylacetonate, tris(dibenzylideneacetone)dipalladium, dichlorobis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)palladium and dichloro(1,1′-bis(diphenylphosphine)palladium. Complex compounds such as phino)ferrocene)palladium can be exemplified. Among them, a palladium complex having a tertiary phosphine as a ligand is more preferable in terms of a good reaction yield, is easily available, and has a good reaction yield. Especially preferred.
A palladium complex having a tertiary phosphine as a ligand can also be prepared in a reaction system by adding a tertiary phosphine to a palladium salt or complex compound. The tertiary phosphine that can be used at this time is not particularly limited. , 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene, 2-(diphenylphosphino)-2′-(N,N-dimethylamino)biphenyl, 2-(di-tert-butylphosphino ) biphenyl, 2-(dicyclohexylphosphino)biphenyl, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis( diphenylphosphino)butane, 1,1′-bis(diphenylphosphino)ferrocene, tri(2-furyl)phosphine, tri(o-tolyl)phosphine, tris(2,5-xylyl)phosphine, (±)-2 ,2'-bis(diphenylphosphino)-1,1'-binaphthyl, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl and the like. 2-Dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl or triphenylphosphine is preferred in terms of availability and good reaction yield. The molar ratio of the tertiary phosphine to the palladium salt or complex compound is preferably 1:10 to 10:1, more preferably 1:2 to 5:1 from the viewpoint of good reaction yield.

The base that can be used in "Step 1" is not particularly limited, but examples include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, potassium phosphate, and sodium phosphate. , sodium fluoride, potassium fluoride, cesium fluoride, etc., and potassium carbonate is preferable because of its high yield. The molar ratio between the base and the compound (3a) is preferably 1:2 to 10:1, more preferably 1:1 to 3:1 for good yield.

The molar ratio of compound (2a) and compound (3a) used in "Step 1" is not particularly limited, but is preferably 1:2 to 5:1, and 1:2 in terms of good yield. to 2:1 is more desirable.

Solvents that can be used in "Step 1" are not particularly limited, but examples include water, dimethylsulfoxide, dimethylformamide, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, toluene, benzene, diethyl ether, ethanol, Methanol, xylene, etc. can be exemplified, and these may be used in appropriate combination. It is desirable to use a mixed solvent of dioxane or tetrahydrofuran and water in terms of good yield.

"Step 1" is not particularly limited, but for example, it can be carried out at a temperature appropriately selected from 0 ° C. to 150 ° C., and it is further carried out at 50 ° C. to 100 ° C. in terms of good yield. desirable.

Compound (4a) can be obtained by normal treatment after completion of "Step 1". If necessary, it may be purified by recrystallization, column chromatography, sublimation, or the like.

In "Step 2", the compound (4a) obtained in "Step 1" is reacted with compound (5a) in the presence or absence of a base in the presence of a palladium catalyst to obtain This is a method for obtaining such a cyclic azine compound (1), and by applying reaction conditions for general coupling reactions such as Suzuki-Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille reaction, etc., a good yield can be obtained. you can get the target. In "Step 2", among the conditions listed in "Step 1", conditions can be applied in which compound (2a) is replaced with compound (5a) and compound (3a) is replaced with compound (4a). However, it is not necessary to use the same reaction conditions as in "step 1". After completion of "Step 2", purification may be performed by recrystallization, column chromatography, sublimation, or the like, if necessary.
The reaction conditions and the like in Reaction Formula (2) are the same as those in Reaction Formula (1). That is, in "Step 3" in Reaction Formula (2), among the conditions listed in "Step 1", compound (2a) is replaced with compound (3b), and compound (3a) is replaced with compound (2b). can be applied. In "Step 4" in Reaction Formula (2), the same reaction conditions as those listed in "Step 1" can be applied. After completion of "Step 4", purification may be performed by recrystallization, column chromatography, sublimation, or the like, if necessary.
The reaction conditions and the like in Reaction Formula (3) are the same as those in Reaction Formula (1). That is, in "step 5" in reaction formula (3), among the conditions listed in "step 1", compound (2a) was replaced with compound (5b), and compound (3a) was replaced with compound (4b). Conditions can apply. However, it is not necessary to use the same reaction conditions as in "step 1". After completion of "Step 5", if necessary, purification may be performed by recrystallization, column chromatography, sublimation, or the like.

Reaction formula (4) is a method of obtaining a cyclic azine compound (1 g) according to one embodiment of the present invention by performing "Step 6". The reaction conditions and the like in Reaction Formula (4) are the same as those in Reaction Formula (1). That is, in "step 6" in reaction formula (4), among the conditions listed in "step 1", compound (2a) was replaced with compound (5a), and compound (3a) was replaced with compound (4c). Conditions can apply. However, it is not necessary to use the same reaction conditions as in "step 1". After completion of "Step 5", if necessary, purification may be performed by recrystallization, column chromatography, sublimation, or the like.

Hereinafter, each aspect of the present invention will be described in more detail based on examples, but each aspect of the present invention should not be construed as being limited by these examples.

¹ H-NMR measurement was performed using Gemini200 (manufactured by Varian).
The glass transition temperature was measured using DSC7020 (manufactured by Hitachi High-Tech Science).
Triplet excitation level measurement was performed using FP-6500 (manufactured by JASCO Corporation). The conversion formula for the triplet excitation level is as follows.
Triplet excitation level (eV) = 1241.6/λonset
"λonset" represents the wavelength value at the intersection of the tangent line drawn on the rising edge of the short wavelength side and the horizontal axis in the phosphorescence spectrum, where the vertical axis represents the phosphorescent intensity and the horizontal axis represents the wavelength.
Gaussian09 (manufactured by Gaussian) was used to calculate the triplet excitation level by molecular orbital calculation.
The luminescence properties of the organic electroluminescence device were evaluated by applying a direct current to the fabricated device at room temperature and using a luminance meter, LUMINANCEMETER (BM-9) (manufactured by TOPCON).

Synthesis example-1

Under an argon stream, 2-[3-chloro-5-(3-pyridyl)phenyl]-4,6-diphenyl-1,3,5-triazine (5.01 g, 11.9 mmol), bis(pinacolato)diboron ( 3.32 g, 13.1 mmol), potassium acetate (3.50 g, 35.6 mmol), palladium acetate (26.7 mg, 0.119 mmol), and 2-dicyclohexylphosphino-2′,4′,6′-tri Isopropylbiphenyl (113.7 mg, 0.238 mmol) was suspended in tetrahydrofuran (70 mL) and stirred at 75° C. for 22 hours. After cooling to room temperature, the reaction solution was concentrated under reduced pressure. Toluene (100 mL) was added to the obtained slurry, and the mixture was stirred at 100° C., and the solid was filtered off. The obtained filtrate is concentrated under reduced pressure, and the solid obtained by drying the concentrate is purified by recrystallization (toluene) to obtain the target 4,6-diphenyl-2-[3-(3-pyridyl). )-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1,3,5-triazine white solid (yield 5.01 g, yield 82 %) was obtained.

Synthetic Example-1

4,6-diphenyl-2-[3-(3-pyridyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]- under an argon stream 1,3,5-triazine (1.10 g, 2.15 mmol), 2-bromo-9,10-dihydro-9,10-[1,2]benzenoanthracene (0.84 g, 2.53 mmol), and Tetrakis(triphenylphosphine)palladium (90.3 mg, 0.078 mmol) was suspended in tetrahydrofuran (60 mL). To this was added 2M potassium carbonate aqueous solution (4.2 mL, 8.4 mmol) and stirred at 75° C. for 72 hours. After cooling to room temperature, the reaction solution was concentrated under reduced pressure. Water (100 mL) was added to the resulting concentrate, the mixture was stirred at 78° C., and the precipitated solid was separated by filtration. The obtained solid was washed with water (30 mL), methanol (30 mL) and hexane (30 mL). This solid was dissolved in chloroform (100 mL), silica gel was added, and the mixture was filtered through celite, and the filtrate was concentrated under reduced pressure. The solid obtained by drying the concentrate was purified twice by recrystallization (toluene) to give the desired 2-[3-(9,10-dihydro-9,10-[1,2]benzene). White solid of noanthracen-2-yl)-5-(3-pyridyl)phenyl]-4,6-diphenyl-1,3,5-triazine (compound A-257) (yield 0.81 g, yield 59% ).

¹ H-NMR (CDCl ₃ ) δ (ppm): 5.50 (d, J = 19.8 Hz, 2H), 6.95-7.00 (m, 4H), 7.34 (d, J = 7 .6Hz, 1H), 7.36-7.42 (m, 4H), 7.49-7.59 (m, 8H), 7.72 (s, 1H), 7.85 (s, 1H), 8.18 (s, 1H), 8.63 (d, J=5.1Hz, 1H), 8.71 (d, J=5.1Hz, 4H), 8.85 (s, 1H), 8. 89 (s, 1H), 9.00 (s, 1H).
The glass transition temperature of compound A-257 was 158°C.
The triplet excitation level of compound A-257 was 2.9 eV.

Synthesis example-2

4,6-diphenyl-2-[3-(3-pyridyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1,3, 5-triazine is 4,6-diphenyl-2-[3-(4-pyridyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]- 2-[3-(9,10-dihydro-9,10-[1,2]benzenoanthracene was obtained by the same experimental procedure as in Synthesis Example-1, except that 1,3,5-triazine was used. -2-yl)-5-(4-pyridyl)phenyl]-4,6-diphenyl-1,3,5-triazine (compound A-337) as a white solid (yield 0.83 g, yield 67%). Obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 5.50 (d, J = 19.8 Hz, 2H), 6.96-7.00 (m, 4H), 7.33 (d, J = 7 .6Hz, 1H), 7.37-7.41 (m, 4H), 7.51-7.61 (m, 7H), 7.70 (s, 1H), 7.93 (s, 1H), 7.97 (d, J = 6.1 Hz, 2H), 8.70 (d, J = 7.5 Hz, 4H), 8.75 (d, J = 5.1 Hz, 2H), 8.96 (d , J=11.9 Hz, 2H).
The glass transition temperature of compound A-337 was 167°C.
The triplet excitation level of compound A-337 was 2.9 eV.

Synthetic Example-3

4,6-diphenyl-2-[3-(3-pyridyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1,3, 5-triazine is 4,6-diphenyl-2-[3-(3-quinolyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]- 2-[3-(9,10-dihydro-9,10-[1,2]benzenoanthracene was obtained by the same experimental procedure as in Synthesis Example-1, except that 1,3,5-triazine was used. -2-yl)-5-(3-quinolyl)phenyl]-4,6-diphenyl-1,3,5-triazine (compound A-705) as a white solid (yield 4.44 g, yield 73%). Obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 5.50 (d, J = 19.9 Hz, 2H), 6.95-6.99 (m, 4H), 7.36-7.41 (m , 5H), 7.50-7.58 (m, 8H), 7.71 (t, J = 7.6Hz, 1H), 7.76 (s, 1H), 7.90 (d, J = 8 .1 Hz, 1 H), 7.98 (s, 1 H), 8.12 (d, J = 8.0 Hz, 1 H), 8.41 (s, 1 H), 8.72 (d, J = 6.5 Hz , 4H), 8.88(s, 1H), 8.98(s, 1H), 9.30(s, 1H).
The glass transition temperature of compound A-705 was 163°C.

Synthetic Example-4

４，６－ジフェニル－２－［３－（３－ピリジル）－５－（４，４，５，５－テトラメチル－１，３，２－ジオキサボロラン－２－イル）フェニル］－１，３，５－トリアジンを４，６－ジフェニル－２－［３－（４－イソキノリル）－５－（４，４，５，５－テトラメチル－１，３，２－ジオキサボロラン－２－イル）フェニル］－１，３，５－トリアジンに変更した以外は合成実施例－１と同様の実験操作を行って、２－［３－（９，１０－ジヒドロ－９，１０－［１，２］ベンゼノアントラセン－２－イル）－５－（４－イソキノリル）フェニル］－４，６－ジフェニル－１，３，５－トリアジン（化合物Ａ－７６９）の白色固体（収量４．１１ｇ，収率７３％）を得た。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）δ（ｐｐｍ）：５．４６（ｄ，Ｊ＝１５．３Ｈｚ，２Ｈ），６．９３－６．９８（ｍ，４Ｈ），７．３４－７．３８（ｍ，５Ｈ），７．４８－７．５６（ｍ，７Ｈ），７．７２－７．８４（ｍ，４Ｈ），８．０３（ｄ，Ｊ＝８．２Ｈｚ，１Ｈ），８．１７（ｄ，Ｊ＝７．９Ｈｚ，１Ｈ），８．５９（ｓ，１Ｈ），８．６８（ｄ，Ｊ＝６．６Ｈｚ，４Ｈ），８．７６（ｓ，１Ｈ），８．９９（ｓ，１Ｈ），９．３６（ｓ，１Ｈ）．
化合物Ａ－７６９のガラス転移温度は１７１℃であった。

4,6-diphenyl-2-[3-(3-pyridyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1,3, 5-triazine was converted to 4,6-diphenyl-2-[3-(4-isoquinolyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]- 2-[3-(9,10-dihydro-9,10-[1,2]benzenoanthracene was obtained by the same experimental procedure as in Synthesis Example-1, except that 1,3,5-triazine was used. -2-yl)-5-(4-isoquinolyl)phenyl]-4,6-diphenyl-1,3,5-triazine (compound A-769) as a white solid (yield 4.11 g, yield 73%). Obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 5.46 (d, J = 15.3 Hz, 2H), 6.93-6.98 (m, 4H), 7.34-7.38 (m , 5H), 7.48-7.56 (m, 7H), 7.72-7.84 (m, 4H), 8.03 (d, J = 8.2Hz, 1H), 8.17 (d , J=7.9Hz, 1H), 8.59(s, 1H), 8.68(d, J=6.6Hz, 4H), 8.76(s, 1H), 8.99(s, 1H ), 9.36(s, 1H).
The glass transition temperature of compound A-769 was 171°C.

Synthetic Example-5

Under an argon stream, 2-[3-chloro-1,1′-biphenyl-5-yl]-4,6-diphenyl-1,3,5-triazine (4.00 g, 9.53 mmol), 2-(9 ,10-dihydro-9,10-[1,2]benzenoanthracene)boronic acid (3.12 g, 10.48 mmol), palladium acetate (22.2 mg, 0.099 mmol), and 2-dicyclohexylphosphino-2 ',4',6'-Triisopropylbiphenyl (92.8 mg, 0.195 mmol) was suspended in tetrahydrofuran (190 mL) and stirred at 75°C for 6 hours. After cooling to room temperature, the reaction solution was concentrated under reduced pressure. Water (100 mL) was added to the resulting slurry, stirred at room temperature, and the solid was filtered off. The solid obtained was washed with water (50 mL), methanol (50 mL) and hexane (50 mL). This solid was dissolved in o-xylene (200 mL), silica gel was added, the mixture was filtered through Celite, and the filtrate was concentrated under reduced pressure. The solid obtained by drying this concentrate is purified by recrystallization (toluene) to give 2-[5-(9,10-dihydro-9,10-[1,2]benzenoanthracene-2 -yl)-1,1′-biphenyl-3-yl]-4,6-diphenyl-1,3,5-triazine (compound A-97) as a white solid (yield 5.58 g, yield 92%) Obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 5.46 (d, J = 15.7 Hz, 2H), 6.92-6.97 (m, 4H), 7.31-7.38 (m , 6H), 7.43-7.56 (m, 9H), 7.66-7.71 (m, 3H), 7.85 (s, 1H), 8.70 (d, J = 6.7Hz , 4H), 8.77(s, 1H), 8.83(s, 1H).
The glass transition temperature of compound A-97 was 155°C.
The triplet excitation level of compound A-97 was 2.9 eV.

Synthetic Example-6

2-[3-Chloro-1,1′-biphenyl-5-yl]-4,6-diphenyl-1,3,5-triazine was converted to 2-(2-biphenyl)-4-(4-biphenyl)-6 -[3-chloro-1,1′-biphenyl-5-yl]-1,3,5-triazine, 2-(9,10-dihydro-9,10-[1,2]benzenoanthracene)boronic acid was changed to 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,10-dihydro-9,10-[1,2]benzenoanthracene 2-(2-biphenyl)-4-(4-biphenyl)-6-[5-(9,10-dihydro-9,10-[1, 2] Benzenoanthracen-2-yl)-1,1′-biphenyl-3-yl]-1,3,5-triazine (compound A-1354) as a white solid (yield 0.55 g, yield 79%) got

¹ H-NMR (CDCl ₃ ) δ (ppm): 5.55 (d, J=14.9 Hz, 2H), 7.01-7.06 (m, 4H), 7.11 (t, J=7 .3Hz, 1H), 7.24 (t, J = 7.9Hz, 2H), 7.32-7.36 (m, 3H), 7.39-7.70 (m, 20H), 7.73 (s, 1H), 7.86 (s, 1H), 8.33 (d, J = 7.6Hz, 1H), 8.42 (d, J = 8.4Hz, 2H), 8.49 (s , 2H).
The glass transition temperature of compound A-1354 was 159°C.

Synthetic Example-7

2-(2-biphenyl)-4-(4-biphenyl)-6-[3-chloro-1,1′-biphenyl-5-yl]-1,3,5-triazine to 4,6-diphenyl-2 -[3-(4-chloro-3-pyridyl)]phenyl-1,3,5-triazine, 2-(9,10-dihydro-9,10-[1,2]benzenoanthracene)boronic acid Synthesis except changing to -(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,10-dihydro-9,10-[1,2]benzenoanthracene By performing the same experimental procedure as in Example-5, 2-{3-[4-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)-3-pyridyl] Phenyl}-4,6-diphenyl-1,3,5-triazine (compound A-8) was obtained as a white solid (3.28 g, 62% yield).

¹ H-NMR (CDCl ₃ ) δ (ppm): 5.47 (d, J = 24.1 Hz, 2H), 6.93-6.97 (m, 4H), 7.34-7.38 (m , 4H), 7.45 (d, J = 7.9Hz, 1H), 7.50-7.65 (m, 8H), 7.75 (d, J = 8.3Hz, 1H), 7.80 (d, J = 8.1 Hz, 1H), 8.00 (d, J = 8.1 Hz, 1H), 8.13 (s, 1H), 8.72-8.76 (m, 5H), 8 .98 (s, 1H), 9.00 (s, 1H).
The glass transition temperature of compound A-8 was 148°C.

Synthetic Example-8

2-(2-biphenyl)-4-(4-biphenyl)-6-[3-chloro-1,1′-biphenyl-5-yl]-1,3,5-triazine to 4,6-diphenyl-2 -[3-(3-chloro-4-pyridyl)]phenyl-1,3,5-triazine, 2-(9,10-dihydro-9,10-[1,2]benzenoanthracene)boronic acid Synthesis except changing to -(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,10-dihydro-9,10-[1,2]benzenoanthracene By performing the same experimental procedure as in Example-5, 2-{3-[3-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)-4-pyridyl] Phenyl}-4,6-diphenyl-1,3,5-triazine (compound A-11) was obtained as a white solid (3.28 g, 62% yield).

¹ H-NMR (CDCl ₃ ) δ (ppm): 5.47 (d, J = 22.9 Hz, 2H), 6.92-6.97 (m, 4H), 7.32-7.37 (m , 4H), 7.46 (d, J = 7.3 Hz, 1H), 7.50-7.59 (m, 7H), 7.64-7.67 (m, 2H), 7.82 (d , J = 8.0 Hz, 1H), 7.92 (s, 1H), 8.12 (s, 1H), 8.71-8.74 (m, 5H), 8.81 (d, J = 8 .0Hz, 1H), 8.96(s, 1H).
The glass transition temperature of compound A-11 was 148°C.

Table 1 shows the glass transition temperatures of the compounds obtained in Synthesis Examples-1 to Synthesis Examples-8 and Reference Example-1.

2-[5-(9-phenanthryl)-3-(4-pyridyl)phenyl]-4,6-diphenyl-1,3,5-triazine (ETL-3) described in JP-A-2011-063584 By comparison, the cyclic azine compound to which the group having a triptycene structure according to one embodiment of the present invention is bonded has an extremely high glass transition temperature.

Synthetic Examples-1, 2, 5, 8 and Reference Example-1, and Examples 9 to 14 (Compound A-1, Compound A-21, Compound A-33, Compound A-1185, Compound A-1305, Tables 2 and 3 show the triplet excitation levels of the compound obtained in Compound A-1333).

2-[5-(9-phenanthryl)-3-(4-pyridyl)phenyl]-4,6-diphenyl-1,3,5-triazine (ETL-3) described in JP-A-2011-063584 By comparison, the cyclic azine compound according to one embodiment of the present invention to which a group having a triptycene structure is bonded has a high triplet excitation level.
However, the triplet excitation levels in Table 2 are actual values measured using the aforementioned FP-6500 (manufactured by JASCO Corporation).
The triplet excitation levels in Table 3 are values obtained by DFT calculation (B3LYP/6-31G(d)) using Gaussian09 (manufactured by Gaussian).

Next, device evaluation will be described.
The structural formulas and abbreviations of the compounds used for element evaluation are shown below.

Device example-1
As the substrate, a glass substrate with an ITO transparent electrode, in which an indium-tin oxide (ITO) film (thickness: 110 nm) with a width of 2 mm was patterned in stripes, was used. After cleaning the substrate with isopropyl alcohol, the surface was treated with ozone ultraviolet cleaning. Each layer was vacuum-deposited on the washed substrate by a vacuum deposition method to fabricate an organic electroluminescence device with a light-emitting area of 4 mm ² whose cross-sectional view is shown in FIG. In addition, each organic material was formed into a film by a resistance heating method.
First, the glass substrate was introduced into a vacuum deposition tank, and the pressure was reduced to 1.0×10 ⁻⁴ Pa.
Thereafter, a hole injection layer 2, a charge generation layer 3, a first hole transport layer 4, a second hole transport layer 5, and a light emitting layer were formed as organic compound layers on a glass substrate with an ITO transparent electrode shown in 1 in FIG. 6, the first electron transport layer 7, the second electron transport layer 8, and the cathode layer 9 were deposited in this order by vacuum deposition.

As the hole injection layer 2, HIL purified by sublimation was deposited at a rate of 0.15 nm/second to a thickness of 55 nm.
As the charge generation layer 3, HAT purified by sublimation was deposited to a thickness of 5 nm at a rate of 0.05 nm/sec.
As the first hole transport layer 4, HTL-1 was deposited to a thickness of 10 nm at a rate of 0.15 nm/sec.
As the second hole transport layer 5, HTL-2 was deposited to a thickness of 10 nm at a rate of 0.15 nm/sec.
As the light-emitting layer 6, EML-1 and EML-2 were deposited at a ratio of 95:5 to a thickness of 25 nm (deposition rate: 0.18 nm/sec).
As the first electron transport layer 7, ETL-1 was deposited to a thickness of 5 nm at a rate of 0.15 nm/sec.
As the second electron transport layer 8, 2-[3-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)-5-( 3-Pyridyl)phenyl]-4,6-diphenyl-1,3,5-triazine (Compound A-257) and Liq were deposited at a ratio of 50:50 (weight ratio) to a thickness of 25 nm (deposition rate: 0.15 nm). /sec).

Finally, a metal mask was placed so as to be perpendicular to the ITO stripes, and a cathode layer 9 was formed.
The cathode layer 9 is formed by depositing silver/magnesium (weight ratio 1/10) and silver in this order at 80 nm (deposition rate: 0.5 nm/sec) and 20 nm (deposition rate: 0.2 nm/sec), respectively. and had a two-layer structure.
Each film thickness was measured with a stylus film thickness meter (DEKTAK).

Further, this device was sealed in a nitrogen atmosphere glove box with an oxygen and water concentration of 1 ppm or less. For sealing, a sealing cap made of glass and the film-forming substrate epoxy-type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation) were used.

A direct current was applied to the organic electroluminescence device produced as described above, and the luminescence characteristics were evaluated using a luminance meter, LUMINANCE METER (BM-9) manufactured by TOPCON. As light emission characteristics, the voltage (V) and current efficiency (cd/A) when a current density of 10 mA/cm ² was applied were measured, and the element life (h) during continuous lighting was measured. The device life in Table 4 was obtained by measuring the luminance decay time during continuous lighting when the manufactured device was driven at an initial luminance of 1000 cd/m ² , and required until the luminance (cd/m ² ) decreased by 10%. time was measured. The voltage, current efficiency, and device life are shown as relative values with the result of device reference example 1 described later as a reference value (100). Table 4 shows the results.

Device example-2
2-[3-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl) synthesized in Synthesis Example-2 instead of Compound A-257 in Element Example 1 -5-(4-Pyridyl)phenyl]-4,6-diphenyl-1,3,5-triazine (Compound A-337) was used to prepare an organic electroluminescent device in the same manner as in Device Example-1. made and evaluated. Table 4 shows the results. The voltage, current efficiency, and device life are shown as relative values using the result of device reference example-1 described later as a reference value (100).

Device Example-3
2-[3-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl) synthesized in Synthesis Example-3 instead of Compound A-257 in Element Example 1 -5-(3-Quinolyl)phenyl]-4,6-diphenyl-1,3,5-triazine (Compound A-705) was used to prepare an organic electroluminescent device in the same manner as in Device Example-1. made and evaluated. Table 4 shows the results. The voltage, current efficiency, and device life are shown as relative values using the result of device reference example-1 described later as a reference value (100).

Device Example-4
2-[3-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl) synthesized in Synthesis Example-4 instead of Compound A-257 in Element Example 1 -5-(4-isoquinolyl)phenyl]-4,6-diphenyl-1,3,5-triazine (Compound A-769) was used to prepare an organic electroluminescent device in the same manner as in Device Example-1. made and evaluated. Table 4 shows the results. The voltage, current efficiency, and device life are shown as relative values using the result of device reference example-1 described later as a reference value (100).

Device Example-5
In Element Example 1, 2-(2-biphenyl)-4-(4-biphenyl)-6-[5-(9,10-dihydro-9 synthesized in Synthesis Example-6 instead of Compound A-257 , 10-[1,2]benzenoanthracen-2-yl)-1,1′-biphenyl-3-yl]-1,3,5-triazine (Compound A-1354) An organic electroluminescence device was produced and evaluated in the same manner as in Example-1. Table 4 shows the results. The voltage, current efficiency, and device life are shown as relative values using the result of device reference example-1 described later as a reference value (100).

Device Example-6
2-{3-[4-(9,10-dihydro-9,10-[1,2]benzenoanthracene-2 synthesized in Synthesis Example-7 instead of Compound A-257 in Element Example 1 -yl)-3-pyridyl]phenyl}-4,6-diphenyl-1,3,5-triazine (Compound A-8) was used to prepare an organic electroluminescent device in the same manner as in Device Example-1. made and evaluated. Table 4 shows the results. The voltage, current efficiency, and device life are shown as relative values using the result of device reference example-1 described later as a reference value (100).

Device Example-7
2-{3-[3-(9,10-dihydro-9,10-[1,2]benzenoanthracene-2 synthesized in Synthesis Example-8 instead of Compound A-257 in Element Example 1 -yl)-4-pyridyl]phenyl}-4,6-diphenyl-1,3,5-triazine (Compound A-11) was used to prepare an organic electroluminescent device in the same manner as in Device Example-1. made and evaluated. Table 4 shows the results. The voltage, current efficiency, and device life are shown as relative values using the result of device reference example-1 described later as a reference value (100).

Element reference example-1
In Element Example-1, 2-[5-(9-phenanthryl)-4′-(2-pyrimidyl)biphenyl-3-yl]- described in JP-A-2011-063584 instead of compound A-257 An organic electroluminescence device was produced and evaluated in the same manner as in Device Example-1 except that 4,6-diphenyl-1,3,5-triazine (ETL-2) was used. Table 4 shows the results. As for the voltage, current efficiency, and device life, the result of this device reference example-1 was used as a reference value (100).

The cyclic azine compound (1) according to one aspect of the present invention is extremely excellent in heat resistance of film quality, and by using the compound, it is possible to provide an organic electroluminescence device excellent in long life and luminous efficiency.
Moreover, the cyclic azine compound (1) according to one aspect of the present invention is used as an electron-transporting material for organic electroluminescence devices, which is excellent in low driving voltage. Furthermore, according to one aspect of the present invention, it is possible to provide an organic electroluminescence device with excellent power consumption.
In addition, the cyclic azine compound according to one aspect of the present invention has good thermal stability during sublimation purification, so that it is excellent in operability in sublimation purification, and provides a material with few impurities that cause deterioration of the organic electroluminescent device. can do. In addition, the cyclic azine compound according to one aspect of the present invention can provide a long-life organic electroluminescence device because the stability of the vapor-deposited film is excellent.
In addition, since the thin film made of the cyclic azine compound (1) according to one aspect of the present invention is excellent in electron-transporting ability, hole-blocking ability, oxidation-reduction resistance, water resistance, oxygen resistance, electron injection characteristics, etc., it is It is useful as a material for devices, and as an electron transport material, a hole block material, a light emitting host material, and the like. It is especially useful when used with an electron transport material.
Further, the cyclic azine compound (1) according to one aspect of the present invention has a wide bandgap and a high triplet excitation level. TADF) can be suitably used for an organic electroluminescence device.

1. Glass substrate with ITO transparent electrode 2 . hole injection layer 3 . charge generating layer;4. First hole transport layer 5 . Second hole transport layer 6 . Light-emitting layer 7 . First electron transport layer 8 . Second electron transport layer 9 . cathode layer

Claims (2)

A cyclic azine compound represented by formula (1):
In formula (1),
Ar ¹ each represents a phenyl group ;
Ar ² represents a hydrogen atom, an unsubstituted pyridyl group, or an unsubstituted quinolyl group ;
Ar ³ and Ar ⁴ each independently represents a hydrogen atom; an unsubstituted phenyl group, a naphthyl group, a pyridyl group; or a single bond that bonds to X ² ;
Ar ⁵ and Ar ⁶ each independently represent a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, hydrogen atom, unsubstituted alkyl group having 1 to 4 carbon atoms, or ^a single represents a bond;
W ¹ , W ² and W ³ all represent CH ;
X ¹ represents a single bond;
X ² represents a single bond or a pyridylene group ;
Y ¹ , Y ² , Y ³ , and Y ⁴ are all groups represented by C—R, and each R is independently a hydrogen atom; an unsubstituted alkyl group having 1 to 4 carbon atoms; represents an alkenyl group having 1 to 4 carbon atoms, a phenyl group, a naphthyl group, or a pyridyl group ;
Z represents a nitrogen atom ;
Any one of Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ and R represents a single bond that bonds to X ² . An electron-transporting material for an organic electroluminescence device, comprising the cyclic azine compound represented by formula (1) according to claim 1 .

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