JP7718043B2 - Fused ring compound and material for organic electroluminescent device - Google Patents

Description

The present invention relates to a fused ring compound and a material for organic electroluminescent devices containing the same.

Organic electroluminescent devices are used not only for small displays but also for large televisions, lighting, and other applications, and their development is being actively pursued.
In recent years, market demands for organic electroluminescent devices have become increasingly high, and materials that are excellent in current efficiency, driving voltage, and long life are being sought.
Here, Patent Document 1 discloses a dibenzo[g,p]chrysene compound substituted with an aromatic hydrocarbon group and a heteroaromatic group as a material for an organic electroluminescent device.

US Patent Application Publication No. 2015/0318486

However, the dibenzo[g,p]chrysene compound described in Patent Document 1 is in need of improvement in terms of current efficiency.

One aspect of the present invention is to provide a dibenzo[g,p]chrysene compound (hereinafter referred to as a fused ring compound) that contributes to the production of an organic electroluminescent device with high current efficiency, and a material for the organic electroluminescent device.
Another aspect of the present invention is to provide an organic electroluminescent device with high current efficiency.

According to one aspect of the present invention, there is provided a fused ring compound represented by formula (1):

In formula (1),
A ¹ to A ⁵ each independently represent a charge transporting group;
k1 to k3 each independently represent an integer of 0 to 4;
k4 is an integer of 0 to 3;
L represents a phenylene group, a biphenylene group, a terphenylene group, a naphthyl group, a pyridylene group, or a single bond, which may have a substituent;
A ¹ to A ⁵ may be the same or different.

According to another aspect of the present invention, there is provided a material for an organic electroluminescent device, which comprises a fused ring compound represented by the above formula (1).
According to another aspect of the present invention, there is provided an organic electroluminescent device comprising a fused ring compound represented by the above formula (1).

According to one aspect of the present invention, it is possible to provide a fused ring compound that contributes to the production of an organic electroluminescent device having excellent current efficiency, and a material for the organic electroluminescent device.
According to another aspect of the present invention, an organic electroluminescent device having excellent current efficiency can be provided.

1 is a schematic cross-sectional view showing an example of a layer structure of an organic electroluminescent device including a fused ring compound according to one embodiment of the present invention. FIG. 1 is a schematic cross-sectional view showing an example of a layer structure of an organic electroluminescent device containing a fused ring compound according to one embodiment of the present invention (Device Example 1).

The fused ring compound according to one embodiment of the present invention is described in detail below.

<Triazine compounds>
A fused ring compound according to one embodiment of the present invention is represented by formula (1):

In formula (1),
A ¹ to A ⁵ each independently represent a charge transporting group;
k1 to k3 each independently represent an integer of 0 to 4;
k4 is an integer of 0 to 3;
L represents a phenylene group, a biphenylene group, a terphenylene group, a naphthyl group, a pyridylene group, or a single bond, which may have a substituent;
A ¹ to A ⁵ may be the same or different.

The definition of the charge-transporting group in the fused ring compound represented by formula (1) (hereinafter also referred to as fused ring compound (1)) and preferred specific examples thereof are as follows:

<Charge-transporting group>
A charge-transporting group is a substituent that has the function of transporting charges, which can be holes, electrons, or both.
Examples of the charge transporting group include the following substituents (a-1) to (a-15).
(a-1) a deuterium atom,
(a-2) a trifluoromethyl group,
(a-3) a pentafluoroethyl group,
(a-4) a cyano group,
(a-5) a nitro group,
(a-6) a hydroxyl group,
(a-7) a thiol group,
(a-8) a monocyclic, linked, or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have a substituent;
(a-9) a monocyclic, linked, or fused ring heteroaromatic group having 3 to 36 carbon atoms which may have a substituent;
(a-10) an optionally substituted phosphine oxide group,
(a-11) a silyl group which may have a substituent,
(a-12) a boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms,
(a-13) a linear or branched alkyl group having 1 to 18 carbon atoms,
(a-14) a linear or branched alkoxy group having 1 to 18 carbon atoms, or (a-15) a trifluoromethylsulfonyloxy group.

<Regarding (a-8)>
Examples of the monocyclic, linked, or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms (a-8) include a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, a fluorenyl group, an anthryl group, a phenanthryl group, a benzofluorenyl group, a fluoranthenyl group, a benzofluoranthenyl group, a triphenylenyl group, a spirobifluorenyl group, a diphenylfluorenyl group, a dibenzo[g,p]chrysenyl group, etc. Furthermore, the monocyclic, linked, or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms is preferably a monocyclic, linked, or fused ring aromatic hydrocarbon group having 6 to 18 carbon atoms.

When the aromatic hydrocarbon group of (a-8) has a substituent, the substituents are preferably each independently a fluorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, an optionally substituted phosphine oxide group, an optionally substituted silyl group, a boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, or a trifluoromethylsulfonyloxy group.

The phosphine oxide group may be an unsubstituted phosphine oxide group or a substituted phosphine oxide group, with a substituted phosphine oxide group being preferred.
The substituted phosphine oxide group is preferably a phosphine oxide group having a monocyclic, linked, or fused ring aromatic hydrocarbon group or a fused ring heteroaromatic group having 6 to 18 carbon atoms. Specific examples include groups substituted with two aryl groups, such as diphenylphosphine oxide.

The silyl group may be an unsubstituted silyl group or a substituted silyl group, with a substituted silyl group being preferred.
The silyl group having a substituent is preferably a silyl group having a monocyclic, linked, or fused ring aromatic hydrocarbon group or a fused ring heteroaromatic group having 6 to 18 carbon atoms. Specific examples include groups substituted with three aryl groups, such as a triphenylsilyl group.

Examples of the boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms include a dihydroxyboryl group (-B(OH) ₂ ), a 4,4,5,5-tetramethyl-[1,3,2]-dioxaborolanyl group, and a 5,5-dimethyl-[1,3,2]-dioxaborinane group.

Examples of linear or branched alkyl groups having 1 to 18 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, tert-butyl, pentyl, n-hexyl, cyclohexyl, octyl, decyl, dodecyl, and octadecyl groups.

Examples of linear or branched alkoxy groups having 1 to 18 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, tert-butoxy, pentyloxy, n-hexyloxy, cyclohexyloxy, octyloxy, decyloxy, dodecyloxy, and octadecyloxy groups.

<Regarding (a-9)>
The monocyclic, linked, or fused ring heteroaromatic group having 3 to 36 carbon atoms (a-9) is a monocyclic, linked, or fused ring heteroaromatic group having 3 to 36 carbon atoms and containing at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom on the aromatic ring. Examples of the heteroaromatic group include a pyrrolyl group, a thienyl group, a furyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a pyridyl group, a phenylpyridyl group, a pyridylphenyl group, a pyrimidyl group, a pyrazyl group, a 1,3,5-triazyl group, a 1,3,5-triazylphenyl group, a 1,3,5-triazylbiphenylyl group, a 4,6-diphenyl-1,3,5-triazyl group, an indolyl group, a benzothienyl group, a benzofuranyl group, a benzimidazolyl group, a benzophenone ... Examples of such groups include an aryl group, an indazolyl group, a benzothiazolyl group, a benzisothiazolyl group, a 2,1,3-benzothiadiazolyl group, a benzoxazolyl group, a benzisoxazolyl group, a 2,1,3-benzoxadiazolyl group, a quinolyl group, an isoquinolyl group, a quinoxalyl group, a quinazolyl group, a carbazolyl group, a 9-phenylcarbazolyl group, a 9-(4-biphenylyl)carbazolyl group, a dibenzothienyl group, a dibenzofuranyl group, a phenoxazinyl group, a phenothiazinyl group, a phenazine group, and a thianthrenyl group.

When the heteroaromatic group of (a-9) has a substituent, the substituents are preferably each independently a cyano group, a fluorine atom, a trifluoromethyl group, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, or a trifluoromethylsulfonyloxy group. Examples of linear or branched alkyl groups having 1 to 18 carbon atoms include the same linear or branched alkyl groups having 1 to 18 carbon atoms as exemplified in (a-8) above. Examples of linear or branched alkoxy groups having 1 to 18 carbon atoms include the same linear or branched alkoxy groups having 1 to 18 carbon atoms as exemplified in (a-8) above.

<Regarding (a-10)>
The phosphine oxide group (a-10) may be an unsubstituted phosphine oxide group or a substituted phosphine oxide group, preferably a substituted phosphine oxide group.
Examples of the substituted phosphine oxide group include the same phosphine oxide groups as exemplified in (a-8) above.

<Regarding (a-11)>
The silyl group (a-11) may be an unsubstituted silyl group or a silyl group having a substituent, and is preferably a silyl group having a substituent.
Examples of the silyl group having a substituent include the same silyl groups as those exemplified in (a-8) above.

<Regarding (a-12)>
Examples of (a-12) boronyl groups which may have a saturated hydrocarbon group having 2 to 10 carbon atoms and boronyl groups which may have a saturated hydrocarbon group having 2 to 10 carbon atoms include the same boronyl groups as exemplified above in (a-8).

(a-13): Linear or branched alkyl group having 1 to 18 carbon atoms Examples of the linear alkyl group having 1 to 18 carbon atoms include the same linear or branched alkyl groups having 1 to 18 carbon atoms as exemplified in (a-8) above.

(a-14): Straight-chain or branched alkoxy group having 1 to 18 carbon atoms Examples of the straight-chain or branched alkoxy group having 1 to 18 carbon atoms include the same straight-chain or branched alkoxy groups having 1 to 18 carbon atoms as exemplified in (a-8) above.

<About k1 to k4>
k1 to k3 are each independently an integer of 0 to 4. k4 is an integer of 0 to 3. When the total of k1 to k4 (k1+k2+k3+k4) is 2 or greater, there are a plurality of A ¹ to A ⁴ , and the plurality of A ¹ to A ⁵ may be the same as or different from one another.
The sum of k1 to k4 is preferably 3 or less, and more preferably 2 or less. When the sum of k1 to k4 is 3 or less, the molecular weight becomes smaller compared to a compound in which the sum of k1 to k4 is 4 or more. As a result, the sublimation temperature of the compound becomes lower, and the heat resistance stability during sublimation is improved, which is preferable.

It is preferable that k1 to k3 are 0 or 1 from the viewpoint of realizing excellent charge transport in the organic electroluminescent device.
From the viewpoint of realizing excellent charge transport in the organic electroluminescent device, k4 is preferably 0 or 1, and more preferably 0.

For the fused ring compound represented by formula (1) above, from the viewpoint of achieving excellent charge transport in an organic electroluminescent device, the sum of k1 to k4 is preferably 0 or more and 3 or less, more preferably 0 or more and 1 or less, and it is particularly preferable that all of k1 to k4 are 0.

<About L>
L represents a phenylene group, biphenylene group, terphenylene group, naphthylene group, pyridylene group, or a single bond, which may have a substituent. L is preferably a phenylene group, biphenylene group, naphthyl group, or a single bond, which may have a substituent, and more preferably a phenylene group, which may have a substituent, or a single bond.

Preferred examples of A ¹ to A ⁵ include the groups (1) to (23) shown below.
(1): Methyl group, ethyl group, cyano group, nitro group, hydroxyl group, thiol group, deuterium atom, methoxy group, trifluoromethylsulfonyloxy group

(2): Phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,6-dimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 4-hydroxyphenyl group, 3-hydroxy group, 2-hydroxyphenyl group, 3,5-dihydroxyphenyl group, 3,4-dihydroxyphenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 3,5-dimethoxyphenyl group, 3,4-dimethoxyphenyl group, 4-trifluoromethylsulfonyloxyphenyl group, 3-trifluoromethylsulfonyloxyphenyl group, 2-trifluoromethylsulfonyloxyphenyl group, 3,5-bis(trifluoromethylsulfonyloxy)phenyl group, 3,4-bis(trifluoromethylsulfonyloxy)phenyl group,

(3): 4-biphenyl group, 3-biphenyl group, 2-biphenyl group, 2-methyl-1,1'-biphenyl-4-yl group, 3-methyl-1,1'-biphenyl-4-yl group, 2'-methyl-1,1'-biphenyl-4-yl group, 3'-methyl-1,1'-biphenyl-4-yl group, 4'-methyl-1,1'-biphenyl-4-yl group, 2,6-dimethyl-1,1'-biphenyl-4-yl group, 2,2'-dimethyl-1,1'-biphenyl-4-yl group, 2,3'-dimethyl 1,1'-biphenyl-4-yl group, 2,4'-dimethyl-1,1'-biphenyl-4-yl group, 3,2'-dimethyl-1,1'-biphenyl-4-yl group, 2',3'-dimethyl-1,1'-biphenyl-4-yl group, 2',4'-dimethyl-1,1'-biphenyl-4-yl group, 2',5'-dimethyl-1,1'-biphenyl-4-yl group, 2',6'-dimethyl-1,1'-biphenyl-4-yl group, 4-phenylbiphenyl group, 2-phenylbiphenyl group

(4): 1-naphthyl group, 2-naphthyl group, 2-methylnaphthalen-1-yl group, 4-methylnaphthalen-1-yl group, 6-methylnaphthalen-2-yl group, 4-(1-naphthyl)phenyl group, 4-(2-naphthyl)phenyl group, 3-(1-naphthyl)phenyl group, 3-(2-naphthyl)phenyl group, 3-methyl-4-(1-naphthyl)phenyl group, 3-methyl-4-(2-naphthyl)phenyl group, 4-(2-methylnaphthalen-1-yl)phenyl group, 3-( (2-methylnaphthalen-1-yl)phenyl group, 4-phenylnaphthalen-1-yl group, 4-(2-methylphenyl)naphthalen-1-yl group, 4-(3-methylphenyl)naphthalen-1-yl group, 4-(4-methylphenyl)naphthalen-1-yl group, 6-phenylnaphthalen-2-yl group, 4-(2-methylphenyl)naphthalen-2-yl group, 4-(3-methylphenyl)naphthalen-2-yl group, 4-(4-methylphenyl)naphthalen-2-yl group

(5): 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, 9,9'-spirobifluorenyl group, 9-phenanthryl group, 2-phenanthryl group, 11,11'-dimethylbenzo[a]fluoren-9-yl group, 11,11'-dimethylbenzo[a]fluoren-3-yl group, 11,11'-dimethylbenzo[b]fluoren-9-yl group, 11,11'-dimethylbenzo[b]fluoren-3-yl group, 11,11'-dimethylbenzo[c]fluoren-9-yl group, 11,11'-dimethylbenzo[c]fluoren-2-yl group, 3-fluoranthenyl group, 8-fluoranthenyl group

(6): 1-imidazolyl group, 2-phenyl-1-imidazolyl group, 2-phenyl-3,4-dimethyl-1-imidazolyl group, 2,3,4-triphenyl-1-imidazolyl group, 2-(2-naphthyl)-3,4-dimethyl-1-imidazolyl group, 2-(2-naphthyl)-3,4-diphenyl-1-imidazolyl group, 1-methyl-2-imidazolyl group, 1-ethyl-2-imidazolyl group, 1-phenyl-2-imidazolyl group, 1-methyl-4-phenyl-2-imidazolyl group, 1-methyl-4,5-dimethyl-2-imidazolyl group, 1-methyl-4,5-diphenyl-2-imidazolyl group, 1-phenyl-4,5-dimethyl-2-imidazolyl group, 1-phenyl-4,5-diphenyl-2-imidazolyl group, 1-phenyl-4,5-dibiphenyl-2-imidazolyl group

(7): 1-methyl-3-pyrazolyl group, 1-phenyl-3-pyrazolyl group, 1-methyl-4-pyrazolyl group, 1-phenyl-4-pyrazolyl group, 1-methyl-5-pyrazolyl group, 1-phenyl-5-pyrazolyl group

(8): 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, 2,1,3-benzothiadiazolyl group

(9): 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 3-isoxazolyl group, 4-isoxazolyl group, 5-isoxazolyl group

(10): 2-pyridyl group, 3-methyl-2-pyridyl group, 4-methyl-2-pyridyl group, 5-methyl-2-pyridyl group, 6-methyl-2-pyridyl group, 3-pyridyl group, 4-methyl-3-pyridyl group, 4-pyridyl group, 2-pyrimidyl group, 2,2'-bipyridin-3-yl group, 2,2'-bipyridin-4-yl group, 2,2'-bipyridin-5-yl group, 2 , 3'-bipyridin-3-yl group, 2,3'-bipyridin-4-yl group, 2,3'-bipyridin-5-yl group, 5-pyrimidyl group, pyrazyl group, 1,3,5-triazin-2-yl group, 4,6-diphenyl-1,3,5-triazin-2-yl group, 4-(biphenyl-4-yl)-6-phenyl-1,3,5-triazin-2-yl group, 4,6-di(biphenyl-4-yl) (biphenyl)-1,3,5-triazin-2-yl group, 4-phenyl-6-[1,1':4',1''-terphenyl]-4-yl-1,3,5-triazin-2-yl group, 4-(biphenyl-3-yl)-6-phenyl-1,3,5-triazin-2-yl group, 4-(biphenyl-3-yl)-6-(biphenyl-4-yl)-1,3,5-triazin-2-yl group, 4-(biphenyl-2-yl)-6-phenyl-1,3,5-triazin-2-yl group, 4-(biphenyl-2-yl)-6-(biphenyl-4-yl)-1,3,5-triazin-2-yl group, 4,6-di(biphenyl-3-yl)-1,3,5-triazin-2-yl group, 4,6-di(biphenyl-2-yl)-1,3,5-triazin-2-yl group

(11): 1-benzimidazolyl group, 2-methyl-1-benzimidazolyl group, 2-phenyl-1-benzimidazolyl group, 1-methyl-2-benzimidazolyl group, 1-phenyl-2-benzimidazolyl group, 1-methyl-5-benzimidazolyl group, 1,2-dimethyl-5-benzimidazolyl group, 1-methyl-2-phenyl-5-benzimidazolyl group, 1-phenyl-5-benzimidazolyl group benzimidazolyl group, 1,2-diphenyl-5-benzimidazolyl group, 1-methyl-6-benzimidazolyl group, 1,2-dimethyl-6-benzimidazolyl group, 1-methyl-2-phenyl-6-benzimidazolyl group, 1-phenyl-6-benzimidazolyl group, 1,2-diphenyl-6-benzimidazolyl group, 1-methyl-3-indazolyl group, 1-phenyl-3-indazolyl group

(12): 2-benzothiazolyl group, 4-benzothiazolyl group, 5-benzothiazolyl group, 6-benzothiazolyl group, 7-benzothiazolyl group, 3-benzoisothiazolyl group, 4-benzoisothiazolyl group, 5-benzoisothiazolyl group, 6-benzoisothiazolyl group, 7-benzoisothiazolyl group, 2,1,3-benzothiadiazol-4-yl group, 2,1,3-benzothiadiazol-5-yl group

(13): 2-benzoxazolyl group, 4-benzoxazolyl group, 5-benzoxazolyl group, 6-benzoxazolyl group, 7-benzoxazolyl group, 3-benzoisoxazolyl group, 4-benzoisoxazolyl group, 5-benzoisoxazolyl group, 6-benzoisoxazolyl group, 7-benzoisoxazolyl group, 2,1,3-benzoxadiazolyl-4-yl group, 2,1,3-benzoxadiazolyl-5-yl group

(14): 2-quinolyl group, 3-quinolyl group, 5-quinolyl group, 6-quinolyl group, 1-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 2-quinoxalyl group, 3-phenyl-2-quinoxalyl group, 6-quinoxalyl group, 2,3-dimethyl-6-quinoxalyl group, 2,3-diphenyl-6-quinoxalyl group, 2-quinazolyl group, 4-quinazolyl group, 2-acridinyl group, 9-acridinyl group, 1,10-phenanthrolin-3-yl group, 1,10-phenanthrolin-5-yl group

(15): 2-thienyl group, 3-thienyl group, 2-benzothienyl group, 3-benzothienyl group, 2-dibenzothienyl group, 4-dibenzothienyl group

(16): 2-furanyl group, 3-furanyl group, 2-benzofuranyl group, 3-benzofuranyl group, 2-dibenzofuranyl group, 4-dibenzofuranyl group

(17): 9-methylcarbazol-2-yl group, 9-methylcarbazol-3-yl group, 9-methylcarbazol-4-yl group, 9-phenylcarbazol-2-yl group, 9-phenylcarbazol-3-yl group, 9-phenylcarbazol-4-yl group, 9-biphenylcarbazol-2-yl group, 9-biphenylcarbazol-3-yl group, 9-biphenylcarbazol-4-yl group

(18): 2-thianthryl group, 10-phenylphenothiazin-3-yl group, 10-phenylphenothiazin-2-yl group, 10-phenylphenoxazin-3-yl group, 10-phenylphenoxazin-2-yl group

(19): 1-methylindol-2-yl group, 1-phenylindol-2-yl group, 9-phenylcarbazol-4-yl group

(20): 4-(2-pyridyl)phenyl group, 4-(3-pyridyl)phenyl group, 4-(4-pyridyl)phenyl group, 3-(2-pyridyl)phenyl group, 3-(3-pyridyl)phenyl group, 3-(4-pyridyl)phenyl group

(21): 4-(2-phenylimidazol-1-yl)phenyl group, 4-(1-phenylimidazol-2-yl)phenyl group, 4-(2,3,4-triphenylimidazol-1-yl)phenyl group, 4-(1-methyl-4,5-diphenylimidazol-2-yl)phenyl group, 4-(2-methylbenzimidazol-1-yl)phenyl group, 4-(2-phenylbenzimidazol-1-yl)phenyl group, 4-(1-methylbenzimidazol-2-yl)phenyl group, 4-(2-phenylbenzimidazol-1-yl)phenyl group, 3-(2-methylbenzimidazol-1-yl)phenyl group, 3-(2-phenylbenzimidazol-1-yl)phenyl group, 3-(1-methylbenzimidazol-2-yl)phenyl group, 3-(1-phenylbenzimidazol-1-yl)phenyl group

(22): 4-(3,5-diphenyltriazin-2-yl)phenyl group, 4-(2-thienyl)phenyl group, 4-(2-furanyl)phenyl group, 5-phenylthiophen-2-yl group, 5-phenylfuran-2-yl group, 4-(5-phenylthiophen-2-yl)phenyl group, 4-(5-phenylfuran-2-yl)phenyl group, 3-(5-phenylthiophen-2-yl)phenyl group, 3-(5-phenylfuran-2-yl)phenyl group, 4-(2-benzothienyl)phenyl group, 4-(3-benzothienyl)phenyl group, 3-(2-benzothienyl)phenyl group, 3-(3 (2-benzothienyl)phenyl group, 4-(2-dibenzothienyl)phenyl group, 4-(4-dibenzothienyl)phenyl group, 3-(2-dibenzothienyl)phenyl group, 3-(4-dibenzothienyl)phenyl group, 4-(2-dibenzofuranyl)phenyl group, 4-(4-dibenzofuranyl)phenyl group, 3-(2-dibenzofuranyl)phenyl group, 3-(4-dibenzofuranyl)phenyl group, 5-phenylpyridin-2-yl group, 4-phenylpyridin-2-yl group, 5-phenylpyridin-3-yl group, 4-(9-carbazolyl)phenyl group, 3-(9-carbazolyl)phenyl group

(23): 2-dibenzo[g,p]chrysenyl group, 3-dibenzo[g,p]chrysenyl group, 2-(7-phenyl)dibenzo[g,p]chrysenyl group, 3-(7-phenyl)dibenzo[g,p]chrysenyl group

In the fused ring compound represented by formula (1), A ¹ to A ⁵ are each independently selected from the viewpoint of ease of raw material availability.
a phenyl group, a biphenylyl group, a pyridylphenyl group, a terphenylyl group, a naphthyl group, a phenanthryl group, a pyrenyl group, a 9,9-spirobi[9H-fluorenyl] group, a triphenylenyl group, a fluoranthenyl group, a benzofluoranthenyl group, a dibenzothienyl group, a dibenzofuranyl group, a pyridyl group, a pyrimidyl group, or a group in which any of these groups is substituted with a cyano group, a nitro group, a hydroxyl group, a thiol group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, a methoxy group, or a trifluoromethylsulfonyloxy group;
a fluorenyl group, a benzofluorenyl group, an anthryl group, a dibenzo[g,p]chrysenyl group, a carbazolyl group, or any of these groups substituted with a cyano group, a nitro group, a hydroxyl group, a thiol group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, a methoxy group, or a phenyl group;
4,6-diphenyl-1,3,5-triazin-2-yl group, (4,6-diphenyl-1,3,5-triazin-2-yl)phenyl group, 4,6-bis(4-biphenyl)-1,3,5-triazin-2-yl group, 4,6-bis(3-biphenyl)-1,3,5-triazin-2-yl group, 4-phenyl-6-[1,1':4',1''-terphenyl]-4-yl-1,3,5-triazin-2-yl group, 4-(biphenyl-3-yl)- 6-phenyl-1,3,5-triazin-2-yl group, 4-(biphenyl-3-yl)-6-(biphenyl-4-yl)-1,3,5-triazin-2-yl group, 4-(biphenyl-2-yl)-6-phenyl-1,3,5-triazin-2-yl group, 4-(biphenyl-2-yl)-6-(biphenyl-4-yl)-1,3,5-triazin-2-yl group, 4,6-bis(biphenyl-2-yl)-1,3,5-triazin-2-yl group;
Preferred are a cyano group, a nitro group, a hydroxyl group, a thiol group, diphenylphosphine oxide, a triphenylsilyl group, a dihydroxyboryl group (-B(OH) ₂ ), a 4,4,5,5-tetramethyl-[1,3,2]-dioxaborolanyl group, a 5,5-dimethyl-[1,3,2]-dioxaborinane group, and a methyl group.

The fused ring compound represented by formula (1) is more preferably an interfused ring compound represented by formula (2).

During the ceremony,
^B1 's each independently represent a phenylene group, biphenylene group, terphenylene group, naphthylene group, pyridylene group, or a single bond, each of which may have a substituent;
^B2 is independently
a monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent;
a monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms which may have a substituent;
a boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms;
a linear or branched alkyl group having 1 to 18 carbon atoms;
a linear or branched alkoxy group having 1 to 18 carbon atoms, or
represents a trifluoromethylsulfonyloxy group;
n is an integer of 0 to 3;
Z represents a carbon atom or a nitrogen atom.

<About ^B1 >
^B1 's each independently represent a phenylene group, biphenylene group, terphenylene group, naphthylene group, pyridylene group, or a single bond, which may have a substituent. ^B1 's are preferably a phenylene group, biphenylene group, naphthylene group, or a single bond, which may have a substituent, and more preferably a phenylene group, which may have a substituent, or a single bond.

<About ^B2 >
^B2 each independently represents a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, a monocyclic, linked, or fused heteroaromatic group having 3 to 36 carbon atoms which may have a substituent, a boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, or a trifluoromethylsulfonyloxy group. ^B2 is preferably a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, or a monocyclic, linked, or fused heteroaromatic group having 3 to 36 carbon atoms which may have a substituent.

<Regarding n>
n is an integer of 0 or more and 3 or less. n is preferably 0 or more and 2 or less, and more preferably 0 or more and 1 or less.

<About Z>
Z represents a carbon atom or a nitrogen atom. Of the three Zs in formula (2), it is preferable that one or more are nitrogen atoms, more preferably two or more are nitrogen atoms. It is particularly preferable that all three are nitrogen atoms.

<Preferred specific examples of fused ring compounds>
Preferred specific examples of the fused ring compound represented by formula (1) are shown below, but the invention is not limited to these.
Tables A-1 to A-5 show compounds (3-1) to (3-200) in which the substituent Ar shown in formula (3) is a group shown in Tables A-1 to A-5. In Table 1, m represents an integer from 1 to 200. Therefore, for example, compound (3-24) shows compound (3-24) which has a skeleton of formula (3) and in which the substituent Ar of the skeleton is a phenyl group. In addition, dashed lines in the tables show bonding positions.

The uses of the fused ring compounds will be described below.
<Material for organic electroluminescent device, electron transport material for organic electroluminescent device>
The fused ring compound (1) can be used, for example, as a material for an organic electroluminescent device, although it is not particularly limited thereto. The fused ring compound (1) can also be used, for example, as an electron transport material for an organic electroluminescent device.

A material for organic electroluminescent devices according to one aspect of the present invention contains a fused ring compound represented by formula (1). Furthermore, an electron transport material for organic electroluminescent devices according to another aspect of the present invention contains fused ring compound (1). Materials for organic electroluminescent devices and electron transport materials for organic electroluminescent devices containing fused ring compound (1) contribute to the production of organic electroluminescent devices with excellent current efficiency.

<Organic electroluminescent device>
The organic electroluminescent device according to one aspect of the present invention includes a fused ring compound (1).
The configuration of the organic electroluminescent device is not particularly limited, but examples thereof include the following configurations (i) to (vi).
(i): anode/light-emitting layer/cathode (ii): anode/hole-transporting layer/light-emitting layer/cathode (iii): anode/light-emitting layer/electron-transporting layer/cathode (iv): anode/hole-transporting layer/light-emitting layer/electron-transporting layer/cathode (v): anode/hole-injection layer/hole-transporting layer/light-emitting layer/electron-transporting layer/electron-injection layer/cathode (vi): anode/hole-injection layer/charge-generating layer/hole-transporting layer/light-emitting layer/electron-transporting layer/cathode

An organic electroluminescent device according to one embodiment of the present invention will be described in more detail below, taking the above-mentioned configuration (vi) as an example, with reference to Fig. 1. Fig. 1 is a schematic cross-sectional view showing an example of a layered structure of an organic electroluminescent device containing a cyclic azine compound according to one embodiment of the present invention.
1 has a so-called bottom-emission type element configuration, the organic electroluminescent element according to one embodiment of the present invention is not limited to the bottom-emission type element configuration. That is, the organic electroluminescent element according to one embodiment of the present invention may have a top-emission type element configuration or any other known element configuration.

The organic electroluminescent device 100 comprises, in this order, a substrate 1, an anode 2, a hole injection layer 3, a charge generation layer 4, a hole transport layer 5, an emissive layer 6, an electron transport layer 7, and a cathode 8. However, some of these layers may be omitted, or other layers may be added. For example, an electron injection layer may be provided between the electron transport layer 7 and the cathode 8, or the charge generation layer 4 may be omitted and the hole transport layer 5 may be provided directly on the hole injection layer 3. Alternatively, a single layer that combines the functions of multiple layers, such as an electron injection/transport layer that combines the functions of both an electron injection layer and an electron transport layer, may be provided instead of the multiple layers. Furthermore, for example, the single-layer hole transport layer 5 and the single-layer electron transport layer 7 may each be composed of multiple layers.

[Layer containing fused ring compound (1)]
An organic electroluminescent device contains a fused ring compound represented by formula (1) in one or more layers selected from the group consisting of an emitting layer and a layer between the emitting layer and a cathode. Accordingly, in the exemplary configuration shown in FIG. 1 , organic electroluminescent device 100 contains fused ring compound (1) in at least one layer selected from the group consisting of an emitting layer 6 and an electron transport layer 7. It is particularly preferred that electron transport layer 7 contains fused ring compound (1). Fused ring compound (1) may be contained in multiple layers of the organic electroluminescent device, and when an electron injection layer is provided between the electron transport layer and the cathode, the electron injection layer may contain fused ring compound (1).
In the following, an organic electroluminescent device 100 in which the electron transport layer 7 contains the fused ring compound (1) will be described.

[Substrate 1]
There are no particular limitations on the substrate, and examples include a glass plate, a quartz plate, a plastic plate, etc. In addition, in the case of a configuration in which light is extracted from the substrate 1 side, the substrate 1 is transparent to the wavelength of light.

Examples of optically transparent plastic films include films made of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), cellulose triacetate (TAC), cellulose acetate propionate (CAP), etc.

[Anode 2]
An anode 2 is provided on the substrate 1 (on the hole injection layer 3 side).
In the case of an organic electroluminescent device in which light is extracted through the anode, the anode is formed from a material that is transparent or substantially transparent to the emitted light.

The transparent material used for the anode is not particularly limited, but examples thereof include indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide, aluminum-doped tin oxide, magnesium-indium oxide, nickel-tungsten oxide, other metal oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, and metal sulfides such as zinc sulfide.
In the case of an organic electroluminescent device configured to extract light only from the cathode side, the transmittance characteristics of the anode are not important, and therefore, examples of materials that can be used for the anode in this case include gold, iridium, molybdenum, palladium, platinum, etc.
A buffer layer (electrode interface layer) may be provided on the anode.

[Hole injection layer 3, hole transport layer 5]
Between the anode 2 and a light-emitting layer 6 (described later), a hole injection layer 3, a charge generation layer 4 (described later), and a hole transport layer 5 are provided in this order from the anode 2 side.
The hole injection layer and the hole transport layer have the function of transporting holes injected from the anode to the light-emitting layer. By interposing the hole injection layer and the hole transport layer between the anode and the light-emitting layer, a large number of holes can be injected into the light-emitting layer with a lower electric field.

The hole injection layer and hole transport layer also function as electron blocking layers. That is, electrons injected from the cathode and transported from the electron injection layer and/or electron transport layer to the light-emitting layer are prevented from leaking into the hole injection layer and/or hole transport layer by the electron barrier present at the interface between the light-emitting layer and the hole injection layer and/or hole transport layer. As a result, the electrons accumulate at the interface within the light-emitting layer, resulting in effects such as improved current efficiency and an organic electroluminescent device with excellent light-emitting performance.

The materials for the hole injection layer and hole transport layer have at least one of hole injection, hole transport, and electron barrier properties. The materials for the hole injection layer and hole transport layer may be either organic or inorganic.

Specific examples of materials for the hole injection layer and hole transport layer 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 (particularly thiophene oligomers), porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds. Among these, porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds are preferred, with aromatic tertiary amine compounds being particularly preferred.

Specific examples of the aromatic tertiary amine compound and the styrylamine compound 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'- Examples thereof include di(4-methoxyphenyl)-4,4'-diaminobiphenyl, N,N,N',N'-tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis(diphenylamino)quadriphenyl, 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-phenylamino]biphenyl (NPD), and 4,4',4''-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine (MTDATA).
Furthermore, inorganic compounds such as p-type Si and p-type SiC can also be given as examples of materials for the hole injection layer and the hole transport layer.

The hole injection layer and hole transport layer may have a single-layer structure made of one or more materials, or a laminate structure made of multiple layers of the same or different compositions.

[Charge Generation Layer 4]
A charge generating layer 4 may be provided between the hole injection layer 3 and the hole transport layer 5 .
The material for the charge generating layer is not particularly limited, but an example thereof is dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile (HAT-CN).
The charge generating layer may have a single layer structure made of one or more materials, or may have a laminate structure made of multiple layers of the same or different compositions.

[Light-emitting layer 6]
The light-emitting layer 6 is provided between the hole transport layer 5 and the electron transport layer 7 described below.
The light-emitting layer may be made of a phosphorescent material, a fluorescent material, or a thermally activated delayed fluorescent material. In the light-emitting layer, electron-hole pairs recombine, resulting in light emission.

The light-emitting layer may consist of a single small molecule material or a single polymer material, but more commonly consists of a host material doped with a guest compound. Light emission comes primarily from the dopant and can be of any color.

Examples of host materials include compounds having a biphenyl group, a fluorenyl group, a triphenylsilyl group, a carbazole group, a pyrenyl group, or an anthryl group. More specific examples include DPVBi (4,4'-bis(2,2-diphenylvinyl)-1,1'-biphenyl), BCzVBi (4,4'-bis(9-ethyl-3-carbazovinylene)1,1'-biphenyl), TBADN (2-tertiarybutyl-9,10-di(2-naphthyl)anthracene), ADN (9,10-di(2-naphthyl)anthracene), CBP (4,4'-bis(carbazol-9-yl)biphenyl), CDBP (4,4'-bis(carbazol-9-yl)-2,2'-dimethylbiphenyl), 2-(9-phenylcarbazol-3-yl)-9-[4-(4-phenylphenylquinazolin-2-yl)carbazole], 9,10-bis(biphenyl)anthracene, and the like.

Examples of fluorescent dopants include anthracene, pyrene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine, quinacridone, dicyanomethylenepyran compounds, thiopyran compounds, polymethine compounds, pyrylium, thiapyrylium compounds, fluorene derivatives, periflanthene derivatives, indenoperylene derivatives, bis(azinyl)amine boron compounds, bis(azinyl)methane compounds, and carbostyril compounds. The fluorescent dopant may be a combination of two or more selected from these.

Phosphorescent dopants include, for example, organometallic complexes of transition metals such as iridium, platinum, palladium, and osmium.

Specific examples of fluorescent dopants and phosphorescent dopants include Alq3 (tris(8-hydroxyquinoline)aluminum), DPAVBi (4,4'-bis[4-(di-p-tolylamino)styryl]biphenyl), perylene, bis[2-(4-n-hexylphenyl)quinoline](acetylacetonate)iridium(III), Ir(PPy)3 (tris(2-phenylpyridine)iridium(III)), and FIrPic (bis(3,5-difluoro-2-(2-pyridyl)phenyl-(2-carboxypyridyl)iridium(III))).

Furthermore, the light-emitting material is not limited to being contained only in the light-emitting layer. For example, the light-emitting material may be contained in a layer adjacent to the light-emitting layer (hole transport layer 5 or electron transport layer 7). This can further increase the current efficiency of the organic electroluminescent device.

The light-emitting layer may have a single-layer structure made of one or more materials, or a laminate structure made of multiple layers of the same or different compositions.

[Electron transport layer 7]
An electron transport layer 7 is provided between the light-emitting layer 6 and a cathode 8 described later.
The electron transport layer has a function of transporting electrons injected from the cathode to the light-emitting layer. By interposing the electron transport layer between the cathode and the light-emitting layer, electrons are injected into the light-emitting layer at a lower electric field.

As mentioned above, the electron transport layer preferably contains a fused ring compound represented by formula (1) above.

In addition to the fused ring compound (1), the electron transport layer may further contain a conventionally known electron transport material. Examples of conventionally known electron transport materials include 8-hydroxyquinolinatolithium (Liq), bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h]quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)(o-cresolate)gallium, and bis(2-methyl-8-quinolinato)-1-naphthol. Examples include bis(2-methyl-8-quinolinato)-2-naphtholatogallium, 2-[3-(9-phenanthrenyl)-5-(3-pyridinyl)phenyl]-4,6-diphenyl-1,3,5-triazine, and 2-(4,''-di-2-pyridinyl[1,1':3',1''-terphenyl]-5-yl)-4,6-diphenyl-1,3,5-triazine, BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), BAlq (bis(2-methyl-8-quinolinolato)-4-(phenylphenolato)aluminum), and bis(10-hydroxybenzo[h]quinolinato)beryllium).

The electron transport layer may have a single layer structure made of one or more materials, or may have a laminate structure made of multiple layers of the same or different compositions.
When the electron transport layer has a two-layer structure in which a first electron transport layer is on the light-emitting layer side and a second electron transport layer is on the cathode side, it is preferable that either or both of the first electron transport layer and the second electron transport layer contain the fused ring compound (1).

[Cathode 8]
A cathode 8 is provided on the electron transport layer 7 .
In the case of an organic electroluminescent device having a configuration in which only light emitted through the anode is extracted, the cathode can be formed from any conductive material.
Cathode 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, and rare earth metals.
A buffer layer (electrode interface layer) may be provided on the cathode (on the electron transport layer side).

[Method of forming each layer]
Each layer except for the electrodes (anode and cathode) described above can be formed by forming a thin film from the material of each layer (together with a material such as a binder resin and a solvent, if necessary) by a known method such as vacuum deposition, spin coating, casting, or LB (Langmuir-Blodgett) method.
There are no particular limitations on the thickness of each layer formed in this way, and it can be selected appropriately depending on the situation, but it is usually in the range of 5 nm to 5 μm.

Anodes and cathodes can be formed by forming a thin film of electrode material using methods such as vapor deposition or sputtering. A pattern can be formed using a mask of the desired shape during vapor deposition or sputtering, or a thin film can be formed by vapor deposition or sputtering, and then a pattern of the desired shape can be formed using photolithography.

The film thickness of the anode and cathode is preferably 1 μm or less, and more preferably 10 nm or more and 200 nm or less.

An organic electroluminescent device according to one embodiment of the present invention may be used as a type of lamp for illumination or as an exposure light source, or as a projection device that projects images, or as a display device that directly views still or moving images. When used as a display device for playing moving images, the driving method may be either a passive matrix method or an active matrix method. Furthermore, by using two or more types of organic electroluminescent devices according to this embodiment that emit different light colors, it is possible to produce a full-color display device.

The present invention will be explained in more detail below based on examples, but the present invention should not be construed as being limited to these examples.

¹ H-NMR measurements were carried out using Gemini 200 (Varian).
The glass transition temperature was measured using a DSC7020 (manufactured by Hitachi High-Tech Science Corporation).
Mass spectrometry was carried out using an LCMS-2020 (Shimadzu Corporation).
The light emitting characteristics of the organic electroluminescent device were evaluated by applying a direct current to the fabricated device at room temperature using a luminance meter (product name: BM-9, manufactured by Topcon Technohouse Co., Ltd.).

Example 1 Synthesis of Compound (3-53)

Under a nitrogen stream, 4-chloro-dibenzo[g,p]chrysene (0.78 g, 2.15 mmol), 4,4,5,5-tetramethyl-2-[3-(3-fluoranthenyl)phenyl]-1,3,5-dioxaborolane (0.96 g, 2.37 mmol), palladium acetate (10 mg, 0.043 mmol), Xphos (43.2 mg, 0.086 mmol), toluene (21 mL), and a 2 M aqueous potassium phosphate solution (7 mL) were placed in a 100 mL two-neck flask and stirred for 24 hours at 100° C. After cooling to room temperature, the aqueous and organic layers were separated, and the resulting organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The concentrate was recrystallized (toluene/hexane) to obtain 1.17 g (1.93 mmol) of colorless powder of compound (3-53) (yield 90.0%, HPLC purity 99.5%). The sublimation temperature of compound (3-53) was 330° C., and it was confirmed that the sublimed product of compound (3-53) was in a glassy state.
The compound was identified by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ) δ (ppm): 8.75-8.69 (m, 5H), 8.60 (d, 1H), 7.99-7.90 (m, 5H), 7.77 (d, 1H) , 7.71-7.61 (m, 11H), 7.57-7.49 (m, 2H), 7.40-7.37 (m, 2H), 7.23 (td, 1H)

Example 2 Synthesis of compound (3-149)

Under a nitrogen stream, 4-chloro-dibenzo[g,p]chrysene (4.00 g, 11.0 mmol), bispinacolatodiboron (3.07 g, 12.1 mmol), potassium acetate (3.24 g, 33.0 mmol), palladium acetate (49.6 mg, 0.22 mmol), tricyclohexylphosphine tetrafluoroborate (163 mg, 0.44 mmol), and o-xylene (110 mL) were added to a 300 mL two-neck flask and stirred at 140°C for 24 hours. After cooling to room temperature, insoluble materials were removed by filtration, and water was added to the filtrate, allowing the aqueous and organic layers to separate. The resulting organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure to yield 6.38 g of a solid containing compound (3-149). The resulting powder was used directly in the next step.

The compound was identified by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ) δ (ppm): 8.75-8.69 (m, 6H), 8.64 (td, 1H), 8.39 (dd, 1H), 7.87 (dd, 1H), 7.71-7.52 (m, 7H), 1.59 (s, 12H)

Example 3 Synthesis of compound (3-160)

Under a nitrogen stream, 2-chloro-4,6-diphenyl-1,3,5-triazine (0.80 g, 3.00 mmol), compound (3-149) obtained in Example 2 (1.50 g, 3.30 mmol), tetrakistriphenylphosphine palladium (69.8 mg, 0.06 mmol), toluene (30 mL), and a 2 M aqueous potassium phosphate solution (10 mL) were placed in a 100 mL two-neck flask and stirred at 100°C for 24 hours. After cooling to room temperature, the aqueous and organic layers were separated. The resulting organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The concentrate was recrystallized (toluene/hexane) to obtain 0.75 g (1.34 mmol) of compound (3-160) as a white powder (yield 44.5%, HPLC purity 99.8%). The sublimation temperature of the compound (3-160) was 290° C., and it was confirmed that the sublimed compound (3-160) was in a glassy state.
The compound was identified by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ) δ (ppm): 8.89-8.84 (m, 2H), 8.76-8.73 (m, 2H), 8.69-8.64 (m, 2H), 8.58 (d, 4H), 8.17 ( dd, 1H), 7.81 (t, 1H), 7.76-7.67 (m, 5H), 7.63-7.52 (m, 6H), 7.48 (td, 1H), 7.12 (td, 1H)

Example 4 Synthesis of Compound (3-161)

Under a nitrogen stream, 2-(4-biphenyl)-4-chloro-6-phenyl-1,3,5-triazine (1.03 g, 3.00 mmol), compound (3-149) obtained in Example 2 (1.50 g, 3.30 mmol), tetrakistriphenylphosphine palladium (69.8 mg, 0.06 mmol), toluene (30 mL), and a 2 M aqueous potassium phosphate solution (10 mL) were placed in a 100 mL two-neck flask and stirred at 100°C for 24 hours. After cooling to room temperature, the aqueous and organic layers were separated. The resulting organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The concentrate was recrystallized (toluene/hexane) to obtain 0.77 g (1.21 mmol) of a yellow powder of compound (3-161) (yield 40.4%, HPLC purity 99.8%). The sublimation temperature of the compound (3-161) was 335° C., and it was confirmed that the sublimed compound (3-161) was in a glassy state.
The compound was identified by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ) δ (ppm): 8.89-8.85 (m, 2H), 8.77-8.73 (m, 2H), 8.69-8.58 (m, 6H), 8.18 (dd, 1H) ), 7.82 (t, 1H), 7.78-7.69 (m, 9H), 7.64-7.47 (m, 6H), 7.42 (t, 1H), 7.13 (t, 1H)

Example 5 Synthesis of Compound (3-164)

Under a nitrogen stream, 2,4-bis[(1,1'-biphenyl)-4-yl]-6-chloro-1,3,5-triazine (1.01 g, 2.40 mmol), compound (3-149) obtained in Example 2 (1.20 g, 2.64 mmol), tetrakistriphenylphosphine palladium (56.9 mg, 0.05 mmol), toluene (24 mL), and a 2 M aqueous potassium phosphate solution (8 mL) were placed in a 100 mL two-neck flask and stirred at 100°C for 24 hours. After cooling to room temperature, hexane was added and the precipitated solid was collected by filtration. The resulting solid was recrystallized (o-xylene) to obtain 0.84 g (1.18 mmol) of a yellow powder of compound (3-164) (yield 49.2%, HPLC purity 99.7%). The sublimation temperature of the compound (3-164) was 375° C., and it was confirmed that the sublimed compound (3-149) was in a glassy state.
The compound was identified by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ) δ (ppm): 8.90-8.85 (m, 2H), 8.77-8.73 (m, 2H), 8.70-8.64 (m, 6H), 8.20 (d, 1H) , 7.83 (t, 1H), 7.80-7.69 (m, 13H), 7.53-7.47 (m, 5H), 7.42 (t, 2H), 7.15 (t, 1H)

Example 7 Synthesis of Compound (3-171)

Under a nitrogen stream, 2-chloro-4-(3-chlorophenyl)-6-phenyl-1,3,5-triazine (151 mg, 0.50 mmol), compound (3-149) obtained in Example 2 (250 mg, 0.55 mmol), tetrakistriphenylphosphine palladium (11.6 mg, 0.01 mmol), toluene (5 mL), and a 2 M aqueous potassium phosphate solution (2 mL) were placed in a 50 mL two-neck flask and stirred at 100°C for 24 hours. After cooling to room temperature, the aqueous and organic layers were separated, and the resulting organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. Hexane was added to the concentrate, and the precipitated solid was collected by filtration to obtain 100 mg of a yellow solid containing compound (3-171).
The compounds were identified by mass spectrometry.
MS (m/z); 595 (M+1)

Example 8 Synthesis of Compound (3-180)

Under a nitrogen stream, 4-chloro-dibenzo[g,p]chrysene (0.60 g, 1.65 mmol), 2,4-diphenyl-6-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1,3,5-triazine (0.80 g, 1.82 mmol), palladium acetate (7.6 mg, 0.033 mmol), Xphos (32.0 mg, 0.066 mmol), toluene (18 mL), and a 2 M aqueous potassium phosphate solution (6 mL) were placed in a 100 mL two-neck flask and stirred at 100° C. for 24 hours. After cooling to room temperature, the aqueous and organic layers were separated, and the resulting organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The concentrate was washed (ethyl acetate/methanol) to obtain 0.87 g (1.37 mmol) of a yellow powder of compound (3-180) (yield 82.9%, HPLC purity 99.8%). The sublimation temperature of compound (3-180) was 340° C., and it was confirmed that the sublimed product of compound (3-180) was in a glassy state.
The compound was identified by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ) δ (ppm): 9.00 (s, 1H), 8.86-8.83 (m, 1H), 8.80-8.71 (m, 9H), 8.57 (d, 1H), 7.82 (dd, 1H), 7.77-7.56 (m, 14H), 7.41 (td, 1H), 7.07 (td, 1H)

The resulting compound was then used for device evaluation.

Element Example 1 (see Figure 2)
(Preparation of the substrate 101 and the anode 102)
A glass substrate with an indium-tin oxide (ITO) transparent electrode, on which a 2 mm wide stripe-patterned ITO film (thickness: 110 nm) was formed, was prepared as a substrate having an anode on its surface. The substrate was then washed with isopropyl alcohol and then subjected to surface treatment using ozone and ultraviolet light.

(Preparation for vacuum deposition)
After cleaning, each layer was deposited on the surface-treated substrate by vacuum deposition using a vacuum deposition method, and each layer was laminated.
First, the glass substrate was placed in a vacuum deposition chamber, and the pressure was reduced to 1.0×10 ⁻⁴ Pa. Then, each layer was formed in the following order according to the film formation conditions.

(Fabrication of Hole Injection Layer 103)
Sublimation-purified N-[1,1′-biphenyl]-4-yl-9,9-dimethyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9H-fluoren-2-amine and 1,2,3-tris[(4-cyano-2,3,5,6-tetrafluorophenyl)methylene]cyclopropane were deposited at a rate of 0.15 nm/sec to form a 10 nm thick film, thereby forming a hole injection layer 103.

(Fabrication of First Hole Transport Layer 1051)
Sublimation-purified N-[1,1′-biphenyl]-4-yl-9,9-dimethyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9H-fluoren-2-amine was formed into a film of 85 nm at a rate of 0.15 nm/sec to form a first hole transport layer 1051.

(Fabrication of Second Hole Transport Layer 1052)
Sublimation-purified N-phenyl-N-(9,9-diphenylfluoren-2-yl)-N-(1,1′-biphenyl-4-yl)amine was deposited at a rate of 0.15 nm/sec to form a film of 5 nm, thereby forming a second hole transport layer 1052 .

(Fabrication of Light-Emitting Layer 106)
Sublimation-purified 3-(10-phenyl-9-anthryl)-dibenzofuran and 2,7-bis[N,N-di-(4-tertbutylphenyl)]amino-bisbenzofurano-9,9′-spirofluorene were mixed in a mass ratio of 95:5 to form a 20 nm film, thereby producing the light-emitting layer 106. The film formation rate was 0.18 nm/sec.

(Fabrication of First Electron Transport Layer 1071)
Sublimation-purified 2-[3′-(9,9-dimethyl-9H-fluoren-2-yl)[1,1′-biphenyl]-3-yl]-4,6-diphenyl-1,3,5-triazine was deposited at a rate of 0.05 nm/sec to form a 6 nm film, thereby forming a first electron transport layer 1071 .

(Fabrication of Second Electron Transport Layer 1072)
A 25 nm film was formed by mixing the compound (1-161) synthesized according to Non-Patent Document 1 and Liq in a mass ratio of 50:50 to prepare a second electron transport layer 1072. The film formation rate was 0.15 nm/sec.

(Fabrication of the cathode 108)
Finally, a metal mask was placed perpendicular to the ITO stripes on the substrate, and a cathode 108 was formed. The cathode had a two-layer structure, with silver/magnesium (mass ratio 1/10) and silver deposited in this order to thicknesses of 80 nm and 20 nm, respectively. The silver/magnesium deposition rate was 0.5 nm/sec, and the silver deposition rate was 0.2 nm/sec.

As a result of the above, an organic electroluminescent device 100 having a light-emitting area of 4 mm ² was produced as shown in Figure 2. The thickness of each film was measured using a stylus film thickness measuring instrument (DEKTAK, manufactured by Bruker).

The device was then sealed in a nitrogen-atmosphere glove box with oxygen and moisture concentrations of 1 ppm or less. The glass sealing cap and the film-formed substrate (device) were sealed using bisphenol F-type epoxy resin (manufactured by Nagase ChemteX Corporation).

A direct current was applied to the organic electroluminescent device prepared as described above, and the light-emitting characteristics were evaluated using a luminance meter (product name: BM-9, manufactured by Topcon Technohouse). As light-emitting characteristics, the current efficiency (cd/A) when a current density of 10 mA/ ^cm2 was applied was measured, and the device life (h) during continuous lighting was measured. Note that the device life (h) was measured by measuring the luminance decay time during continuous lighting when the prepared device was driven at an initial luminance of 1000 cd/ ^m2 , and measuring the time required for the luminance (cd/ ^m2 ) to decrease by 5%.

The voltage, current efficiency, and element life are relative values, with the results for Element Reference Example 1 set as the reference value (100). The measurement results are shown in Table 1.

Element Example 2, Element Reference Examples 1 and 2
Organic electroluminescent devices were fabricated and evaluated in the same manner as in Element Example 1, except that compound (1-164), compound (X1), and compound (X2) were used in this order instead of compound (1-161). The measurement results are shown in Table 1.

The fused ring compounds according to one embodiment of the present invention can be suitably used not only in conventional fluorescent devices, but also in phosphorescent devices and organic electroluminescent devices that utilize thermally activated delayed fluorescence (TADF). Furthermore, because the fused ring compounds according to one embodiment of the present invention have high current efficiency, they can be used in the charge transport portion of various organic electronic devices. Therefore, they can be used not only in organic electroluminescent devices, but also in imaging devices such as organic imaging sensors and photoelectric conversion devices such as organic solar cells.

1,101 Substrate 2,102 Anode 3,103 Hole injection layer
4 Charge generation layer 5, 105 Hole transport layer 6, 106 Light-emitting layer 7, 107 Electron transport layer 8, 108 Cathode 51, 1051 First hole transport layer 52, 1052 Second hole transport layer 71, 1071 First electron transport layer 72, 1072 Second electron transport layer 100 Organic electroluminescent device

Claims (10)

A fused ring compound represented by formula (1):
In formula (1),
A1 to A5 each independently represent a charge transporting group;
The charge transporting groups each independently represent
a trifluoromethyl group,
pentafluoroethyl group,
nitro group,
hydroxyl groups,
thiol groups,
a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, a fluorenyl group, an anthryl group, a benzofluorenyl group, a fluoranthenyl group, a benzofluoranthenyl group, a triphenylenyl group, a spirobifluorenyl group, a diphenylfluorenyl group, or a dibenzo[g,p]chrysenyl group, which may have a substituent;
a monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms which may have a substituent;
an optionally substituted phosphine oxide group,
a silyl group which may have a substituent;
a linear or branched alkyl group having 1 to 18 carbon atoms;
a linear or branched alkoxy group having 1 to 18 carbon atoms, or
a trifluoromethylsulfonyloxy group;
When the optionally substituted phenyl group, biphenylyl group, terphenylyl group, naphthyl group, fluorenyl group, anthryl group, benzofluorenyl group, fluoranthenyl group, benzofluoranthenyl group, triphenylenyl group, spirobifluorenyl group, diphenylfluorenyl group, or dibenzo[g,p]chrysenyl group has a substituent, the substituent is each independently a group selected from the group consisting of a fluorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a phosphine oxide group, a silyl group, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, and a trifluoromethylsulfonyloxy group;
When the monocyclic, linked, or fused ring heteroaromatic group having 3 to 36 carbon atoms which may have a substituent has a substituent, the substituents are each independently a group selected from the group consisting of a cyano group, a fluorine atom, a trifluoromethyl group, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, and a trifluoromethylsulfonyloxy group;
When the optionally substituted phosphine oxide group has a substituent, the substituent is a group selected from the group consisting of monocyclic, linked, or fused ring aromatic hydrocarbon groups having 6 to 18 carbon atoms and monocyclic, linked, or fused ring heteroaromatic groups having 6 to 18 carbon atoms;
When the optionally substituted silyl group has a substituent, the substituent is a group selected from the group consisting of monocyclic, linked, or fused ring aromatic hydrocarbon groups having 6 to 18 carbon atoms and monocyclic, linked, or fused ring heteroaromatic groups having 6 to 18 carbon atoms;
k1 to k3 each independently represent an integer of 0 to 4;
k4 is an integer of 0 to 3;
L represents a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, a pyridylene group, or a single bond;
The multiple A1 to A5 may be the same or different. The fused ring compound according to claim 1, wherein the sum of k1 to k4 is 0 or more and 3 or less. The fused ring compound according to claim 1, wherein the sum of k1 to k4 is 0 or more and 1 or less. The fused ring compound according to claim 1, wherein k1 to k4 are 0. The charge transporting groups each independently represent
a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, a fluorenyl group, an anthryl group, a benzofluorenyl group, a fluoranthenyl group, a benzofluoranthenyl group, a triphenylenyl group, a spirobifluorenyl group, a diphenylfluorenyl group, or a dibenzo[g,p]chrysenyl group, which may have a substituent;
a monocyclic, linked, or fused ring heteroaromatic group having 3 to 36 carbon atoms which may have a substituent;
a linear or branched alkyl group having 1 to 18 carbon atoms;
a linear or branched alkoxy group having 1 to 18 carbon atoms; or
trifluoromethylsulfonyloxy group;
and
When the optionally substituted phenyl group, biphenylyl group, terphenylyl group, naphthyl group, fluorenyl group, anthryl group, benzofluorenyl group, fluoranthenyl group, benzofluoranthenyl group, triphenylenyl group, spirobifluorenyl group, diphenylfluorenyl group, or dibenzo[g,p]chrysenyl group has a substituent, the substituent is each independently a group selected from the group consisting of a fluorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a phosphine oxide group, a silyl group, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, and a trifluoromethylsulfonyloxy group;
The fused ring compound according to any one of claims 1 to 4, wherein when the monocyclic, linked, or fused-ring heteroaromatic group having 3 to 36 carbon atoms which optionally has a substituent has a substituent, the substituents are each independently selected from the group consisting of a cyano group, a fluorine atom, a trifluoromethyl group, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms , and a trifluoromethylsulfonyloxy group. A fused ring compound represented by formula (2):
During the ceremony,
B1 each independently represent a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, a pyridylene group, or a single bond;
B2 is independently
a monocyclic, linked, or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms;
a monocyclic, linked, or fused ring heteroaromatic group having 3 to 36 carbon atoms;
a linear or branched alkyl group having 1 to 18 carbon atoms;
a linear or branched alkoxy group having 1 to 18 carbon atoms, or
represents a trifluoromethylsulfonyloxy group;
n is an integer of 0 to 3;
Z represents a carbon atom or a nitrogen atom. A material for organic electroluminescent devices comprising the fused ring compound described in any one of claims 1 to 6. An organic electroluminescent device comprising the fused ring compound according to any one of claims 1 to 6. An organic electroluminescent device material comprising a fused ring compound represented by the following formula (1):
In formula (1),
A1 to A5 each independently represent a charge transporting group;
The charge transporting groups each independently represent
trifluoromethyl group,
pentafluoroethyl group,
nitro group,
hydroxyl groups,
thiol groups,
a monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent;
a monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms which may have a substituent;
an optionally substituted phosphine oxide group,
a silyl group which may have a substituent;
a linear or branched alkyl group having 1 to 18 carbon atoms;
a linear or branched alkoxy group having 1 to 18 carbon atoms, or
a trifluoromethylsulfonyloxy group;
When the monocyclic, linked, or fused-ring aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent has a substituent, the substituents are each independently a group selected from the group consisting of a fluorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a phosphine oxide group, a silyl group, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, and a trifluoromethylsulfonyloxy group;
When the monocyclic, linked, or fused ring heteroaromatic group having 3 to 36 carbon atoms which may have a substituent has a substituent, the substituents are each independently a group selected from the group consisting of a cyano group, a fluorine atom, a trifluoromethyl group, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, and a trifluoromethylsulfonyloxy group;
When the optionally substituted phosphine oxide group has a substituent, the substituent is a group selected from the group consisting of monocyclic, linked, or fused ring aromatic hydrocarbon groups having 6 to 18 carbon atoms and monocyclic, linked, or fused ring heteroaromatic groups having 6 to 18 carbon atoms;
When the optionally substituted silyl group has a substituent, the substituent is a group selected from the group consisting of monocyclic, linked, or fused ring aromatic hydrocarbon groups having 6 to 18 carbon atoms and monocyclic, linked, or fused ring heteroaromatic groups having 6 to 18 carbon atoms;
k1 to k3 each independently represent an integer of 0 to 4;
k4 is an integer of 0 to 3;
L represents a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, a pyridylene group, or a single bond;
The multiple A1 to A5 may be the same or different. An organic electroluminescent device comprising a fused ring compound represented by the following formula (1):
In formula (1),
A1 to A5 each independently represent a charge transporting group;
The charge transporting groups each independently represent
a trifluoromethyl group,
pentafluoroethyl group,
nitro group,
hydroxyl groups,
thiol groups,
a monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent;
a monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms which may have a substituent;
an optionally substituted phosphine oxide group,
a silyl group which may have a substituent;
a linear or branched alkyl group having 1 to 18 carbon atoms;
a linear or branched alkoxy group having 1 to 18 carbon atoms, or
a trifluoromethylsulfonyloxy group;
When the monocyclic, linked, or fused-ring aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent has a substituent, the substituents are each independently a group selected from the group consisting of a fluorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a phosphine oxide group, a silyl group, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, and a trifluoromethylsulfonyloxy group;
When the monocyclic, linked, or fused ring heteroaromatic group having 3 to 36 carbon atoms which may have a substituent has a substituent, the substituents are each independently a group selected from the group consisting of a cyano group, a fluorine atom, a trifluoromethyl group, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, and a trifluoromethylsulfonyloxy group;
When the optionally substituted phosphine oxide group has a substituent, the substituent is a group selected from the group consisting of monocyclic, linked, or fused ring aromatic hydrocarbon groups having 6 to 18 carbon atoms and monocyclic, linked, or fused ring heteroaromatic groups having 6 to 18 carbon atoms;
When the optionally substituted silyl group has a substituent, the substituent is a group selected from the group consisting of monocyclic, linked, or fused ring aromatic hydrocarbon groups having 6 to 18 carbon atoms and monocyclic, linked, or fused ring heteroaromatic groups having 6 to 18 carbon atoms;
k1 to k3 each independently represent an integer of 0 to 4;
k4 is an integer of 0 to 3;
L represents a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, a pyridylene group, or a single bond;
The multiple A1 to A5 may be the same or different.