Material for photoelectric conversion element for imaging element, and imaging element

Abstract

A purpose of the present disclosure is to provide a material for a photoelectric conversion element for an imaging element, the material having high thermal stability and achieving an imaging element having improved properties in terms of at least one selected from among responsiveness, external quantum efficiency, and dark current. An imaging element according to one embodiment of the present invention includes a layer comprising the material for a photoelectric conversion element for an imaging element, wherein the material for a photoelectric conversion element for an imaging element is represented by formula (1) or formula (1').　

Description

Photoelectric conversion element material for imaging device and imaging device

[0001] The present invention relates to a material for a photoelectric conversion element for an imaging device and an imaging device.

[0002] Photoelectric conversion elements are widely used in solar cells, optical sensors, image sensors, etc., and their applications and markets are expanding, leading to vigorous development.

[0003] For example, Patent Document 1 discloses a photoelectric conversion element containing a pyrimidine derivative in a hole-blocking layer.

[0004] For example, Patent Document 2 discloses a photoelectric conversion element containing a triazine derivative in a hole-blocking layer.

[0005] Japanese Patent Publication No. 2022-17302 Korean Patent Publication No. 10-2021-053141

[0006] In photoelectric conversion elements used in applications such as image sensors, improvements in external quantum efficiency are desired to increase sensitivity, reductions in dark current to reduce noise, and improvements in response to reduce image lag. In addition, some applications, such as in-vehicle applications, require extremely high heat resistance, and materials are required to have a high glass transition temperature (Tg).

[0007] An object of one aspect of the present invention is to provide a novel compound that can provide an imaging element with improved at least one of response, external quantum efficiency, and dark current, and that also has very high heat resistance.

[0008] In order to solve the above problems, there is provided an imaging element including a layer containing a material for a photoelectric conversion element for an imaging element, wherein the material for a photoelectric conversion element for an imaging element is represented by the following formula (1) or formula (1′): In the formula (1), CA is represented by the following formula (1a): Ar １ , and Ar ２each independently represents a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent heteroaromatic group, or a substituted or unsubstituted divalent cycloaliphatic hydrocarbon group; Ar ３ each independently represents a substituted or unsubstituted mono- to pentavalent aromatic hydrocarbon group, a substituted or unsubstituted mono- to pentavalent heteroaromatic group, or a substituted or unsubstituted mono- to pentavalent cycloaliphatic hydrocarbon group; L １ ~L ３ each independently represents a substituted or unsubstituted di- to tetra-valent aromatic hydrocarbon group, a substituted or unsubstituted di- to tetra-valent heteroaromatic group, or a substituted or unsubstituted di- to tetra-valent cycloaliphatic hydrocarbon group; R １ and R ２ are each independently hydrogen or Ar ３ represents; １ , a ２ , b １ , b ２ and c each independently represent an integer of 1 to 3; d and e each independently represent an integer of 1 or 2; and c+d+e represents an integer of 1 to 3; p, q and r each independently represent an integer of 0 to 3; n represents an integer of 1 to 3; Ar １ , Ar ２ , Ar ３ , L １ , L ２ and L ３ at least one of which is selected from the group consisting of a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, and a tetrazinyl group, or a fused ring group consisting of 2 to 4 aromatic monocyclic groups and partially containing at least one selected from the heteroaromatic monocyclic groups; with regard to the material for a photoelectric conversion element for an imaging element represented by the following formula (1'): In the formula (1′), Ar １１ ~Ar ３１ each independently represents a substituted or unsubstituted di- or trivalent aromatic hydrocarbon group, a substituted or unsubstituted di- or trivalent heteroaromatic group, or a substituted or unsubstituted di- or trivalent cycloaliphatic hydrocarbon group; L １１ ~L ３１each independently represents a substituted or unsubstituted di- to tetra-valent aromatic hydrocarbon group, a substituted or unsubstituted di- to tetra-valent heteroaromatic group, or a substituted or unsubstituted di- to tetra-valent cycloaliphatic hydrocarbon group; １１ , a ２１ , b １１ , b ２１ , c １１ , and c ２１ each independently represents an integer of 1 to 3; １ , q １ and r １ each independently represents an integer of 0 to 3; １１ , Ar ２１ , Ar ３１ , L １１ , L ２１ , and L ３１ At least one of Ar has a cyano group; １１ , Ar ２１ , Ar ３１ , L １１ , L ２１ , and L ３１ wherein the sum of the number of cyano groups contained in these groups and the number of nitrogen-containing heteroaromatic rings constituted by six-membered rings is 2 or more.

[0009] According to another aspect of the present invention, there is provided a compound represented by formula (11), formula (12), formula (13), formula (14), formula (3) or formula (4), wherein the compound represented by the following formula (11) is: In the formula (11), Ar １１１ and Ar ２１１ each independently represents a 3-pyridyl group or a 4-pyridyl group; Ar ３１１ represents a mono- or divalent phenanthryl group, a mono- or divalent dimethylfluorenyl group, a mono- or divalent diphenylfluorenyl group, a mono- or divalent spirobifluorenyl group, a mono- or divalent triptycenyl group, an aromatic group having 6 to 26 carbon atoms and at least one sulfone group, or a cycloaliphatic hydrocarbon group having 10 to 16 carbon atoms; L ３１１ represents a divalent phenyl group or a divalent pyridyl group, L ３１１ When there are a plurality of r, they may be the same or different;１１ represents an integer of 0 to 2; １１ represents an integer of 1 or 2; a compound having a triazine ring represented by the following formula (12): In the formula (12), L １１２ and L ２１２ represents a divalent pyridyl group; the divalent pyridyl group is bonded to the triazine ring at the 3-position or the 4-position; when the divalent pyridyl group is bonded to the triazine ring at the 4-position, Ar １１２ and Ar ２１２ each independently represents an aromatic hydrocarbon group having 10 to 26 carbon atoms, a nitrogen-containing heteroaromatic group having 6 to 26 carbon atoms and consisting only of a 6-membered ring, an aromatic group having 6 to 26 carbon atoms and having at least one sulfone group, or a cyclic aliphatic hydrocarbon group having 10 to 16 carbon atoms; when the divalent pyridyl group is bonded to the triazine ring at the 3-position, Ar １１２ and Ar ２１２ each independently represents a biphenylyl group, a terphenylyl group, a phenanthryl group, a dimethylfluorenyl group, a diphenylfluorenyl group, a spirobifluorenyl group, a triptycenyl group, an aromatic group having 6 to 26 carbon atoms and at least one sulfone group, or a cycloaliphatic hydrocarbon group having 10 to 16 carbon atoms; Ar ３１２ represents an aromatic hydrocarbon group having 6 to 26 carbon atoms, a nitrogen-containing heteroaromatic group having 6 to 26 carbon atoms and consisting only of a 6-membered ring, an oxygen- or sulfur-containing heteroaromatic group having 4 to 26 carbon atoms, an aromatic group having 6 to 26 carbon atoms and having at least one sulfone group, or a cycloaliphatic hydrocarbon group having 10 to 16 carbon atoms; L ３１２ represents a single bond, a divalent or trivalent phenyl group, or a divalent or trivalent pyridyl group; ４１２ represents a divalent phenyl group or a divalent pyridyl group, L ４１２ When there are a plurality of, they may be the same or different; １２ represents an integer of 1 or 2; a compound represented by the following formula (13): In the formula (13), Ar １１３ and Ar ２１３each independently represents a 3-pyridyl group or a 4-pyridyl group; Ar ３１３ represents an aromatic hydrocarbon group having 10 to 26 carbon atoms, a nitrogen-containing heteroaromatic group having 2 to 26 carbon atoms and consisting only of a 6-membered ring, an oxygen- or sulfur-containing heteroaromatic group having 4 to 26 carbon atoms, an aromatic group having 6 to 26 carbon atoms and having at least one sulfone group, or a cycloaliphatic hydrocarbon group having 10 to 16 carbon atoms; ３１３ represents a single bond, a divalent or trivalent phenyl group, or a divalent or trivalent pyridyl group; ４１３ represents a divalent phenyl group or a divalent pyridyl group, L ４１３ When there are a plurality of, they may be the same or different; １３ represents an integer of 1 or 2; a compound represented by the following formula (14): In the formula (14), Ar １１４ and Ar ２１４ each independently represents a 3-pyridyl group or a 4-pyridyl group; Ar ３１４ represents an aromatic hydrocarbon group having 10 to 24 carbon atoms, a nitrogen-containing heteroaromatic group having 6 to 26 carbon atoms and consisting only of a 6-membered ring, an oxygen- or sulfur-containing heteroaromatic group having 4 to 26 carbon atoms, an aromatic group having 6 to 26 carbon atoms and having at least one sulfone group, or a cycloaliphatic hydrocarbon group having 10 to 16 carbon atoms; ３１４ represents a single bond, a divalent or trivalent phenyl group, or a divalent or trivalent pyridyl group; ４１４ represents a divalent phenyl group or a divalent pyridyl group, L ４１４ When there are a plurality of, they may be the same or different; １４ represents an integer of 1 or 2; a compound represented by the following formula (3): In the formula (3), L ３１Ａ represents a phenylene group; １Ａ represents an integer of 0 or 1; ３１ is represented by any one of formulas (31a) to (34a); In the formulas (31a) to (34a), Ar ３１Ａare the same or different and represent a phenyl group substituted with one or more cyano groups, a pyridyl group, a pyridyl group substituted with one or more alkyl groups having 1 to 6 carbon atoms, a pyridyl group substituted with one or more cyano groups, or an optionally substituted naphthyl group; R ３２ , and R ３３ are each independently represented by any one of formulas (31b) to (35b); In the formulas (31b) to (35b), Ar ３２Ａ are the same or different and represent a phenyl group, a phenyl group substituted with one or more alkyl groups having 1 to 6 carbon atoms, a phenyl group substituted with one or more cyano groups, a pyridyl group, a pyridyl group substituted with one or more alkyl groups having 1 to 6 carbon atoms, a pyridyl group substituted with one or more cyano groups, or a biphenylyl group; L ３２Ａ represents a phenylene group or a single bond; * represents a bonding site; Ar in the formulae (31a) to (34a) ３１Ａ and Ar in the formulas (31b) to (35b). ３２Ａ At least one of R has a cyano group; ３１ is represented by the formula (31a), and / or R ３２ and R ３３ When at least one of the above is represented by the formula (31b), Ar in the formula (31a) ３１Ａ and Ar in the formula (31b). ３２Ａ are the same or different and are a phenyl group substituted with one or more cyano groups, or a pyridyl group substituted with one or more cyano groups, and the compound represented by the following formula (4) is: In the formula (4), Ar ４１ , and Ar ４２ each independently represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 26 carbon atoms, a substituted or unsubstituted nitrogen-containing heteroaromatic group having 3 to 26 carbon atoms and consisting only of a 6-membered ring, a substituted or unsubstituted oxygen-containing or sulfur-containing heteroaromatic group having 3 to 26 carbon atoms, or a cycloaliphatic hydrocarbon group having 10 to 16 carbon atoms; L ４１ ~L ４３each independently represents a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 26 carbon atoms, a substituted or unsubstituted divalent nitrogen-containing heteroaromatic group having 3 to 26 carbon atoms and consisting only of a 6-membered ring, a substituted or unsubstituted divalent oxygen-containing or sulfur-containing heteroaromatic group having 3 to 26 carbon atoms, or a divalent cycloaliphatic hydrocarbon group having 10 to 16 carbon atoms; ４ , q ４ and r ４ each independently represents an integer of 0 to 2; ４１ , Ar ４２ , L ４１ , L ４２ , and L ４３ at least one of which has a cyano group.

[0010] According to one aspect of the present invention, a photoelectric conversion element material for an imaging element can be obtained that has improved at least one of the characteristics of responsiveness, external quantum efficiency, and dark current, and a novel compound with extremely high heat resistance can be realized.

[0011] 1 is a cross-sectional view showing an outline of a layer structure of a photoelectric conversion element for an imaging element including a photoelectric conversion element material for an imaging element according to one aspect of the present invention.

[0012] Hereinafter, a material for a photoelectric conversion element for an imaging element contained in a layer of an imaging element according to one embodiment of the present invention will be described in detail.

[0013] A "photoelectric conversion element" having a layer containing a photoelectric conversion element material, such as a photoelectric conversion element material for an imaging element, refers to a light-receiving element that utilizes the photoelectric effect or the photovoltaic effect. Examples of light-receiving elements include photodiodes, phototransistors, image sensors (imaging elements), solar cells, etc., and preferably image sensors. A light-receiving element is typically an element that converts irradiated light into electric current. In such cases, the light-receiving element operates on a different operating principle from that of a light-emitting element that converts applied electric current into light. Therefore, a "photoelectric conversion element material" used in a "photoelectric conversion element" refers to a "photoelectric conversion element material" used in a "light-receiving element," and a "photoelectric conversion element material" used in an image sensor is referred to as a "photoelectric conversion element material for an imaging element."

[0014] The definitions of each group in each formula explained below and preferred specific examples thereof are as follows. In this specification, functional groups such as aromatic hydrocarbon groups, heteroaromatic groups, and cyclic aliphatic hydrocarbon groups are described without distinction based on their valence. For example, a "phenyl group" described in the context of a monovalent to trivalent aromatic hydrocarbon group encompasses a monovalent benzene ring (i.e., a phenyl group in the narrow sense) as well as a divalent benzene ring (i.e., a phenylene group) and a trivalent benzene ring (i.e., a benzenetriyl group). Furthermore, a "pyridyl group" encompasses a "pyridylene group" and a "pyridinetriyl group."

[0015] Furthermore, the triazine ring specifically shown in each formula is described as a "triazine ring" to be distinguished from the alternatively described "triazine" and "triazinyl group."

[0016] <Photoelectric conversion element material for imaging element> An imaging element according to one aspect of the present invention includes a layer containing a photoelectric conversion element material for imaging elements. The photoelectric conversion element material for imaging elements is represented by formula (1) or formula (1') described below. Hereinafter, the photoelectric conversion element material for imaging elements represented by formula (1) will be referred to as "photoelectric conversion element material for imaging elements (1)," and the photoelectric conversion element material for imaging elements represented by formula (1') will be referred to as "photoelectric conversion element material for imaging elements (1')."

[0017] <Photoelectric conversion element material (1) for image sensor> An image sensor according to one aspect of the present invention is an image sensor including a layer containing a photoelectric conversion element material for image sensor, which is one aspect of the material for photoelectric conversion elements, and the material for photoelectric conversion elements for image sensor is represented by the following formula (1).

[0018] Here, in the formula (1), CA is represented by the following formula (1a).

[0019] The material for a photoelectric conversion element for an imaging device represented by formula (1) is an electron transport material that is excellent in the transport property of charge, i.e., electrons, and is a hole blocking material that is excellent in the blocking property of the opposite charge, i.e., holes, and can be suitably used as a material for a photoelectric conversion element for an imaging device.

[0020] <Ar １ , Ar ２ , Ar ３ > In formula (1), Ar １ , and Ar ２ each independently represents a divalent aromatic hydrocarbon group, a divalent heteroaromatic group, or a divalent cycloaliphatic hydrocarbon group. ３ each independently represents a substituted or unsubstituted mono- to pentavalent aromatic hydrocarbon group, a substituted or unsubstituted mono- to pentavalent heteroaromatic group, or a substituted or unsubstituted mono- to pentavalent cyclic aliphatic hydrocarbon group. １ and R ２ is hydrogen or Ar ３ Represents.

[0021] Ar １ ~Ar ３ The number of carbon atoms in each of Ar is preferably 5 to 50, more preferably 5 to 30, and even more preferably 6 to 26. １ ~Ar ３ When the number of carbon atoms in Ar is larger than the above range, the thermal stability of the layer included in the imaging element can be improved. １ ~Ar ３ When the number of carbon atoms is smaller within the above range, the solubility of the material for a photoelectric conversion element for an imaging element can be increased, and the ease of production of the material for a photoelectric conversion element for an imaging element can be improved. Furthermore, the film-forming properties of the material for a photoelectric conversion element for an imaging element in the layer formation, i.e., the coating process of the material for a photoelectric conversion element for an imaging element can be improved.

[0022] Ar １ ~Ar ３ The aromatic hydrocarbon group represented by may be a single ring, or a linked or condensed ring containing multiple rings. Examples of the aromatic hydrocarbon group include, but are not limited to, a phenyl group, a naphthyl group, a phenanthryl group, an anthryl group, a fluorenyl group, a dimethylfluorenyl group, a diphenylfluorenyl group, a spirofluorenyl group, a pyrenyl group, a fluoranthenyl group, a triphenylenyl group, a tetracenyl group, and a chrysenyl group.

[0023] Ar１ ~Ar ３ The heteroaromatic group represented by is not particularly limited, but may be, for example, a functional group containing a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a silicon atom, and / or a germanium atom as a heteroatom on an aromatic ring, and may be a single ring, or a linked ring or condensed ring containing multiple rings. In the heteroaromatic group, the heteroatom contained on the aromatic ring may be one or two or more. When the heteroatom contained on the aromatic ring is two or more, the heteroatoms may be the same or different from each other.

[0024] Examples of the nitrogen-containing heteroaromatic group include heteroaromatic monocyclic groups such as pyridyl, pyrimidinyl, pyrazyl, triazinyl, tetrazinyl, and imidazolyl groups, quinolyl, isoquinolyl, quinoxalyl, azaanthryl, diazaanthryl, triazanthryl, tetraazanthryl, azaphenanthryl, diazaphenanthryl, triazaphenanthryl, tetraazaphenanthryl, azapyrenyl, diazapyrenyl, triazapyrenyl, tetraazapyrenyl, azafluoranthenyl, and diaza. Examples of the fused ring of a heteroaromatic monocycle include a fluoranthenyl group, a triazafluoranthenyl group, a tetraazafluoranthenyl group, an azatriphenylenyl group, a diazatriphenylenyl group, a triazatriphenylenyl group, a tetraazatriphenylenyl group, a pentaazatriphenylenyl group, a hexaazatriphenylenyl group, an oxazolyl group, a pyrrolyl group, an imidazolyl group, a triazolyl group, a thiadiazolyl group, an oxadiazolyl group, a benzothiazolyl group, a benzoxazolyl group, a benzothiadiazolyl group, and a benzoxadiazolyl group.

[0025] Examples of oxygen-containing heteroaromatic groups include heteroaromatic monocyclic rings such as a furyl group, and fused rings of heteroaromatic monocyclic rings such as a benzofuryl group, a dibenzofuryl group, a benzonaphthofuryl group, a xanthenyl group, a dibenzodioxinyl group, a fluorenonyl group, and a benzoxadiazolyl group.

[0026] Examples of sulfur-containing heteroaromatic groups include heteroaromatic monocyclic groups such as thienyl groups, and condensed rings of heteroaromatic monocyclic groups such as benzothienyl groups, dibenzothienyl groups, thioxanthenyl groups, and thianthrenyl groups.

[0027] Ar １ ~Ar ３ Examples of the cyclic aliphatic hydrocarbon group represented by include an adamantyl group, a diamantyl group, a norbornyl group, a cyclopentyl group, and a cyclohexyl group. From the viewpoint of increasing the thermal stability of the layer included in the photoelectric conversion element for an imaging device, an adamantyl group or a diamantyl group having 10 or more carbon atoms is preferred.

[0028] Ar １ ~Ar ３ In the above formula, the aromatic hydrocarbon group, heteroaromatic group, and cycloaliphatic hydrocarbon group may each independently have a substituent, or may not have a substituent. In other words, the aromatic hydrocarbon group, heteroaromatic group, and cycloaliphatic hydrocarbon group are substituted or unsubstituted. Examples of the substituent that these functional groups may have include a deuterium atom, a cyano group, a halogen atom, a halogenated alkyl group, an acyl group, a nitro group, a sulfonyl group, a phosphoryl group, an alkyl group, an alkenyl group, and a cycloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, -P(=O)(Ar') ２ a group represented by -S(=O) ２ A group represented by —Ar′, a group represented by —S(═O)Ar′, —B(Ar′) ２ a group represented by —B(OAr′) ２ a group represented by —Si(Ar′) ３ and aromatic hydrocarbon groups having 6 to 30 carbon atoms, and heteroaryl groups having 3 to 30 carbon atoms (Ar' represents an aryl group or a heteroaryl group).

[0029] Ar １ ~Ar ３ But -P(=O)(Ar') ２Examples of groups substituted with include a triphenylphosphine oxide group, a diphenylnaphthylphosphine oxide group, a diphenylphenanthrylphosphine oxide group, a diphenyl(dimethylfluorenyl)phosphine oxide group, a diphenyl(diphenylfluorenyl)phosphine oxide group, and a diphenylspirobifluorenylphosphine oxide group.

[0030] Also, Ar １ ~Ar ３ But -S(=O) ２ Examples of the group substituted by Ar' include a diphenylsulfone group and a dibenzothiophene-5,5-dioxide group, which may be one form of an aromatic group having 6 to 26 carbon atoms and at least one sulfone group.

[0031] a １ , a ２ , b １ , b ２ and c each independently represent an integer of 1 to 3, preferably an integer of 1 or 2. The material for a photoelectric conversion element for an imaging element represented by formula (1) is １ , a ２ , b １ , b ２ By optimizing each of c and c within such ranges, the glass transition temperature (T ｇ ) can be prevented from decreasing, the LUMO level of the material for a photoelectric conversion element for an imaging device can be deepened, and the response speed of the photoelectric conversion element for an imaging device can be increased.

[0032] In formula (1a) representing CA, d and e each independently represent an integer of 1 or 2, and c+d+e represents an integer of 1 to 3.

[0033] The compound represented by formula (1), which is a material for a photoelectric conversion element for an imaging element, is represented by Ar １ , Ar ２ and Ar ３ When there are a plurality of Ar １ Each of Ar ２ Each of Ar ３may be the same or different, and are preferably the same from the viewpoint of ease of production.

[0034] <L １ , L ２ , L ３ > In formula (1), L １ , L ２ , and L ３ each independently represents a divalent to tetravalent aromatic hydrocarbon group, a divalent to tetravalent heteroaromatic group, or a divalent to tetravalent cycloaliphatic hydrocarbon group.

[0035] L １ ~L ３ The aromatic hydrocarbon group represented by may be a single ring, or a linked or condensed ring containing multiple rings. Examples of the aromatic hydrocarbon group include, but are not limited to, a phenyl group, a naphthyl group, a phenanthryl group, an anthryl group, a fluorenyl group, a dimethylfluorenyl group, a spirofluorenyl group, a pyrenyl group, a fluoranthenyl group, a triphenylenyl group, a tetracenyl group, and a chrysenyl group.

[0036] L １ ~L ３ The heteroaromatic group represented by is not particularly limited, but is, for example, a functional group containing a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a silicon atom, and / or a germanium atom as a heteroatom on an aromatic ring, and may be a single ring, or a linked ring or condensed ring containing multiple rings. １ ~Ar ３ Preferred examples of the nitrogen-containing heteroaromatic groups include the above-mentioned nitrogen-containing heteroaromatic groups exemplified by a pyridyl group, a pyrimidinyl group, a pyrazinyl group, and a triazinyl group.

[0037] L １ ~L ３ Examples of the cyclic aliphatic hydrocarbon group represented by include Ar １ ~Ar ３ Similarly, examples of the alicyclic hydrocarbon groups include alicyclic hydrocarbon groups having 10 or more carbon atoms, such as the above-mentioned adamantyl group.

[0038] L １ ~L ３ In the above, the aromatic hydrocarbon group, heteroaromatic group, and alicyclic hydrocarbon group may or may not have a substituent. In other words, the aromatic hydrocarbon group, heteroaromatic group, and alicyclic hydrocarbon group may be substituted or unsubstituted. Specific examples of the substituent that these functional groups may have include Ar １ ~Ar ３ The specific examples of the substituents that may be possessed by the group are the same as those of the group.

[0039] p, q, and r each independently represent an integer of 0 to 3, and preferably an integer of 0 to 2. By optimizing p, q, and r within such ranges, the T of the material for a photoelectric conversion element for an imaging element represented by formula (1) can be improved. ｇ Therefore, the LUMO level of the material for a photoelectric conversion element for an imaging element can be deepened, and the response speed of the imaging element can be increased. １ represents a single bond, and therefore, in formula (1), Ar １ and the triazine ring are directly bonded by a single bond. Similarly, when q and r are each 0, L ２ and L ３ Each represents a single bond.

[0040] The compound represented by formula (1), which is a material for a photoelectric conversion element for an imaging element, is represented by formula (1), １ , L ２ and L ３ When there are multiple of each, L １ Each of L ２ Each of L ３ may be the same or different.

[0041] <Characteristics of Ar, L, and Triazine Ring> In formula (1), Ar １ , Ar ２ , Ar ３ , L １ , L ２ and L ３At least one of the heteroaromatic rings is selected from (1) a heteroaromatic monocycle selected from the group consisting of a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a tetrazine ring, or (2) a fused ring consisting of two to four aromatic monocycles, the fused ring partially including at least one heteroaromatic monocycle selected from the heteroaromatic monocycles. The heteroaromatic monocycles of the pyridine ring, the pyridazine ring, the pyrimidine ring, the pyrazine ring, and the tetrazine ring contain a nitrogen atom as a ring-forming atom in a completely conjugated aromatic ring, and no hydrogen atom is covalently bonded to the nitrogen atom. In this specification, unless otherwise specified, the term "aromatic monocycle" includes both the meanings of "heteroaromatic monocycle" and "aromatic hydrocarbon monocycle."

[0042] Ar １ , Ar ２ , Ar ３ , L １ , L ２ and L ３ When at least one of the heteroaromatic rings is such a heteroaromatic ring or is a polycyclic aromatic ring containing such a heteroaromatic ring therein, the LUMO level of the material for a photoelectric conversion element for an imaging element can be deepened, and the response speed of the imaging element can be increased.

[0043] That is, in formula (1), Ar １ , Ar ２ , Ar ３ , L １ , L ２ and L ３ At least one of the groups is preferably selected from heteroaromatic monocyclic rings exemplified by the pyridyl group, pyrimidinyl group, and pyrazyl group described above, and aromatic fused rings partially containing a heteroaromatic monocyclic ring.

[0044] The material for a photoelectric conversion element for an image sensor represented by formula (1) and the compounds represented by the formulas described below each contain Ar bonded directly or indirectly to a triazine ring. １ , Ar ２ , Ar ３ , L １ , L ２ and L ３where at least one of the groups is a heteroaromatic monocycle selected from the group consisting of a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, and a tetrazinyl group, the LUMO level can be deepened as described above, and the response speed of the image sensor can be increased. Furthermore, the material can be used as a photoelectric conversion material for an image sensor that can achieve, for example, a lower dark current and a higher external quantum efficiency.

[0045] Among them, Ar １ ~Ar ３ , and L １ ~L ３ At least one of the heteroaromatic rings is preferably a pyridyl group or a pyrimidinyl group, and more preferably a pyridyl group. With this configuration, the LUMO of the material for a photoelectric conversion element for an image sensor can be deepened, and the response speed of the image sensor can be increased.

[0046] The functional group selected from (1) the heteroaromatic monocycles described above or (2) a fused ring of an aromatic monocycle containing at least one of the heteroaromatic monocycles as a part thereof is Ar １ ~Ar ３ , and L １ ~L ３ It is preferable that at least two of the following are present. １ , Ar ２ , Ar ３ , L １ , L ２ , and L ３ Preferably, at least two of the groups are pyridyl groups or pyrimidinyl groups. With this configuration, the LUMO of the material for a photoelectric conversion element for an image sensor can be made deeper, and the response speed of the image sensor can be increased.

[0047] <n> In formula (1), n ​​represents an integer of 1 to 3, and preferably represents an integer of 1 or 2. By optimizing n within this range, the T ｇTherefore, the LUMO level of the material for a photoelectric conversion element for an imaging element can be deepened, and the response speed of the imaging element can be increased.

[0048] <Compound (11)> In one embodiment of the present invention, the material (1) for a photoelectric conversion element for an imaging element may be a compound represented by the following formula (11): The compound represented by formula (11) also falls within the scope of the present invention.

[0049]

[0050] <Ar １１１ , Ar ２１１ , Ar ３１１ > In formula (11), Ar １１１ and Ar ２１１ each independently represents a 3-pyridyl group or a 4-pyridyl group, and preferably represents a 4-pyridyl group from the viewpoint of deepening the LUMO level. １１１ and Ar ２１１ may be the same as or different from each other.

[0051] In formula (11), Ar ３１１ represents a mono- or divalent phenanthryl group, a mono- or divalent dimethylfluorenyl group, a mono- or divalent diphenylfluorenyl group, a mono- or divalent spirobifluorenyl group, a mono- or divalent triptycenyl group, an aromatic group having 6 to 26 carbon atoms and at least one sulfone group, or a cycloaliphatic hydrocarbon group having 10 to 16 carbon atoms. ３１１is preferably a 2-phenanthryl group, a 3-phenanthryl group, a 9-phenanthryl group, a 9,9-dimethylfluoren-1-yl group, a 9,9-dimethylfluoren-2-yl group, a 9,9-dimethylfluoren-3-yl group, a 9,9-dimethylfluoren-4-yl group, a 9,9-diphenylfluoren-1-yl group, a 9,9-diphenylfluoren-2-yl group, a 9,9-diphenylfluoren-3-yl group, a 9,9-diphenylfluoren-4-yl group, a 1-spirobifluorenyl group, -spirobifluorenyl group, 3-spirobifluorenyl group, 4-spirobifluorenyl group, 1-triptycenyl group, 2-triptycenyl group, 2-phenylphenylsulfone group, 3-phenylphenylsulfone group, 4-phenylphenylsulfone group, dibenzothiophene-5,5-dioxid-1-yl group, dibenzothiophene-5,5-dioxid-2-yl group, dibenzothiophene-5,5-dioxid-3-yl group, dibenzothiophene-5,5-dioxid-4-yl group, 1-adamantyl group a 9-phenanthryl group, a 9,9-dimethylfluorene-2,7-diyl group, a 9,9-diphenylfluorene-2,7-diyl group, a spirobifluorene-2,7-diyl group, or a triptycene-2,6-diyl group; and more preferably a 9-phenanthryl group, a 9,9-dimethylfluorene-2-yl group, a 9,9-dimethylfluorene-4-yl group, a 9,9-diphenylfluorene-2-yl group, or a 9,9-diphenylfluorene-4-yl group. 2-spirobifluorenyl group, 4-spirobifluorenyl group, 2-triptycenyl group, 4-phenylphenylsulfone group, dibenzothiophene-5,5-dioxid-2-yl group, dibenzothiophene-5,5-dioxid-3-yl group, 1-adamantyl group, phenanthrene-9,10-diyl group, 9,9-dimethylfluorene-2,7-diyl group, 9,9-diphenylfluorene-2,7-diyl group, spirobifluorene-2,7-diyl group, triptycen-2,6-diyl group.

[0052] <L ３１１ , r １１ > In formula (11), L ３１１ represents a divalent phenyl group or a divalent pyridyl group, L ３１１When there are multiple, they may be the same or different.

[0053] r １１ represents an integer of 0 to 2. １１ If is 0, L ３１１ represents a single bond, and therefore, in formula (11), Ar ３１１ and the triazine ring are directly bonded by a single bond.

[0054] <n １１ > In formula (11), n １１ represents an integer of 1 or 2.

[0055] Preferred specific examples of the compound represented by formula (11) are shown in the table below, but are not limited thereto. The table below shows compounds having the skeletons (CA1) to (CA33) shown below, and groups (GA1) to (GA29) shown below are bonded to the multiple *'s in the skeleton at the # positions of the groups (CAx １ -GAy １ ) is shown. However, the same group among the groups shown in (GA1) to (GA29) is bonded to the multiple * in the skeletons of (CA1) to (CA33). Here, x １ represents an integer from 1 to 33, and y １ represents any integer from 1 to 29. That is, (CAx １ -GAy １ ) refers to compounds (CA1-GA1) to (CA33-GA29). However, among these compounds, compounds having any of the skeletons (CA1) to (CA17) and the group (GA3) and compounds having any of the skeletons (CA25) to (CA33) and the group (GA3) are not included. Therefore, for example, x １ = 31, y １ In the case of a compound (CA31-GA1) where =1, it has a skeleton of (CA31), and the group (GA1) is bonded to the two *'s on the skeleton at the #'s on the group, which represents the compound (CA31-GA1) below.

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070] <Compound (12)> In one embodiment of the present invention, the material (1) for a photoelectric conversion element for an imaging element may be a compound represented by the following formula (12): The compound represented by formula (12) also falls within the scope of the present invention.

[0071]

[0072] <L １１２ , L ２１２ , Ar １１２ , Ar ２１２ > In formula (12), L １１２ and L ２１２ represents a divalent pyridyl group, and the divalent pyridyl group is bonded to the triazine ring at the 3- or 4-position. １２ represents an integer of 1 or 2, preferably 1.

[0073] The compound represented by the above formula (12) is L １１２ and L ２１２When the divalent pyridyl group in the formula (12A) is bonded to the triazine ring at the 4-position, the compound is represented by the following formula (12A).

[0074]

[0075] In formula (12A), Ar １１２Ａ and Ar ２１２Ａ each independently represents an aromatic hydrocarbon group having 10 to 26 carbon atoms, a nitrogen-containing heteroaromatic group having 6 to 26 carbon atoms and consisting only of a 6-membered ring, an aromatic group having 6 to 26 carbon atoms and at least one sulfone group, or a cyclic aliphatic hydrocarbon group having 10 to 16 carbon atoms.

[0076] In formula (12A), Ar １１２Ａ and Ar ２１２Ａ is an aromatic hydrocarbon group having 10 to 26 carbon atoms, Ar １１２Ａ and Ar ２１２Ａ are preferably each independently a naphthyl group, a biphenylyl group, a terphenylyl group, a phenanthryl group, a dimethylfluorenyl group, a diphenylfluorenyl group, a spirobifluorenyl group, or a triptycenyl group.

[0077] In formula (12A), Ar １１２Ａ and Ar ２１２Ａ is a nitrogen-containing heteroaromatic group having 6 to 26 carbon atoms and consisting of only a 6-membered ring, １１２Ａ and Ar ２１２Ａ are preferably each independently a quinolyl group, an isoquinolyl group, a quinoxalyl group, an azaanthryl group, a diazaanthryl group, a triazaanthryl group, a tetraazaanthryl group, an azaphenanthryl group, a diazaphenanthryl group, a triazaphenanthryl group, a tetraazaphenanthryl group, an azapyrenyl group, a diazapyrenyl group, a triazapyrenyl group, a tetraazapyrenyl group, an azatriphenylenyl group, a diazatriphenylenyl group, a triazatriphenylenyl group, a tetraazatriphenylenyl group, a pentaazatriphenylenyl group, or a hexaazatriphenylenyl group.

[0078] In formula (12A), Ar １１２Ａ and Ar ２１２Ａis an aromatic group having 6 to 26 carbon atoms and at least one sulfonic acid group, １１２Ａ and Ar ２１２Ａ Examples of the aromatic groups include aromatic groups having a sulfone group, such as a diphenyl sulfone group and a dibenzothiophene-5,5-dioxide group.

[0079] In addition, in formula (12A), Ar １１２Ａ and Ar ２１２Ａ represents a cyclic aliphatic hydrocarbon group having 10 to 16 carbon atoms, １１２Ａ and Ar ２１２Ａ Examples of the alicyclic hydrocarbon groups include the above-mentioned adamantyl group.

[0080] The compound represented by the above formula (12) is L １１２ and L ２１２ When the divalent pyridyl ring is bonded to the triazine ring at the 3-position, the compound is represented by the following formula (12B).

[0081]

[0082] In formula (12B), Ar １１２Ｂ and Ar ２１２Ｂ each independently represents a biphenyl group, a terphenyl group, a phenanthryl group, a dimethylfluorenyl group, a diphenylfluorenyl group, a spirobifluorenyl group, a triptycenyl group, an aromatic group having 6 to 26 carbon atoms and at least one sulfone group, or a cycloaliphatic hydrocarbon group having 10 to 16 carbon atoms.

[0083] In formula (12B), Ar １１２Ｂ and Ar ２１２Ｂ represents an aromatic group having 6 to 26 carbon atoms or a cycloaliphatic hydrocarbon group having 10 to 16 carbon atoms having at least one sulfonic acid group, Ar １１２Ｂ and Ar ２１２Ｂ In Ar １１２Ａ and Ar ２１２Ａ Since an aromatic group having 6 to 26 carbon atoms and a sulfone group similar to those in the above or a cyclic aliphatic hydrocarbon group having 10 to 16 carbon atoms can be selected, the description thereof will be omitted.

[0084] <Ar ３１２ > In formula (12), Ar３１２ represents an aromatic hydrocarbon group having 6 to 26 carbon atoms, a nitrogen-containing heteroaromatic group having 6 to 26 carbon atoms consisting only of a 6-membered ring, an oxygen- or sulfur-containing heteroaromatic group having 4 to 26 carbon atoms, an aromatic group having 6 to 26 carbon atoms and at least one sulfone group, or a cycloaliphatic hydrocarbon group having 10 to 16 carbon atoms, and the nitrogen-containing heteroaromatic group having 6 to 26 carbon atoms consisting only of a 6-membered ring, an aromatic group having 6 to 26 carbon atoms and at least one sulfone group, or a cycloaliphatic hydrocarbon group having 10 to 16 carbon atoms can be represented by Ar １１２Ａ and Ar ２１２Ａ Since the same as the above is selected, the explanation thereof will be omitted.

[0085] In formula (12), Ar ３１２ is an aromatic hydrocarbon group having 6 to 26 carbon atoms, it is preferably, for example, a phenyl group, a naphthyl group, a biphenylyl group, a terphenylyl group, a phenanthryl group, a dimethylfluorenyl group, a diphenylfluorenyl group, a spirobifluorenyl group, or a triptycenyl group.

[0086] In formula (12), Ar ３１２ is an oxygen-containing heteroaromatic group having 4 to 26 carbon atoms, examples of which include a heteroaromatic monocycle such as a furyl group, and a fused ring of a heteroaromatic monocycle such as a benzofuryl group, a dibenzofuryl group, a benzonaphthofuryl group, a xanthenyl group, a dibenzodioxinyl group, and a benzoxadiazolyl group.

[0087] In formula (12), Ar ３１２ is a sulfur-containing heteroaromatic group having 4 to 26 carbon atoms, examples of which include a heteroaromatic monocycle such as a thienyl group, and a fused ring of a heteroaromatic monocycle such as a benzothienyl group, a dibenzothienyl group, a thioxanthenyl group, and a thianthrenyl group.

[0088] <L ３１２ , L ４１２ , c １２ > In formula (12), L ３１２ represents a single bond, a divalent or trivalent phenyl group, or a divalent or trivalent pyridyl group. １２ represents an integer of 1 or 2.

[0089] L４１２ represents a divalent phenyl group or a divalent pyridyl group, L ４１２ When there are multiple, they may be the same or different.

[0090] Preferred specific examples of the compound represented by formula (12) are shown in the table below, but are not limited thereto. The table below shows compounds (CBx) having the skeletons (CB1) to (CB38) shown below, and having * in the skeleton and having groups (GB1) to (GB50) shown below bonded at the positions marked with # in the groups. ２ -GBy ２ ) where x ２ is an integer between 1 and 38, y ２ represents any integer from 1 to 50. That is, (CBx ２ -GBy ２ ) refers to the compounds (CB1-GB1) to (CB38-GB50). However, among these compounds, compounds having the skeleton of (CB3) and any of the groups (GB1) to (GB7), (GB9) to (GB15), (GB23) to (GB26), (GB28) to (GB38), and (GB47) to (GB50), that is, (CB3-GB1) to (CB3-GB7), (CB3-GB9) to (CB3-GB15), (CB3-GB23) to (CB3-GB26), (CB3-GB28) to (CB3-GB38), and (CB3-GB47) to (CB3-GB50), are not included. Therefore, for example, x ２ = 4, y ２ In the case of a compound (CB4-GB2) where =2, the compound has a skeleton of (CB4), and the group of (GB2) is bonded to the * of the skeleton at the # position of the group, which represents the following compound (CB4-GB2).

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106] <Compound (13)> In one embodiment of the present invention, the material (1) for a photoelectric conversion element for an imaging element may be a compound represented by the following formula (13): The compound represented by formula (13) also falls within the scope of the present invention.

[0107]

[0108] In formula (13), Ar １１３ and Ar ２１３ each independently represents a 3-pyridyl group or a 4-pyridyl group, preferably a 4-pyridyl group.

[0109] In formula (13), Ar ３１３ represents an aromatic hydrocarbon group having 10 to 26 carbon atoms, a nitrogen-containing heteroaromatic group having 2 to 26 carbon atoms and consisting only of a 6-membered ring, an oxygen- or sulfur-containing heteroaromatic group having 4 to 26 carbon atoms, an aromatic group having 6 to 26 carbon atoms and having at least one sulfone group, or a cyclic aliphatic hydrocarbon group having 10 to 16 carbon atoms.

[0110] In formula (13), Ar ３１３is an aromatic hydrocarbon group having 10 to 26 carbon atoms, Ar ３１３ are preferably each independently a naphthyl group, a biphenylyl group, a terphenylyl group, a phenanthryl group, a dimethylfluorenyl group, a diphenylfluorenyl group, a spirobifluorenyl group, or a triptycenyl group.

[0111] In formula (13), Ar ３１３ is a nitrogen-containing heteroaromatic group having 2 to 26 carbon atoms and consisting of only 6-membered rings, Ar ３１３ are each independently preferably a pyridyl group, a pyrazyl group, a triazinyl group, a tetrazinyl group, a quinolyl group, an isoquinolyl group, a quinoxalyl group, an azaanthryl group, a diazaanthryl group, a triazaanthryl group, a tetraazaanthryl group, an azaphenanthryl group, a diazaphenanthryl group, a triazaphenanthryl group, a tetraazaphenanthryl group, an azapyrenyl group, a diazapyrenyl group, a triazapyrenyl group, azatriphenylenyl group, a diazatriphenylenyl group, a triazatriphenylenyl group, a tetraazatriphenylenyl group, a pentaazatriphenylenyl group, or a hexaazatriphenylenyl group.

[0112] In formula (13), Ar ３１３ is an oxygen-containing heteroaromatic group having 4 to 26 carbon atoms, Ar ３１３ each independently represents a heteroaromatic monocyclic ring such as a furyl group, or a fused ring of a heteroaromatic monocyclic ring such as a benzofuryl group, a dibenzofuryl group, a benzonaphthofuryl group, a xanthenyl group, a dibenzodioxinyl group, or a benzoxadiazolyl group.

[0113] In formula (13), Ar ３１３ is a sulfur-containing heteroaromatic group having 4 to 26 carbon atoms, Ar ３１３ are each independently a heteroaromatic monocyclic ring such as a thienyl group, or a condensed ring of a heteroaromatic monocyclic ring such as a benzothienyl group, a dibenzothienyl group, a thioxanthenyl group, or a thianthrenyl group.

[0114] In formula (13), Ar ３１３ is an aromatic group having 6 to 26 carbon atoms and at least one sulfonic acid group, ３１３Examples of the aromatic groups include aromatic groups having a sulfone group, such as a diphenyl sulfone group and a dibenzothiophene-5,5-dioxide group.

[0115] In addition, in formula (13), Ar ３１３ represents a cyclic aliphatic hydrocarbon group having 10 to 16 carbon atoms, ３１３ Examples of the alicyclic hydrocarbon groups include the above-mentioned adamantyl group.

[0116] In formula (13), L ３１３ represents a single bond, a divalent or trivalent phenyl group, or a divalent or trivalent pyridyl group. ４１３ represents a divalent phenyl group or a divalent pyridyl group, L ４１３ When there are a plurality of groups, they may be the same or different. １３ represents an integer of 1 or 2.

[0117] Preferred specific examples of the compound represented by formula (13) are shown in the table below, but are not limited thereto. The table below shows compounds having the skeleton (CC1) or (CC2) shown below, and the above-mentioned groups (GB1) to (GB50) are bonded to the * in the skeleton at the # position in the group, (CCx ３ -GBy ２ ) where x ３ is an arbitrary integer of 1 or 2, y ２ represents any integer from 1 to 50. That is, (CCx ３ -GBy ２ ) refers to compounds (CC1-GB1) to (CC2-GB50). ３ = 1, y ２ In the case of a compound (CC1-GB39) where =39, the compound has a skeleton of (CC1), and the group of (GB39) is bonded to the * of the skeleton at the # position of the group, which represents the following compound (CC1-GB39).

[0118]

[0119]

[0120]

[0121] <Compound (14)> In one embodiment of the present invention, the material (1) for a photoelectric conversion element for an imaging element may be a compound represented by the following formula (14): The compound represented by formula (14) also falls within the scope of the present invention.

[0122]

[0123] In formula (14), Ar １１４ and Ar ２１４ each independently represents a 3-pyridyl group or a 4-pyridyl group, preferably a 4-pyridyl group.

[0124] In formula (14), Ar ３１４ represents an aromatic hydrocarbon group having 10 to 24 carbon atoms, a nitrogen-containing heteroaromatic group having 6 to 26 carbon atoms and consisting only of a 6-membered ring, an oxygen- or sulfur-containing heteroaromatic group having 4 to 26 carbon atoms, an aromatic group having 6 to 26 carbon atoms and having at least one sulfone group, or a cyclic aliphatic hydrocarbon group having 10 to 16 carbon atoms.

[0125] In formula (14), Ar ３１４ is an aromatic hydrocarbon group having 10 to 24 carbon atoms, Ar ３１４ are each preferably independently a naphthyl group, a biphenylyl group, a terphenylyl group, a phenanthryl group, a dimethylfluorenyl group, or a triptycenyl group.

[0126] In formula (14), Ar ３１４ is a nitrogen-containing heteroaromatic group having 6 to 26 carbon atoms and consisting of only a 6-membered ring, ３１４ are each independently preferably a quinolyl group, an isoquinolyl group, a quinoxalyl group, an azaanthryl group, a diazaanthryl group, a triazaanthryl group, a tetraazaanthryl group, an azaphenanthryl group, a diazaphenanthryl group, a triazaphenanthryl group, a tetraazaphenanthryl group, an azapyrenyl group, a diazapyrenyl group, a triazapyrenyl group, a tetraazapyrenyl group, an azatriphenylenyl group, a diazatriphenylenyl group, a triazatriphenylenyl group, a tetraazatriphenylenyl group, a pentaazatriphenylenyl group, or a hexaazatriphenylenyl group.

[0127] In formula (14), Ar ３１４ is an oxygen-containing heteroaromatic group having 4 to 26 carbon atoms, Ar ３１４ each independently represents a heteroaromatic monocyclic ring such as a furyl group, or a fused ring of a heteroaromatic monocyclic ring such as a benzofuryl group, a dibenzofuryl group, a benzonaphthofuryl group, a xanthenyl group, a dibenzodioxinyl group, or a benzoxadiazolyl group.

[0128] In formula (14), Ar ３１４ is a sulfur-containing heteroaromatic group having 4 to 26 carbon atoms, Ar ３１４ are each independently a heteroaromatic monocyclic ring such as a thienyl group, or a condensed ring of a heteroaromatic monocyclic ring such as a benzothienyl group, a dibenzothienyl group, a thioxanthenyl group, or a thianthrenyl group.

[0129] In formula (14), Ar ３１４ is an aromatic group having 6 to 26 carbon atoms and at least one sulfonic acid group, ３１４ Examples of the aromatic groups include aromatic groups having a sulfone group, such as a diphenyl sulfone group and a dibenzothiophene-5,5-dioxide group.

[0130] In addition, in formula (14), Ar ３１４ represents a cyclic aliphatic hydrocarbon group having 10 to 16 carbon atoms, ３１４ Examples of the alicyclic hydrocarbon groups include the above-mentioned adamantyl group.

[0131] L ３１４ represents a single bond, a divalent or trivalent phenyl group, or a divalent or trivalent pyridyl group. ４１４ represents a divalent phenyl group or a divalent pyridyl group, L ４１４ When there are a plurality of groups, they may be the same or different. １４ represents an integer of 1 or 2.

[0132] Preferred specific examples of the compound represented by formula (14) are shown in the table below, but are not limited thereto. The table below shows compounds (CDx) which have the skeleton (CD1) or (CD2) shown below, and in which the above-mentioned groups (GB1) to (GB50) are bonded to the * in the skeleton at the # position in the group. ３ -GBy ２ ) where x ３ is an arbitrary integer of 1 or 2, y ２ represents any integer from 1 to 50. That is, (CDx ３ -GBy ２ ) refers to compounds (CD1-GB1) to (CD2-GB50). ３ = 1, y ２ In the case of a compound (CD1-GB28) where =28, the compound has a skeleton of (CD1), and the group of (GB28) is bonded to the * of the skeleton at the # position of the group, which represents the compound (CD1-GB28) below.

[0133]

[0134]

[0135]

[0136] <Other Materials for Photoelectric Conversion Elements of Image Sensors> In one embodiment of the present invention, the material (1) for photoelectric conversion elements of image sensors is not limited to the compounds represented by the above-mentioned formulas (11), (12), (13), or (14). Other preferred specific examples of the material (1) for photoelectric conversion elements of image sensors are shown below, but the material is not limited thereto.

[0137]

[0138] <Photoelectric conversion element material (1′) for imaging element> An imaging element according to one aspect of the present invention is an imaging element including a layer containing a photoelectric conversion element material for imaging element, and the photoelectric conversion element material for imaging element is represented by the following formula (1′):

[0139] In the formula (1′), Ar １１ ~Ar ３１ each independently represents a substituted or unsubstituted di- or trivalent aromatic hydrocarbon group, a substituted or unsubstituted di- or trivalent heteroaromatic group, or a substituted or unsubstituted di- or trivalent cycloaliphatic hydrocarbon group; L １１ ~L ３１ each independently represents a substituted or unsubstituted di- to tetra-valent aromatic hydrocarbon group, a substituted or unsubstituted di- to tetra-valent heteroaromatic group, or a substituted or unsubstituted di- to tetra-valent cycloaliphatic hydrocarbon group; １１ , a ２１ , b １１ , b ２１ , c １１ , and c ２１ each independently represents an integer of 1 to 3; １ , q １ and r １ each independently represents an integer of 0 to 3; １１ , Ar ２１ , Ar ３１ , L １１ , L ２１ , and L ３１ At least one of Ar has a cyano group; １１ , Ar ２１ , Ar ３１ , L １１ , L ２１ , and L ３１In the formula (I), the sum of the number of cyano groups contained in these groups and the number of nitrogen-containing heteroaromatic rings constituted by six-membered rings is 2 or more.

[0140] Ar １１ ~Ar ３１ The number of carbon atoms in each of Ar is preferably 5 to 50, more preferably 5 to 30, and even more preferably 6 to 26. １１ ~Ar ３１ When the number of carbon atoms in Ar is larger than the above range, the thermal stability of the layer included in the imaging element can be improved. １１ ~Ar ３１ When the number of carbon atoms is smaller within the above range, the solubility of the material for a photoelectric conversion element for an imaging element can be increased, and the ease of production of the material for a photoelectric conversion element for an imaging element can be improved. Furthermore, the film-forming properties of the material for a photoelectric conversion element for an imaging element in the layer formation, i.e., the coating process of the material for a photoelectric conversion element for an imaging element can be improved.

[0141] Ar １１ ~Ar ３１ The aromatic hydrocarbon group represented by may be a single ring, or a linked ring or condensed ring containing multiple rings. Examples of the aromatic hydrocarbon group include, but are not limited to, a phenyl group, a naphthyl group, a phenanthryl group, an anthryl group, a fluorenyl group, a dimethylfluorenyl group, a diphenylfluorenyl group, a spirofluorenyl group, a pyrenyl group, a fluoranthenyl group, a triphenylenyl group, a tetracenyl group, a triptycenyl group, and a chrysenyl group.

[0142] Ar １１ ~Ar ３１ The heteroaromatic group represented by is not particularly limited, but may be, for example, a functional group containing a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a silicon atom, and / or a germanium atom as a heteroatom in an aromatic ring, and may be a single ring, or a linked ring or condensed ring containing multiple rings. In the heteroaromatic group, the heteroatom contained in the aromatic ring may be one or two or more. When the aromatic ring contains two or more heteroatoms, the heteroatoms may be the same or different from each other.

[0143] Examples of the nitrogen-containing heteroaromatic group include heteroaromatic monocyclic groups such as pyridyl, pyrimidinyl, pyrazyl, triazinyl, tetrazinyl, and imidazolyl groups, quinolyl, isoquinolyl, quinoxalyl, azaanthryl, diazaanthryl, triazanthryl, tetraazanthryl, azaphenanthryl, diazaphenanthryl, triazaphenanthryl, tetraazaphenanthryl, azapyrenyl, diazapyrenyl, triazapyrenyl, tetraazapyrenyl, azafluoranthenyl, and diaza. Examples of the fused ring of a heteroaromatic monocycle include a fluoranthenyl group, a triazafluoranthenyl group, a tetraazafluoranthenyl group, an azatriphenylenyl group, a diazatriphenylenyl group, a triazatriphenylenyl group, a tetraazatriphenylenyl group, a pentaazatriphenylenyl group, a hexaazatriphenylenyl group, an oxazolyl group, a pyrrolyl group, an imidazolyl group, a triazolyl group, a thiadiazolyl group, an oxadiazolyl group, a benzothiazolyl group, a benzoxazolyl group, a benzothiadiazolyl group, and a benzoxadiazolyl group.

[0144] Examples of oxygen-containing heteroaromatic groups include heteroaromatic monocyclic groups such as a furyl group, and fused rings of heteroaromatic monocyclic groups such as a benzofuryl group, a dibenzofuryl group, a benzonaphthofuryl group, a xanthenyl group, a dibenzodioxinyl group, a fluorenonyl group, and a benzoxadiazolyl group.

[0145] Examples of sulfur-containing heteroaromatic groups include heteroaromatic monocyclic groups such as thienyl groups, and condensed rings of heteroaromatic monocyclic groups such as benzothienyl groups, dibenzothienyl groups, thioxanthenyl groups, and thianthrenyl groups.

[0146] Ar １１ ~Ar ３１ Examples of the cyclic aliphatic hydrocarbon group represented by include an adamantyl group, a diamantyl group, a norbornyl group, a cyclopentyl group, and a cyclohexyl group. From the viewpoint of increasing the thermal stability of the layer included in the photoelectric conversion element, an adamantyl group or a diamantyl group having 10 or more carbon atoms is preferred.

[0147] Ar １１ ~Ar ３１ In the above formula, the aromatic hydrocarbon group, heteroaromatic group, and cycloaliphatic hydrocarbon group may each independently have a substituent, or may not have a substituent. In other words, the aromatic hydrocarbon group, heteroaromatic group, and cycloaliphatic hydrocarbon group are substituted or unsubstituted. Examples of the substituent that these functional groups may have include a deuterium atom, a cyano group, a halogen atom, a halogenated alkyl group, an acyl group, a nitro group, a sulfonyl group, a phosphoryl group, an alkyl group, an alkenyl group, and a cycloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, -P(=O)(Ar') ２ a group represented by -S(=O) ２ A group represented by —Ar′, a group represented by —S(═O)Ar′, —B(Ar′) ２ a group represented by —B(OAr′) ２ a group represented by —Si(Ar′) ３ and aromatic hydrocarbon groups having 6 to 30 carbon atoms, and heteroaryl groups having 3 to 30 carbon atoms (Ar' represents an aryl group or a heteroaryl group).

[0148] Ar １１ ~Ar ３１ But -P(=O)(Ar') ２ Examples of groups substituted with include a triphenylphosphine oxide group, a diphenylnaphthylphosphine oxide group, a diphenylphenanthrylphosphine oxide group, a diphenyl(dimethylfluorenyl)phosphine oxide group, a diphenyl(diphenylfluorenyl)phosphine oxide group, and a diphenylspirobifluorenylphosphine oxide group.

[0149] Also, Ar １１ ~Ar ３１ But -S(=O) ２ Examples of the group substituted by Ar' include a diphenylsulfone group and a dibenzothiophene-5,5-dioxide group, which can be one form of an aromatic group having 6 to 26 carbon atoms and at least one sulfone group.

[0150] a １１ , a ２１ , b１１ , b ２１ , c １１ , and c ２１ each independently represents an integer of 1 to 3, preferably an integer of 1 or 2. The material for a photoelectric conversion element for an imaging element represented by formula (1′) comprises a １１ , a ２１ , b １１ , b ２１ , c １１ , and c ２１ By optimizing each of these within such ranges, the glass transition temperature (T ｇ ) can be prevented from decreasing, the LUMO level of the material for a photoelectric conversion element for an imaging device can be deepened, and the response speed of the photoelectric conversion element for an imaging device can be increased.

[0151] The compound represented by formula (1') which is a material for a photoelectric conversion element for an imaging element is Ar １１ , Ar ２１ and Ar ３１ When there are a plurality of Ar １１ Each of Ar ２１ Each of Ar ３１ may be the same or different, and are preferably the same from the viewpoint of ease of production.

[0152] <L １１ , L ２１ , L ３１ > In formula (1'), L １１ , L ２１ , and L ３１ each independently represents a divalent to tetravalent aromatic hydrocarbon group, a divalent to tetravalent heteroaromatic group, or a divalent to tetravalent cycloaliphatic hydrocarbon group.

[0153] L １１ ~L ３１The aromatic hydrocarbon group represented by may be a single ring, or a linked ring or condensed ring containing multiple rings. Examples of the aromatic hydrocarbon group include, but are not limited to, a phenyl group, a naphthyl group, a phenanthryl group, an anthryl group, a fluorenyl group, a dimethylfluorenyl group, a spirofluorenyl group, a pyrenyl group, a fluoranthenyl group, a triphenylenyl group, a tetracenyl group, and a chrysenyl group.

[0154] L １１ ~L ３１ The heteroaromatic group represented by is not particularly limited, but is, for example, a functional group containing a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a silicon atom, and / or a germanium atom as a heteroatom on an aromatic ring, and may be a single ring, or a linked ring or condensed ring containing multiple rings. １１ ~Ar ３１ Preferred examples of the nitrogen-containing heteroaromatic groups include the above-mentioned nitrogen-containing heteroaromatic groups exemplified by a pyridyl group, a pyrimidinyl group, a pyrazinyl group, and a triazinyl group.

[0155] L １１ ~L ３１ Examples of the cyclic aliphatic hydrocarbon group represented by include Ar １１ ~Ar ３１ Similarly, examples of the alicyclic hydrocarbon groups include those having 10 or more carbon atoms, such as the above-mentioned adamantyl group.

[0156] L １１ ~L ３１ In the above, the aromatic hydrocarbon group, heteroaromatic group, and alicyclic hydrocarbon group may each independently have a substituent, or may not have a substituent. In other words, the aromatic hydrocarbon group, heteroaromatic group, and hydrocarbon group may be substituted or unsubstituted. Specific examples of the substituent that these functional groups may have include Ar １１ ~Ar ３１ The specific examples of the substituents that may be possessed by the group are the same as those of the group.

[0157] p １ , q １ and r １Each independently represents an integer of 0 to 3, preferably an integer of 0 to 2. The material for a photoelectric conversion element for an imaging element represented by formula (1′) is １ , q １ and r １ By optimizing each of them within such ranges, the T ｇ It is possible to suppress the decrease in the LUMO level of the material for a photoelectric conversion element for an imaging element, thereby deepening the LUMO level of the material for a photoelectric conversion element for an imaging element, and thereby increasing the response speed of the imaging element. １ If is 0, L １１ represents a single bond, and therefore, in formula (1′), Ar １１ and the triazine ring are directly bonded by a single bond. １ and r １ If each is 0, L ２１ and L ３１ Each represents a single bond.

[0158] The compound represented by formula (1′) is a material for a photoelectric conversion element for an imaging element, and is represented by formula (1′) １１ , L ２１ and L ３１ When there are multiple of each, L １１ Each of L ２１ Each of L ３１ may be the same or different.

[0159] <Characteristics of Ar, L, and Triazine Ring> In formula (1′), Ar １１ , Ar ２１ , Ar ３１ , L １１ , L ２１ and L ３１ At least one of Ar has a cyano group. １１ , Ar ２１ , Ar ３１ , L １１ , L ２１ and L ３１ At least one of the groups is substituted with a cyano group or a group having a cyano group.

[0160] In formula (1'), Ar １１ , Ar ２１, Ar ３１ , L １１ , L ２１ and L ３１ In formula (1'), the sum of the number of cyano groups contained in these groups and the number of nitrogen-containing heteroaromatic rings composed of 6-membered rings is 2 or more. １１ , Ar ２１ , Ar ３１ , L １１ , L ２１ , and L ３１ In the formula (1), the sum of the number of cyano groups and the number of pyridyl groups contained in these groups is preferably 2 or more. The nitrogen-containing heteroaromatic ring composed of a 6-membered ring is selected from (1) a heteroaromatic monocycle selected from the group consisting of a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, and a tetrazine ring, or (2) a fused ring consisting of 2 to 4 aromatic monocycles containing at least one heteroaromatic monocycle selected from the heteroaromatic monocycles. The heteroaromatic monocycles of the pyridine ring, the pyridazine ring, the pyrimidine ring, the pyrazine ring, the triazine ring, and the tetrazine ring contain a nitrogen atom as a ring-forming atom in a completely conjugated aromatic ring, and no hydrogen atom is covalently bonded to the nitrogen atom. In this specification, unless otherwise specified, the term "aromatic monocycle" includes both the meanings of "heteroaromatic monocycle" and "aromatic hydrocarbon monocycle." However, when -[L １１ ] ｐ １ - [(Ar １１ ) ａ １１ -H] ａ ２１ , -[L ２１ ] ｑ １ - [(Ar ２１ ) ｂ １１ -H] ｂ ２１ , and −[L ３１ ] ｒ １ - [(Ar ３１ ) ｃ １１ -H] ｃ ２１ The central triazine ring to which Ar is bonded is １１, Ar ２１ , Ar ３１ , L １１ , L ２１ and L ３１ In other words, the sum of the number of cyano groups and the number of six-membered nitrogen-containing heteroaromatic rings contained in the three substituents of the central triazine ring is preferably 2 or more.

[0161] That is, for example, in the following compound CC'119-GC'5, the sum of the number of cyano groups and the number of nitrogen-containing heteroaromatic rings composed of six-membered rings in the substituents of the central triazine ring is three.

[0162] Furthermore, for example, in the following compound CA'11-GA'45, the sum of the number of cyano groups and the number of 6-membered nitrogen-containing heteroaromatic rings in the substituents of the central triazine ring is 4. That is, in the 2-cyanopyridin-5-yl group in compound CA'11-GA'45, the sum of the number of cyano groups and the number of 6-membered nitrogen-containing heteroaromatic rings is 2 per group.

[0163] Ar １１ , Ar ２１ , Ar ３１ , L １１ , L ２１ and L ３１ When at least one of the above has such a characteristic, the LUMO level of the material for a photoelectric conversion element for an imaging element can be deepened, and the response speed of the imaging element can be increased.

[0164] That is, in formula (1′), Ar １１ , Ar ２１ , Ar ３１ , L １１ , L ２１ and L ３１It is preferable that at least one of the groups has a cyano group, and the sum of the number of cyano groups contained in these groups and the number of heteroaromatic monocycles exemplified by the above-mentioned pyridyl group, pyrimidinyl group, pyrazyl group, triazinyl group, etc., and the number of nitrogen-containing heteroaromatic rings composed of 6-membered rings partially containing a heteroaromatic monocycle is 2 or more.

[0165] Furthermore, in the material for a photoelectric conversion element for an image sensor represented by formula (1'), and the materials for a photoelectric conversion element for an image sensor represented by each formula described below, and the compounds, at least one of the three groups in the central triazine ring has at least one cyano group, and the sum of the number of cyano groups and the number of nitrogen-containing heteroaromatic rings composed of 6-membered rings contained in the three groups is 2 or more, the LUMO level can be deepened as described above, and the materials can be used as materials for a photoelectric conversion element for an image sensor that can achieve at least one of a faster response speed, a lower dark current, and a higher external quantum efficiency in the image sensor.

[0166] In formula (1'), Ar １１ , Ar ２１ , Ar ３１ , L １１ , L ２１ and L ３１ In the above, it is preferred that the total number of cyano groups contained is 1 to 10, 1 to 8, 1 to 6, or 1 to 4, in this order.

[0167] The nitrogen-containing heteroaromatic ring composed of the six-membered ring is preferably a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, or a tetrazine ring, more preferably a pyridyl group or a pyrimidinyl group, and even more preferably a pyridyl group. With such a configuration, the LUMO of the material for a photoelectric conversion element for an imaging element can be deepened, and the response speed of the imaging element can be increased.

[0168] Preferred specific examples of the compound represented by formula (1') are shown in the table below, but are not limited thereto. The table below shows compounds (CA'x) having the skeletons (CA'1) to (CA'163) shown below, and R contained in the skeleton is bonded to the groups (GA'1) to (GA'50) shown below at the # position of the groups.１１ -GA'y １１ ) where x １１ represents an integer from 1 to 163, and y １１ represents any integer from 1 to 50. That is, (CA'x １１ -GA'y １１ The compound of (CA'1-GA'1) to (CA'163-GA'50) is a compound of (CA'1-GA'1). １１ = 4, y １１ In the case of a compound (CA'4-GA'43) where =43, it has a skeleton of (CA'4), and the group of (GA'43) is bonded to R of the skeleton at the # position of the group, which represents the following compound (CA'4-GA'43).

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214]

[0215] Furthermore, preferred specific examples of the compound represented by formula (1') are shown in the table below, but are not limited thereto. The table below shows compounds (CB'x) having the skeletons (CB'1) to (CB'160) shown below, and R contained in the skeleton is bonded to the groups (GB'1) to (GB'50) shown below at the # position of the groups. ２１ -GB'y ２１ ) where x ２１ represents an integer from 1 to 160, and y ２１ represents any integer from 1 to 50. That is, (CB'x ２１ -GB'y ２１ The compound of (CB'1-GB'1) to (CB'160-GB'50) is therefore a compound of, for example, x ２１ = 95, y ２１ In the case of a compound (CB'95-GB'1) where =1, the compound has a skeleton of (CB'95), and the group of (GB'1) is bonded to the R of the skeleton at the # site of the group, which represents the following compound (CB'95-GB'1).

[0216]

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246]

[0247]

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261]

[0262]

[0263]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270]

[0271] <Compound (2)> In one embodiment of the present invention, the material (1′) for a photoelectric conversion element for an imaging element may be a compound represented by the following formula (2): The compound represented by formula (2) also falls within the scope of the present invention. In the formula (2), L ２１Ａ represents a phenylene group; １Ａ represents an integer of 0 or 1; ２１ is represented by any one of formulas (21a) to (24a); In the formulas (21a) to (24a), Ar ２１Ａ are the same or different and represent a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heteroaromatic group; R ２２ , and R ２３ are each independently represented by any one of formulas (21b) to (25b); In the formulas (21b) to (25b), Ar ２２Ａ are the same or different and represent a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heteroaromatic group; L ２２Ａ represents a phenylene group or a single bond; * represents a bonding site; Ar in the formulae (21a) to (24a) ２１Ａ and Ar in the formulas (21b) to (25b). ２２Ａ At least one of the Ar groups in the formulae (21a) to (24a) has a cyano group; ２１Ａ and Ar in the formulas (21b) to (25b). ２２Ａwherein the sum of the number of cyano groups and the number of pyridyl rings contained in these groups is 2 or more; ２１ is represented by the formula (21a), and / or R ２２ and R ２３ When at least one of the above is represented by the formula (21b), Ar in the formula (21a) ２１Ａ and Ar in the formula (21b). ２２Ａ are the same or different and are an aromatic hydrocarbon group substituted with one or more cyano groups, or a heteroaromatic group substituted with one or more cyano groups.

[0272] <L ２１Ａ > In formula (2), L ２１Ａ represents a phenylene group, and from the viewpoint of increasing thermal stability, preferably represents an o-phenylene group or a p-phenylene group. ２１Ａ is L in formula (1'). ２１ Corresponds to.

[0273] <q １Ａ > In formula (2), q １Ａ represents an integer of 0 or 1. １Ａ When is 0, L ２１Ａ represents a single bond. １Ａ is q in formula (1') １ Corresponds to.

[0274] <R ２１ > R ２１ is represented by any one of formulas (21a) to (24a); In the formulas (21a) to (24a), Ar ２１Ａ are the same or different and represent a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heteroaromatic group.

[0275] Ar ２１Ａ and are more preferably the same or different and are an aromatic hydrocarbon group substituted with a cyano group, or a substituted or unsubstituted heteroaromatic group.

[0276] Ar ２１ＡSpecific examples of the substituted aryl group include, but are not limited to, a phenyl group, a tolyl group, a biphenyl group, a pyridylphenyl group, a naphthylphenyl group, a pyridyl group, a pyrimidinyl group, a pyrazyl group, a triazinyl group, a naphthyl group, a quinolyl group, an isoquinolyl group, a benzothienyl group, a benzofuryl group, an anthryl group, a phenanthryl group, a fluorenyl group, a dibenzothienyl group, a dibenzofuryl group, a fluoranthenyl group, a pyrenyl group, a triphenylenyl group, a triptycenyl group, a cyanophenyl group, a cyanonaphthyl group, or a cyanopyridyl group, which may be substituted with, the same or different, a deuterium atom, a halogen atom, a cyano group, an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 26 carbon atoms, or a heteroaromatic group having 3 to 26 carbon atoms.

[0277] Among these substituents, in terms of excellent properties of the material for a photoelectric conversion element for an imaging element, the following can be independently selected: 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, a 4-(2-pyridyl)phenyl group, a 3-(3-pyridyl)phenyl group, a 4-(3-pyridyl)phenyl group, a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 2-phenylpyridin-6-yl group, a 2-phenylpyridin-5-yl group, a 2-phenylpyridin-4-yl group, a 3-phenylpyridin-6-yl group, a 2-phenylpyridin-5-yl group, a 2-phenylpyridin-4-yl group, a 3-phenylpyridin-4-yl group, a 2-phenylpyridin-6-yl group, a 2-phenylpyridin-5-yl group, a 2-phenylpyridin-4 ... pyridin-5-yl group, 3-phenylpyridin-6-yl group, 2,6-diphenylpyridin-4-yl group, 4,6-diphenylpyridin-2-yl group, 2-pyrimidinyl 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-dimethylfluoren-3-yl group, 9,9-dimethylfluoren-4-yl group, 9,9-diphenylfluoren-2-yl group, a 9,9-diphenylfluoren-3-yl group, a 9,9-diphenylfluoren-4-yl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 9-phenanthryl group, a 2-dibenzothienyl group, a 2-dibenzofuryl group, a 4-dibenzothienyl group, a 4-dibenzofuryl group, a 3-fluoranthenyl group, a 1-pyrenyl group, a 2-triphenylenyl group, a 1-triptycenyl group, a 2-triptycenyl group, a 2-phenylphenylsulfone group, a 3-phenylphenylsulfone group, a 4-phenylfuryl group, a 1-pyrenyl group, a 2-triphenylenyl group, a 1 ... dibenzothiophene-5,5-dioxid-1-yl group, dibenzothiophene-5,5-dioxid-2-yl group, dibenzothiophene-5,5-dioxid-3-yl group, dibenzothiophene-5,5-dioxid-4-yl group, 1-adamantyl group, 2-adamantyl group, 2-cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group, 2,3-dicyanophenyl group, 2,4-dicyanophenyl group, 2,5-dicyanophenyl group, 2,6-dicyanophenyl group, 3,4-dicyanophenyl group, 3,5-dicyanophenyl group, 3-cyanopyridin-2-yl group, 4-cyanopyridin-2-yl group, 5-cyanopyridin-2-yl group, 6-cyanopyridin-2-yl group, 2-cyanopyridin-3-yl group, 4-cyanopyridin-3-yl group, 5-cyanopyridin-3-yl group, 6-cyanopyridin-3-yl group, 2-cyanopyridin-4-yl group, 3-cyanopyridin-4-yl group, 2,4-dicyanopyridin-3-yl group, 2,5-dicyanopyridin-3-yl group, 2,6-dicyanopyridin-3-yl group, 2,3-dicyanopyridin-4-yl group More preferred are aryl groups, 2,5-dicyanopyridin-4-yl groups, 2,6-dicyanopyridin-4-yl groups, 2-cyano-1-naphthyl groups, 3-cyano-1-naphthyl groups, 4-cyano-1-naphthyl groups, 5-cyano-1-naphthyl groups, 6-cyano-1-naphthyl groups, 7-cyano-1-naphthyl groups, 8-cyano-1-naphthyl groups, 1-cyano-2-naphthyl groups, 3-cyano-2-naphthyl groups, 4-cyano-2-naphthyl groups, 5-cyano-2-naphthyl groups, 6-cyano-2-naphthyl groups, 7-cyano-2-naphthyl groups, and 8-cyano-2-naphthyl groups.

[0278] <R ２２ , R ２３ > R ２２ , and R ２３ are each independently represented by any one of formulas (21b) to (25b); In the formulas (21b) to (25b), Ar ２２Ａ are the same or different and represent a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heteroaromatic group; L ２２Ａ represents a phenylene group or a single bond.

[0279] Ar ２２Ａ More preferably, Ar may be the same or different and represent an unsubstituted or cyano-substituted aromatic hydrocarbon group, or a substituted or unsubstituted heteroaromatic group. ２２Ａ Specific examples of the group include, but are not limited to, Ar ２１Ａ The same groups as those shown below can be mentioned.

[0280] In formula (2), Ar in formulas (21a) to (24a)２１Ａ and Ar in the formulas (21b) to (25b). ２２Ａ It is more preferable that at least two of the above have a cyano group. According to this configuration, the LUMO of the material for a photoelectric conversion element for an imaging element can be deepened, and the response speed of the imaging element can be increased.

[0281] <Compound (3)> In one embodiment of the present invention, the material (1′) for a photoelectric conversion element for an imaging element may be a compound represented by the following formula (3): The compound represented by formula (3) also falls within the scope of the present invention.

[0282] In the formula (3), L ３１Ａ represents a phenylene group; １Ａ represents an integer of 0 or 1; ３１ is represented by any one of formulas (31a) to (34a); In the formulas (31a) to (34a), Ar ３１Ａ are the same or different and represent a phenyl group substituted with one or more cyano groups, a pyridyl group, a pyridyl group substituted with one or more alkyl groups having 1 to 6 carbon atoms, a pyridyl group substituted with one or more cyano groups, or an optionally substituted naphthyl group; R ３２ , and R ３３ are each independently represented by any one of formulas (31b) to (35b); In the formulas (31b) to (35b), Ar ３２Ａ are the same or different and represent a phenyl group, a phenyl group substituted with one or more alkyl groups having 1 to 6 carbon atoms, a phenyl group substituted with one or more cyano groups, a pyridyl group, a pyridyl group substituted with one or more alkyl groups having 1 to 6 carbon atoms, a pyridyl group substituted with one or more cyano groups, or a biphenylyl group; L ３２Ａ represents a phenylene group or a single bond; * represents a bonding site; Ar in the formulae (31a) to (34a) ３１Ａ and Ar in the formulas (31b) to (35b). ３２Ａ At least one of R has a cyano group; ３１is represented by the formula (31a), and / or R ３２ and R ３３ When at least one of the above is represented by the formula (31b), Ar in the formula (31a) ３１Ａ and Ar in the formula (31b). ３２Ａ are the same or different and are a phenyl group substituted with one or more cyano groups, or a pyridyl group substituted with one or more cyano groups.

[0283] <L ３１Ａ > In formula (3), L ３１Ａ represents a phenylene group, and preferably represents an o-phenylene group or a p-phenylene group from the viewpoint of improving thermal stability. ３１Ａ When L is an optionally substituted naphthyl group, ３１Ａ is preferably a phenylene group. ３１Ａ is L in formula (1'). ３１ Corresponds to.

[0284] <r １Ａ > In formula (3), r １Ａ represents an integer of 0 or 1. １Ａ When is 0, L ３１Ａ represents a single bond. １Ａ is r in formula (1'). １ Corresponds to.

[0285] <R ３１ > R ３１ is represented by any one of formulas (31a) to (34a); In the formulas (31a) to (34a), Ar ３１Ａ are the same or different and represent a phenyl group substituted with one or more cyano groups, a pyridyl group, a pyridyl group substituted with one or more alkyl groups having 1 to 6 carbon atoms, a pyridyl group substituted with one or more cyano groups, or a naphthyl group which may be substituted, and from the viewpoint of enhancing thermal stability, preferably represent a phenyl group substituted with one or more cyano groups, a pyridyl group, a pyridyl group substituted with one or more cyano groups, a naphthyl group, or a naphthyl group substituted with one or more cyano groups.

[0286] <R ３２ , R ３３ > R ３２ , and R ３３ are each independently represented by any one of formulas (31b) to (35b); In the formulas (31b) to (35b), Ar ３２Ａ are the same or different and represent a phenyl group, a phenyl group substituted with one or more alkyl groups having 1 to 6 carbon atoms, a phenyl group substituted with one or more cyano groups, a pyridyl group, a pyridyl group substituted with one or more alkyl groups having 1 to 6 carbon atoms, a pyridyl group substituted with one or more cyano groups, or a biphenylyl group, and from the viewpoint of enhancing thermal stability, preferably represent a phenyl group, a phenyl group substituted with one or more cyano groups, a pyridyl group, a pyridyl group substituted with one or more cyano groups, or a biphenylyl group; L ３２Ａ represents a phenylene group or a single bond; * represents a bonding site.

[0287] Preferred specific examples of the compounds represented by formula (2) and (3) are shown in the table below, but are not limited thereto. The table below shows compounds having a skeleton of (CC'1) to (CC'132) shown below, and groups of (GC'1) to (GC'50) shown below bonded to R of the skeleton at the # position of the group, (CC'x ３１ -GC'y ３１ ) where x ３１ is an integer between 1 and 132, y ３１ represents any integer from 1 to 50. That is, (CC'x ３１ -GC'y ３１ The compound of (CC'1-GC'1) to (CC'132-GC'50) is a compound of (CC'1-GC'1). ３１ = 105, y ３１ In the case of a compound (CC'105-GC'1) where =1, it has a skeleton of (CC'105), and the group of (GC'1) is bonded to the R of the skeleton at the # position of the group, which represents the compound (CC'105-GC'1) below.

[0288]

[0289]

[0290]

[0291]

[0292]

[0293]

[0294]

[0295]

[0296]

[0297]

[0298]

[0299]

[0300]

[0301]

[0302]

[0303]

[0304]

[0305]

[0306]

[0307]

[0308]

[0309]

[0310]

[0311]

[0312]

[0313]

[0314]

[0315]

[0316]

[0317]

[0318]

[0319]

[0320]

[0321]

[0322]

[0323]

[0324]

[0325]

[0326]

[0327]

[0328]

[0329]

[0330]

[0331]

[0332]

[0333]

[0334]

[0335]

[0336]

[0337]

[0338]

[0339]

[0340]

[0341]

[0342] Other preferred specific examples of the material (2) or (3) for a photoelectric conversion element for an imaging device are shown below, but the material is not limited to these.

[0343]

[0344] <Compound (4)> In one embodiment of the present invention, the material (1′) for a photoelectric conversion element for an imaging element may be a compound represented by the following formula (4): The compound represented by formula (4) also falls within the scope of the present invention. In the formula (4), Ar ４１ , and Ar ４２ each independently represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 26 carbon atoms, a substituted or unsubstituted nitrogen-containing heteroaromatic group having 3 to 26 carbon atoms and consisting only of a 6-membered ring, a substituted or unsubstituted oxygen-containing or sulfur-containing heteroaromatic group having 3 to 26 carbon atoms, or a cycloaliphatic hydrocarbon group having 10 to 16 carbon atoms; L ４１ ~L ４３ each independently represents a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 26 carbon atoms, a substituted or unsubstituted divalent nitrogen-containing heteroaromatic group having 3 to 26 carbon atoms and consisting only of a 6-membered ring, a substituted or unsubstituted divalent oxygen-containing or sulfur-containing heteroaromatic group having 3 to 26 carbon atoms, or a divalent cycloaliphatic hydrocarbon group having 10 to 16 carbon atoms; ４ , q ４ and r ４each independently represents an integer of 0 to 2; ４１ , Ar ４２ , L ４１ , L ４２ , and L ４３ At least one of the groups has a cyano group.

[0345] <Ar ４１ , Ar ４２ > In formula (4), Ar ４１ , and Ar ４２ each independently represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 26 carbon atoms, a substituted or unsubstituted nitrogen-containing heteroaromatic group having 3 to 26 carbon atoms and consisting only of a 6-membered ring, a substituted or unsubstituted oxygen-containing or sulfur-containing heteroaromatic group having 3 to 26 carbon atoms, or a cyclic aliphatic hydrocarbon group having 10 to 16 carbon atoms.

[0346] Ar ４１ , and Ar ４２ Specific examples of the group include, but are not limited to, Ar １１ , Ar ２１ , Ar ３１ , Ar ２１Ａ , and Ar ２２ＡAmong these groups, for example, a phenyl group, a tolyl group, a biphenyl group, a pyridylphenyl group, a naphthylphenyl group, a pyridyl group, a pyrimidinyl group, a pyrazyl group, a triazinyl group, a naphthyl group, a quinolyl group, an isoquinolyl group, a benzothienyl group, each of which may independently be substituted with a deuterium atom, a halogen atom, a cyano group, an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 26 carbon atoms, or a heteroaromatic group having 3 to 26 carbon atoms, can be mentioned. Preferred are a phenyl group, a benzofuryl group, an anthryl group, a phenanthryl group, a fluorenyl group, a dibenzothienyl group, a dibenzofuryl group, a fluoranthenyl group, a pyrenyl group, a triphenylenyl group, a triptycenyl group, a cyanophenyl group, a cyanonaphthyl group, or a cyanopyridyl group, and further, in terms of excellent properties of the material for a photoelectric conversion element for an imaging element, a phenyl group, a p-tolyl group, a biphenyl-2-yl group, a biphenyl-3-yl group, a biphenyl-4-yl group, or a phenyl-5-yl group, each independently selected from the group consisting of phenyl, p-tolyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, and the like. a 3-(2-pyridyl)phenyl group, a 4-(2-pyridyl)phenyl group, a 3-(3-pyridyl)phenyl group, a 4-(3-pyridyl)phenyl group, a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 2-phenylpyridin-6-yl group, a 2-phenylpyridin-5-yl group, a 2-phenylpyridin-4-yl group, a 3-phenylpyridin-5-yl group, a 3-phenylpyridin-6-yl group, a 2,6-diphenylpyridin-4-yl group, a 4,6-diphenyl Pyridin-2-yl group, 2-pyrimidinyl 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-dimethylfluoren-3-yl group, 9,9-dimethylfluoren-4-yl group, 9,9-diphenylfluoren-2-yl group, 9,9-diphenylfluoren-3-yl group, 9,9-diphenylfluoren-4-yl group, 9-anthryl 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-fluoranthenyl group, 1-pyrenyl group, 2-triphenylenyl group, 1-triptycenyl group, 2-triptycenyl group, 2-phenylphenylsulfone group, 3-phenylphenyl sulfone group, 4-phenylphenyl sulfone group, dibenzothiophene-5,5-dioxid-1-yl group, dibenzothiophene-5,5-dioxid-2-yl group, dibenzothiophene-5,5-dioxid-3-yl group, dibenzothiophene-5,5-dioxid-4-yl group, 1-adamantyl group, 2-adamantyl group, 2-cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group a 2,3-dicyanophenyl group, a 2,4-dicyanophenyl group, a 2,5-dicyanophenyl group, a 2,6-dicyanophenyl group, a 3,4-dicyanophenyl group, a 3,5-dicyanophenyl group, a 3-cyanopyridin-2-yl group, a 4-cyanopyridin-2-yl group, a 5-cyanopyridin-2-yl group, a 6-cyanopyridin-2-yl group, a 2-cyanopyridin-3-yl group, a 4-cyanopyridin-3 ... A cyanopyridin-3-yl group, a 6-cyanopyridin-3-yl group, a 2-cyanopyridin-4-yl group, a 3-cyanopyridin-4-yl group, a 2,4-dicyanopyridin-3-yl group, a 2,5-dicyanopyridin-3-yl group, a 2,6-dicyanopyridin-3-yl group, a 2,3-dicyanopyridin-4-yl group, a 2,5-dicyanopyridin-4-yl group, or a 2,6-dicyanopyridin-4-yl group is more preferred.

[0347] <L ４１ , L ４２ , L ４３ > In formula (4), L ４１ ~L ４３each independently represents a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 26 carbon atoms, a substituted or unsubstituted divalent nitrogen-containing heteroaromatic group having 3 to 26 carbon atoms and consisting only of a 6-membered ring, a substituted or unsubstituted oxygen- or sulfur-containing divalent heteroaromatic group having 3 to 26 carbon atoms, or a divalent cycloaliphatic hydrocarbon group having 10 to 16 carbon atoms.

[0348] L ４１ , L ４２ , and L ４３ Specific examples of are not particularly limited, but include, for example, １１ , L ２１ , and L ３１ Among these groups, for example, a phenyl group, a biphenyl group, a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, a triazinyl group, a naphthyl group, a quinolyl group, a benzothienyl group, a benzofuryl group, an anthryl group, a phenanthryl group, a fluorenyl group, a dibenzothienyl group, a dibenzofuryl group, a fluoranthenyl group, a pyrenyl group, a triphenylenyl group, or a triptycenyl group, each of which may independently be substituted with a deuterium atom, a halogen atom, a cyano group, an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 26 carbon atoms, or a heteroaromatic group having 3 to 26 carbon atoms, is preferred, and from the viewpoint of excellent properties of the material for a photoelectric conversion element for an imaging element, a phenyl group which may be substituted with a cyano group, or a pyridyl group which may be substituted with a cyano group is more preferred.

[0349] <p ４ , q ４ , r ４ > p ４ , q ４ and r ４ each independently represents an integer of 0 to 2.

[0350] <Ar ４１ , Ar ４２ , L ４１ , L ４２ , L ４３ and characteristics of the triazine ring> In formula (4), Ar ４１ , Ar ４２ , L ４１ , L４２ , and L ４３ At least one of Ar has a cyano group. ４１ , Ar ４２ , L ４１ , L ４２ , and L ４３ At least one of the groups is substituted with a cyano group or a group having a cyano group.

[0351] In formula (4), Ar ４１ , Ar ４２ , L ４１ , L ４２ , and L ４３ In the formula (4), it is preferable that the sum of the number of cyano groups contained in these groups and the number of nitrogen-containing heteroaromatic rings constituted by 6-membered rings is 2 or more, and ４１ , Ar ４２ , L ４１ , L ４２ , and L ４３ In the formula (1), the sum of the number of cyano groups and the number of pyridyl groups contained in these groups is preferably 2 or more. The nitrogen-containing heteroaromatic ring composed of a 6-membered ring is selected from (1) a heteroaromatic monocycle selected from the group consisting of a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, and a tetrazine ring, or (2) a fused ring consisting of 2 to 4 aromatic monocycles, which partially contains at least one heteroaromatic monocycle selected from the heteroaromatic monocycles. The heteroaromatic monocycles of the pyridine ring, the pyridazine ring, the pyrimidine ring, the pyrazine ring, the triazine ring, and the tetrazine ring contain a nitrogen atom as a ring-forming atom in a completely conjugated aromatic ring, and no hydrogen atom is covalently bonded to the nitrogen atom. In this specification, unless otherwise specified, the term "aromatic monocycle" includes both the meanings of "heteroaromatic monocycle" and "aromatic hydrocarbon monocycle." However, when -[L ４１ ] ｐ ４ -Ar ４１ , -[L ４２ ] ｑ ４ -Ar ４２ , and −[L ４３ ] ｒ ４The central triazine ring to which -(triptycene) is bonded is ４１ , Ar ４２ , L ４１ , L ４２ , and L ４３ In other words, the sum of the number of cyano groups and the number of 6-membered nitrogen-containing heteroaromatic rings contained in the three substituents of the central triazine ring is preferably 2 or more, and the sum of the number of cyano groups and the number of pyridyl groups contained in the three substituents of the central triazine ring is more preferably 2 or more.

[0352] Preferred specific examples of the compound represented by formula (4) include, but are not limited to, compounds having groups GA'45 to GA'50 among the compounds (CA'1-GA'1) to (CA'163-GA'50) above. Preferred specific examples of the compound represented by formula (4) further include the compounds shown in the table below. (CE'x) which have the skeletons (CE'1) to (CE'38) shown below, and to R which the skeleton has, groups (GE'1) to (GE'6) shown below are bonded at the # position which the groups have. ４１ -GE'y ４１ ) where x ４１ is an integer between 1 and 38, y ４１ represents any integer from 1 to 6. That is, (CE'x ４１ -GE'y ４１ The compound of (CE'1-GE'1) to (CE'38-GE'6) means a compound of (CE'1-GE'1) to (CE'38-GE'6). ４１ = 1, y ４１ In the case of a compound (CE'1-GE'1) where =1, it has a skeleton of (CE'1), and the group of (GE'1) is bonded to the R of the skeleton at the # position of the group, which represents the compound (CE'1-GE'1) below.

[0353]

[0354]

[0355]

[0356]

[0357]

[0358]

[0359]

[0360]

[0361]

[0362]

[0363]

[0364]

[0365]

[0366]

[0367]

[0368] <Photoelectric Conversion Element Material for Image Sensor, Hole-Blocking Material for Image Sensor> A photoelectric conversion element material for an image sensor according to one embodiment of the present invention consists of or contains a compound represented by formula (1) (e.g., a compound represented by formula (11), (12), (13), or (14)) or a compound represented by formula (1′) (e.g., a compound represented by formula (2), (3), or (4)). Applications of the photoelectric conversion element material for an image sensor according to one embodiment of the present invention will be described below. As described above, the photoelectric conversion element material for an image sensor achieves both high response speed and external quantum efficiency, and therefore can be suitably used in layers provided in an image sensor, such as a photoelectric conversion layer and a hole-blocking layer.

[0369] In addition, the material for a photoelectric conversion element for an imaging element according to one embodiment of the present invention has a high T ｇ

[0023] By virtue of this, changes in the film state, such as crystallization, caused by annealing during the manufacture of a photoelectric conversion element are prevented. As a result, a decrease in external quantum efficiency is prevented and dark current is reduced in an imaging element formed from the photoelectric conversion element material for an imaging element according to one embodiment of the present invention. Therefore, the photoelectric conversion element material for an imaging element according to one embodiment of the present invention can be suitably used as a photoelectric conversion element material for an imaging element and a hole-blocking material, which are required to be resistant to annealing after the formation of a photoelectric conversion layer.

[0370] The material for a photoelectric conversion element for an imaging element according to one embodiment of the present invention can be used, for example, as a material for a photoelectric conversion layer in an imaging element or a hole-blocking material that is a material for a hole-blocking layer in the imaging element.

[0371] A photoelectric conversion element material for an image sensor according to one embodiment of the present invention includes a skeleton represented by the above formula (1) or (1'). The photoelectric conversion element material for an image sensor and the hole-blocking material including the skeleton represented by the formula (1) or (1') contribute to the production of a photoelectric conversion element material for an image sensor having excellent response speed and external quantum efficiency characteristics.

[0372] <Regarding LUMO Level> In order to reduce dark current, improve external quantum efficiency, and improve response speed, materials for photoelectric conversion elements for imaging devices may need to rapidly transfer charges generated in the photoelectric conversion layer. For rapid charge transfer, it is preferable that the LUMO levels of the n-type semiconductor material of the photoelectric conversion layer and the material used in the hole blocking layer are close to each other. For example, when fullerene (C60) is used in the photoelectric conversion layer, the LUMO levels of the hole blocking layer are more preferably −2.0 eV or less, −2.1 eV or less, −2.2 eV or less, −2.3 eV or less, −2.4 eV or less, −2.5 eV or less, −2.6 eV or less, −2.7 eV or less, −2.8 eV or less, −2.9 eV or less, and −3.0 eV or less, respectively, as quantum chemical calculation values ​​obtained by density functional theory (DFT) as described below. The LUMO level of the hole blocking layer is not limited, but may be −5.0 eV or higher, and is preferably −4.0 eV or higher.

[0373] In an image sensor according to one aspect of the present invention, the LUMO level of the material for a photoelectric conversion element for an image sensor is a value calculated by quantum chemical calculation, and the optimization of the molecular structure and the calculation of the LUMO level can be obtained by density functional theory (DFT) under calculation conditions of a B3LYP functional and a 6-31G(d) basis set using a Gaussian program.

[0374] <Regarding Glass Transition Temperature> The material for a photoelectric conversion element for an imaging element used to form a layer included in an imaging element according to one embodiment of the present invention is a material for a photoelectric conversion element for an imaging element represented by formula (1) or (1′), and the glass transition temperature of the material for a photoelectric conversion element for an imaging element represented by formula (1) or (1′) is not particularly limited, but from the viewpoint of compatibility with the imaging element, i.e., the photoelectric conversion element for the imaging element, the glass transition temperature is preferably 130° C. or higher, more preferably 140° C. or higher, and even more preferably 150° C. or higher. Note that this glass transition temperature is a value obtained by differential scanning calorimetry.

[0375] The differential scanning calorimeter and test conditions were as follows: Differential scanning calorimeter model: Hitachi High-Tech DSC7020; operating conditions: heating rate, 10°C / min, temperature range, 40°C to 400°C; the glass transition temperature was determined from the peak after two scans.

[0376] <Molecular Weight> The compound represented by formula (1) or (1') used for forming a layer included in an imaging element according to one embodiment of the present invention preferably has a molecular weight of 550 or more as a material for a photoelectric conversion element for an imaging element, which can increase the glass transition temperature and improve the thermal stability of the film. The molecular weight of the material for a photoelectric conversion element for an imaging element may be evaluated by mass spectrometry.

[0377] <Regarding Amorphous Properties> The photoelectric conversion element material for an imaging element according to one embodiment of the present invention, i.e., the photoelectric conversion element material for an imaging element represented by formula (1) or (1'), preferably forms an amorphous layer in a vapor-deposited film of the material. If the vapor-deposited film is a crystalline layer, the interface with an adjacent layer will not be uniform, which will cause defects in the element.

[0378] There are no particular limitations on the method for determining whether a vapor-deposited film is an amorphous layer. For example, it can be determined by visually checking whether crystallization is present or not, or by XRD measurement of the vapor-deposited film to see whether a sharp diffraction peak is observed.

[0379] <Imaging Device> An imaging device according to an aspect of the present invention includes a layer containing the material for a photoelectric conversion element for an imaging device according to an aspect of the present invention.

[0380] The configuration of the imaging element is not particularly limited, but examples thereof include the following configurations (i) to (vi).

[0381] (i) first electrode / photoelectric conversion layer / second electrode (ii) first electrode / hole blocking layer / photoelectric conversion layer / second electrode (iii) first electrode / photoelectric conversion layer / electron blocking layer / second electrode (iv) first electrode / hole blocking layer / photoelectric conversion layer / electron blocking layer / second electrode (v) first electrode / hole blocking layer / photoelectric conversion layer / electron blocking layer / hole transport layer / second electrode (vi) first electrode / electron transport layer / hole blocking layer / photoelectric conversion layer / electron blocking layer / hole transport layer / second electrode

[0382] An imaging element according to an embodiment of the present invention will be described in more detail below, taking the above-mentioned configuration (v) as an example, with reference to Fig. 1. Fig. 1 is a schematic cross-sectional view showing an example of the layer configuration of an imaging element including a layer containing a material for a photoelectric conversion element for an imaging element according to an embodiment of the present invention.

[0383] The imaging device 100 includes a first electrode 1, a hole blocking layer 2, a photoelectric conversion layer 3, an electron blocking layer 4, a hole transport layer 5, and a second electrode 6, in this order. However, some of these layers may be omitted, or other layers may be added. Of the above layers, the hole blocking layer 2, the photoelectric conversion layer 3, the electron blocking layer 4, and the hole transport layer 5 constitute an organic layer 10.

[0384] 1 may specifically be an imaging photoelectric conversion element. In the imaging element 100, light is incident from below the transparent first electrode 1 and is received by the photoelectric conversion layer 3, which is a light-receiving layer. The direction of light incidence is not particularly limited, and the second electrode 6 may be transparent so that light is incident from the second electrode 6 side.

[0385] In the imaging device 100, due to an internal electric field caused by differences in the concentration of carriers constituting each layer and differences in the work function between the first electrode 1 and the second electrode 6, of the charges (holes and electrons) generated by light reception in the photoelectric conversion layer 3, the electrons move to the first electrode 1 and the holes move to the second electrode 6. Charges can also be moved by applying a voltage between the first electrode 1 and the second electrode 6. In this way, the first electrode 1 serves as an electron collecting electrode, and the second electrode 6 serves as a hole collecting electrode.

[0386] Each layer may be replaced with a layer having a different name or function, as necessary. Examples of layers having a different name or function include a hole injection layer, a work function adjustment layer, and a hole transport promotion layer, which are alternative names for the hole transport layer.

[0387] In Fig. 1, the substrate provided on the lower surface of the first electrode 1 is omitted. The substrate here is not particularly limited, and examples thereof include a glass plate, a quartz plate, and a plastic plate. In addition, in a configuration in which light is incident from the substrate side, the substrate is transparent to the wavelength of light. The substrate may be provided on the second electrode 6 side. Each of the above layers will be described below.

[0388] [Layer Containing a Photoelectric Conversion Material for an Image Sensor] An image sensor, which is one embodiment of a photoelectric conversion element, may contain a photoelectric conversion material for an image sensor represented by the above formula (1) or (1') in one or more layers selected from the group consisting of a photoelectric conversion layer and a layer between the photoelectric conversion layer and a second electrode. In the configuration example shown in FIG. 1 , the image sensor 100 contains a photoelectric conversion material for an image sensor in at least one layer selected from the group consisting of the hole blocking layer 2 and the photoelectric conversion layer 3. In an image sensor according to one embodiment of the present invention, the hole blocking layer 2 preferably contains a photoelectric conversion material for an image sensor. This has the effect of rapidly transferring required charges while controlling reverse hole migration.

[0389] The material for a photoelectric conversion element for an imaging element represented by the above formula (1) or (1′) may be contained in multiple layers of the imaging element, and when an electron transport layer is provided, the electron transport layer may contain the material for a photoelectric conversion element for an imaging element.

[0390] The imaging photoelectric conversion element 100 in which the hole blocking layer 2 contains a material for an imaging photoelectric conversion element will be described below.

[0391] [First Electrode 1] A first electrode 1 is provided on the substrate.

[0392] In the case of an imaging element configured so that light passes through the first electrode and enters the photoelectric conversion layer 3, the first electrode 1 is preferably formed of a transparent material that transmits or substantially transmits the light.

[0393] The transparent material used for the lower electrode, which is the first electrode 1, is not particularly limited, and 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.

[0394] When the imaging element 100 is configured so that light enters the photoelectric conversion layer 3 only from the second electrode 6 side, the light transmission characteristics of the first electrode 1 are not important. Therefore, examples of materials that can be used for the first electrode 1 in this case include gold, iridium, molybdenum, palladium, and platinum.

[0395] [Hole Blocking Layer 2] The hole blocking layer 2 is provided between the first electrode 1 and the photoelectric conversion layer 3, which is a light-receiving layer described below.

[0396] The hole blocking layer 2 has a role of transporting electrons generated in the photoelectric conversion layer 3 to the first electrode 1 and a role of blocking holes from moving from the photoelectric conversion layer 3 to the first electrode 1, which is the electron transport destination. Depending on the application, the hole blocking layer 2 may also have a role of blocking hole injection from the first electrode 1.

[0397] The hole blocking layer 2 may further contain a conventionally known hole blocking material (electron transporting material) in addition to the material for a photoelectric conversion element for an imaging element represented by the above formula (1) or (1'). Examples of conventionally known hole blocking materials (electron transporting materials) include bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, 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), 4,6-bis(3,5-di(pyridin-4-yl)phenyl)-2-methylpyrimidine, N,N'-diphenyl-1,4,5,8-naphthalenetetracarboxylic acid diimide, and N,N'-di(4-pyridyl)-1,4,5,8-naphthalenetetracarboxylic acid diimide.

[0398] The hole blocking layer 2 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.

[0399] [Photoelectric Conversion Layer 3] The photoelectric conversion layer 3, which is a light-receiving layer, is provided between the hole blocking layer 2 and the electron blocking layer 4 described below. Examples of materials for the photoelectric conversion layer 3 include materials having a photoelectric conversion function.

[0400] The photoelectric conversion layer 3 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. In particular, in order to increase the photoelectric conversion efficiency, the photoelectric conversion layer 3 is preferably made of a layer containing at least two materials (organic components).

[0401] Examples of materials used for the photoelectric conversion layer 3, which has a single layer structure made of one type of material, include (i) coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives, and the like.

[0402] Examples of materials used for the photoelectric conversion layer 3, which has a single layer structure made of two materials, include the above-mentioned combinations of (i) coumarin and its derivatives, quinacridone and its derivatives, and phthalocyanine and its derivatives with (ii) fullerene and its derivatives. The photoelectric conversion layer 3 made of these materials may be formed by depositing a mixture of powders in advance, or by co-depositing the materials in any ratio.

[0403] Examples of materials used for the photoelectric conversion layer 3, which has a single layer structure made of three materials, include the above-mentioned combinations of (i) coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives, (ii) fullerene and its derivatives, and (iii) hole transport materials. The photoelectric conversion layer 3 made of these materials may be formed by depositing a mixture of powders in advance, or by co-depositing the materials in any ratio.

[0404] (i) Specific examples of coumarin derivatives include coumarin 6 and coumarin 30. Specific examples of quinacridone derivatives include N,N-dimethylquinacridone. Specific examples of phthalocyanine derivatives include boron subphthalocyanine chloride and boron subnaphthalocyanine chloride (SubNC).

[0405] (ii) Specific examples of fullerenes and derivatives thereof include

[60] fullerene,

[70] fullerene, and [6,6]-phenyl-C61-methyl butyrate (

[60] PCBM).

[0406] (iii) The hole transport material may be a known hole transport material. Examples of the hole transport material include aromatic tertiary amine compounds, naphthalene compounds, anthracene compounds, tetracene compounds, pentacene compounds, phenanthrene compounds, pyrene compounds, perylene compounds, fluorene compounds, carbazole compounds, indole compounds, pyrrole compounds, picene compounds, thiophene compounds, benzotrifuran compounds, benzotrithiophene compounds, naphthodithiophene compounds, naphthothienothiophene compounds, benzodifuran compounds, benzodithiophene compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, chrysenodithiophene compounds, benzothienobenzothiophene compounds, and indolocarbazole compounds. Among these, fluorene compounds, naphthodithiophene compounds, naphthothienothiophene compounds, benzodifuran compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, chrysenodithiophene compounds, benzothienobenzothiophene compounds, indolocarbazole compounds, and the like are preferred, and fluorene compounds, chrysenodithiophene compounds, benzothienobenzothiophene compounds, and indolocarbazole compounds are more preferred.

[0407] Specific examples of hole transport materials include 9,9'-(9,9'-spirobi[9H-fluorene]-2,7'-diyl)bis[9H-carbazole], 2,7-diphenyl[1]benzothieno[3,2-b][1]benzothiophene (DiPh-BTBT), benzo[1,2-b:3,4-b':5,6-b'']trifuran compounds, benzo[1,2-b:3,4-b':5,6-b'']trithiophene compounds, naphtho[1,2-b:5,6-b']dithiophene, naphtho[2,3-b]naphtho[2' ,3':4,5]thieno[2,3-d]thiophene, benzo[1,2-b:4,5-b']difuran, benzo[1,2-b:4,5-b']dithiophene, benzo[1,2-b:4,5-b']bis[1]benzothiophene, naphtho[1,2-b:5,6-b']bis[1]benzothiophene, chryseno[1,2-b:8,7-b']dithiophene, [1]benzothieno[3,2-b][1]benzothiophene, and the following compounds (ic-1), (ic-2) and (ic-3).

[0408]

[0409] Furthermore, the material for a photoelectric conversion element for an imaging device is not limited to being contained only in the photoelectric conversion layer 3. For example, the material for a photoelectric conversion element for an imaging device may be contained in a layer adjacent to the photoelectric conversion layer 3 (hole blocking layer 2 or electron blocking layer 4).

[0410] [Electron Blocking Layer 4 ] The electron blocking layer 4 is provided between the photoelectric conversion layer 3 and the hole transport layer 5 .

[0411] The electron blocking layer 4 has a role of transporting holes generated in the photoelectric conversion layer 3 from the photoelectric conversion layer 3 to the second electrode 6, and a role of blocking electrons generated in the photoelectric conversion layer 3 from moving toward the second electrode 6. Depending on the application, the electron blocking layer 4 may also have a role of blocking electron injection from the second electrode 6.

[0412] The electron blocking layer 4 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. For example, it may have a two-layer structure including a layer made of a material specialized for electron blocking properties and adjacent to the photoelectric conversion layer 3, and a layer made of a material specialized for hole transport properties and adjacent to the hole transport layer 5.

[0413] The electron blocking layer 4 preferably contains a known hole transport material. Examples of known hole transport materials include the same materials as those used in the photoelectric conversion layer 3 described above.

[0414] [Hole Transport Layer 5] The hole transport layer 5 is provided between the electron blocking layer 4 and the second electrode 6 described later. The hole transport layer 5 is provided to promote hole transport from the electron blocking layer 4 to the second electrode 6. The promotion of hole transport is brought about by changing the internal electric field due to the interaction of the hole transport material with surrounding materials. Furthermore, when the second electrode 6 is formed by a sputtering method, the hole transport layer 5 serves to reduce damage to the organic layer (e.g., the electron blocking layer 4) during sputtering.

[0415] The hole transport layer 5 may be made of a known material, such as naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN), or the like.

[0416] The hole transport layer 5 may have a single layer structure made of one or more materials, and may contain, for example, the above-mentioned material and a conventionally known hole transport material. Conventionally known hole transport materials can be used, including the same materials as those used in the photoelectric conversion layer 3.

[0417] [Second Electrode 6 ] The second electrode 6 is provided on the electron blocking layer 5 .

[0418] The material of the second electrode 6 may be sodium, a sodium-potassium alloy, magnesium, lithium, a magnesium / copper mixture, a magnesium / silver mixture, a magnesium / aluminum mixture, a magnesium / indium mixture, or aluminum / aluminum oxide (Al ２ O ３ ) mixtures, indium, lithium / aluminum mixtures, gold, and rare earth metals.

[0419] [Method of Forming Each Layer] Each layer except for the first electrode 1 and the second electrode 6 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.

[0420] 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.

[0421] The first electrode 1 serving as the lower electrode and the second electrode 6 serving as the upper electrode can be formed by thinning an electrode material by a method such as vapor deposition or sputtering. A pattern may be formed using a mask of a desired shape during vapor deposition or sputtering, or a pattern of a desired shape may be formed by photolithography after forming a thin film by vapor deposition or sputtering.

[0422] The film thickness of the first electrode 1 and the second electrode 6 is preferably 1 μm or less, and more preferably 10 nm or more and 200 nm or less.

[0423] An imaging element including a photoelectric conversion element according to one aspect of the present invention can be used, for example, as an imaging element for a digital camera or a digital video camera, or as an imaging element built into a mobile phone or the like.

[0424] <Summary> As can be understood from the above description, the present disclosure includes the following aspects.

[0425] Aspect 1: An imaging element including a layer containing a material for a photoelectric conversion element for an imaging element, wherein the material for a photoelectric conversion element for an imaging element is represented by the following formula (1) or formula (1′): In the formula (1), CA is represented by the following formula (1a): Ar １ , and Ar ２ each independently represents a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent heteroaromatic group, or a substituted or unsubstituted divalent cycloaliphatic hydrocarbon group; Ar ３ each independently represents a substituted or unsubstituted mono- to pentavalent aromatic hydrocarbon group, a substituted or unsubstituted mono- to pentavalent heteroaromatic group, or a substituted or unsubstituted mono- to pentavalent cycloaliphatic hydrocarbon group; L １ ~L ３ each independently represents a substituted or unsubstituted di- to tetra-valent aromatic hydrocarbon group, a substituted or unsubstituted di- to tetra-valent heteroaromatic group, or a substituted or unsubstituted di- to tetra-valent cycloaliphatic hydrocarbon group; R １ and R ２ are each independently hydrogen or Ar ３ represents; １ , a ２ , b １ , b ２ and c each independently represent an integer of 1 to 3; d and e each independently represent an integer of 1 or 2; and c+d+e represents an integer of 1 to 3; p, q and r each independently represent an integer of 0 to 3; n represents an integer of 1 to 3; Ar １ , Ar ２ , Ar ３ , L １ , L ２ and L ３at least one of which is selected from the group consisting of a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, and a tetrazinyl group, or a fused ring group consisting of 2 to 4 aromatic monocyclic groups and partially containing at least one selected from the heteroaromatic monocyclic groups; with regard to the material for a photoelectric conversion element for an imaging element represented by the following formula (1'): In the formula (1′), Ar １１ ~Ar ３１ each independently represents a substituted or unsubstituted di- or trivalent aromatic hydrocarbon group, a substituted or unsubstituted di- or trivalent heteroaromatic group, or a substituted or unsubstituted di- or trivalent cycloaliphatic hydrocarbon group; L １１ ~L ３１ each independently represents a substituted or unsubstituted di- to tetra-valent aromatic hydrocarbon group, a substituted or unsubstituted di- to tetra-valent heteroaromatic group, or a substituted or unsubstituted di- to tetra-valent cycloaliphatic hydrocarbon group; １１ , a ２１ , b １１ , b ２１ , c １１ , and c ２１ each independently represents an integer of 1 to 3; １ , q １ and r １ each independently represents an integer of 0 to 3; １１ , Ar ２１ , Ar ３１ , L １１ , L ２１ , and L ３１ At least one of Ar has a cyano group; １１ , Ar ２１ , Ar ３１ , L １１ , L ２１ , and L ３１ wherein the sum of the number of cyano groups contained in these groups and the number of nitrogen-containing heteroaromatic rings constituted by six-membered rings is 2 or more.

[0426] Aspect 2: The imaging element of Aspect 1, wherein in formula (1), n ​​is 1 or 2.

[0427] Aspect 3: In the formula (1), the a １, a ２ , b １ , b ２ and c each independently represent an integer of 1 or 2, and p, q, and r each independently represent an integer of 0 to 2.

[0428] Aspect 4: In the formula (1), the Ar １ , Ar ２ , Ar ３ , L １ , L ２ and L ３ The imaging element according to any one of Aspects 1 to 3, wherein at least one of the groups is a pyridyl group or a pyrimidinyl group.

[0429] Aspect 5: In the formula (1), the Ar １ , Ar ２ , Ar ３ , L １ , L ２ and L ３ and at least two of the groups are pyridyl groups or pyrimidinyl groups.

[0430] Aspect 6: In the formula (1′), the Ar １１ , Ar ２１ , Ar ３１ , L １１ , L ２１ , and L ３１ The imaging element of Aspect 1, wherein the sum of the number of cyano groups and the number of pyridyl groups contained in these groups is 2 or more.

[0431] Aspect 7: An imaging element including a layer containing a material for a photoelectric conversion element for an imaging element, wherein the material for a photoelectric conversion element for an imaging element is represented by the following formula (2): In the formula (2), L ２１Ａ represents a phenylene group; １Ａ represents an integer of 0 or 1; ２１ is represented by any one of formulas (21a) to (24a); In the formulas (21a) to (24a), Ar ２１Ａ are the same or different and represent a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heteroaromatic group; R２２ , and R ２３ are each independently represented by any one of formulas (21b) to (25b); In the formulas (21b) to (25b), Ar ２２Ａ are the same or different and represent a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heteroaromatic group; L ２２Ａ represents a phenylene group or a single bond; * represents a bonding site; Ar in the formulae (21a) to (24a) ２１Ａ and Ar in the formulas (21b) to (25b). ２２Ａ At least one of the Ar groups in the formulae (21a) to (24a) has a cyano group; ２１Ａ and Ar in the formulas (21b) to (25b). ２２Ａ In the formula (I), the sum of the number of cyano groups and the number of pyridyl rings contained in these groups is 2 or more, and ２１ is represented by the formula (21a), and / or R ２２ and R ２３ When at least one of the above is represented by the formula (21b), Ar in the formula (21a) ２１Ａ and Ar in the formula (21b). ２２Ａ and are the same or different and are an aromatic hydrocarbon group substituted with one or more cyano groups or a heteroaromatic group substituted with one or more cyano groups.

[0432] Aspect 8: In the formula (2), the L ２１Ａ The imaging element of Aspect 7, wherein is an o-phenylene group, a p-phenylene group, or a single bond.

[0433] Aspect 9: In the formula (2), the Ar ２１Ａ and are the same or different and are an aromatic hydrocarbon group substituted with a cyano group, or a substituted or unsubstituted heteroaromatic group.

[0434] Aspect 10: In the formula (2), the Ar ２２Ａ and are the same or different and are an aromatic hydrocarbon group substituted with a cyano group, or a substituted or unsubstituted heteroaromatic group.

[0435] Aspect 11: In the formula (2), Ar in the formulas (21a) to (24a) ２１Ａ and Ar in the formulas (21b) to (25b). ２２Ａ The imaging element according to any one of Aspects 7 to 10, wherein at least two of the groups have a cyano group.

[0436] Aspect 12: The imaging element according to any one of Aspects 1 to 11, wherein the material for a photoelectric conversion element for an imaging element has a molecular weight of 550 or more.

[0437] Aspect 13: The imaging element of any one of Aspects 1 to 12, wherein the layer containing the material for a photoelectric conversion element for an imaging element is a hole-blocking layer.

[0438] Aspect 14: A compound represented by formula (11), formula (12), formula (13), formula (14), formula (3) or formula (4), wherein the compound represented by the following formula (11) is: In the formula (11), Ar １１１ and Ar ２１１ each independently represents a 3-pyridyl group or a 4-pyridyl group; Ar ３１１ represents a mono- or divalent phenanthryl group, a mono- or divalent dimethylfluorenyl group, a mono- or divalent diphenylfluorenyl group, a mono- or divalent spirobifluorenyl group, a mono- or divalent triptycenyl group, an aromatic group having 6 to 26 carbon atoms and at least one sulfone group, or a cycloaliphatic hydrocarbon group having 10 to 16 carbon atoms; L ３１１ represents a divalent phenyl group or a divalent pyridyl group, L ３１１ When there are a plurality of r, they may be the same or different; １１ represents an integer of 0 to 2; １１ represents an integer of 1 or 2; a compound having a triazine ring represented by the following formula (12): In the formula (12), L １１２ and L ２１２ represents a divalent pyridyl group; the divalent pyridyl group is bonded to the triazine ring at the 3-position or the 4-position; when the divalent pyridyl group is bonded to the triazine ring at the 4-position, Ar１１２ and Ar ２１２ each independently represents an aromatic hydrocarbon group having 10 to 26 carbon atoms, a nitrogen-containing heteroaromatic group having 6 to 26 carbon atoms and consisting only of a 6-membered ring, an aromatic group having 6 to 26 carbon atoms and having at least one sulfone group, or a cyclic aliphatic hydrocarbon group having 10 to 16 carbon atoms; when the divalent pyridyl group is bonded to the triazine ring at the 3-position, Ar １１２ and Ar ２１２ each independently represents a biphenylyl group, a terphenylyl group, a phenanthryl group, a dimethylfluorenyl group, a diphenylfluorenyl group, a spirobifluorenyl group, a triptycenyl group, an aromatic group having 6 to 26 carbon atoms and at least one sulfone group, or a cycloaliphatic hydrocarbon group having 10 to 16 carbon atoms; Ar ３１２ represents an aromatic hydrocarbon group having 6 to 26 carbon atoms, a nitrogen-containing heteroaromatic group having 6 to 26 carbon atoms and consisting only of a 6-membered ring, an oxygen- or sulfur-containing heteroaromatic group having 4 to 26 carbon atoms, an aromatic group having 6 to 26 carbon atoms and having at least one sulfone group, or a cycloaliphatic hydrocarbon group having 10 to 16 carbon atoms; L ３１２ represents a single bond, a divalent or trivalent phenyl group, or a divalent or trivalent pyridyl group; ４１２ represents a divalent phenyl group or a divalent pyridyl group, L ４１２ When there are a plurality of, they may be the same or different; １２ represents an integer of 1 or 2; a compound represented by the following formula (13): In the formula (13), Ar １１３ and Ar ２１３ each independently represents a 3-pyridyl group or a 4-pyridyl group; Ar ３１３ represents an aromatic hydrocarbon group having 10 to 26 carbon atoms, a nitrogen-containing heteroaromatic group having 2 to 26 carbon atoms and consisting only of a 6-membered ring, an oxygen- or sulfur-containing heteroaromatic group having 4 to 26 carbon atoms, an aromatic group having 6 to 26 carbon atoms and having at least one sulfone group, or a cycloaliphatic hydrocarbon group having 10 to 16 carbon atoms; ３１３ represents a single bond, a divalent or trivalent phenyl group, or a divalent or trivalent pyridyl group; ４１３represents a divalent phenyl group or a divalent pyridyl group, L ４１３ When there are a plurality of, they may be the same or different; １３ represents an integer of 1 or 2; a compound represented by the following formula (14): In the formula (14), Ar １１４ and Ar ２１４ each independently represents a 3-pyridyl group or a 4-pyridyl group; Ar ３１４ represents an aromatic hydrocarbon group having 10 to 24 carbon atoms, a nitrogen-containing heteroaromatic group having 6 to 26 carbon atoms and consisting only of a 6-membered ring, an oxygen- or sulfur-containing heteroaromatic group having 4 to 26 carbon atoms, an aromatic group having 6 to 26 carbon atoms and having at least one sulfone group, or a cycloaliphatic hydrocarbon group having 10 to 16 carbon atoms; ３１４ represents a single bond, a divalent or trivalent phenyl group, or a divalent or trivalent pyridyl group; ４１４ represents a divalent phenyl group or a divalent pyridyl group, L ４１４ When there are a plurality of, they may be the same or different; １４ represents an integer of 1 or 2; a compound represented by the following formula (3): In the formula (3), L ３１Ａ represents a phenylene group; １Ａ represents an integer of 0 or 1; ３１ is represented by any one of formulas (31a) to (34a); In the formulas (31a) to (34a), Ar ３１Ａ are the same or different and represent a phenyl group substituted with one or more cyano groups, a pyridyl group, a pyridyl group substituted with one or more alkyl groups having 1 to 6 carbon atoms, a pyridyl group substituted with one or more cyano groups, or an optionally substituted naphthyl group; R ３２ , and R ３３ are each independently represented by any one of formulas (31b) to (35b); In the formulas (31b) to (35b), Ar ３２Ａare the same or different and represent a phenyl group, a phenyl group substituted with one or more alkyl groups having 1 to 6 carbon atoms, a phenyl group substituted with one or more cyano groups, a pyridyl group, a pyridyl group substituted with one or more alkyl groups having 1 to 6 carbon atoms, a pyridyl group substituted with one or more cyano groups, or a biphenylyl group; L ３２Ａ represents a phenylene group or a single bond; * represents a bonding site; Ar in the formulae (31a) to (34a) ３１Ａ and Ar in the formulas (31b) to (35b). ３２Ａ At least one of R has a cyano group; ３１ is represented by the formula (31a), and / or R ３２ and R ３３ When at least one of the above is represented by the formula (31b), Ar in the formula (31a) ３１Ａ and Ar in the formula (31b). ３２Ａ are the same or different and are a phenyl group substituted with one or more cyano groups, or a pyridyl group substituted with one or more cyano groups, and the compound represented by the following formula (4) is: In the formula (4), Ar ４１ , and Ar ４２ each independently represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 26 carbon atoms, a substituted or unsubstituted nitrogen-containing heteroaromatic group having 3 to 26 carbon atoms and consisting only of a 6-membered ring, a substituted or unsubstituted oxygen-containing or sulfur-containing heteroaromatic group having 3 to 26 carbon atoms, or a cycloaliphatic hydrocarbon group having 10 to 16 carbon atoms; L ４１ ~L ４３ each independently represents a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 26 carbon atoms, a substituted or unsubstituted divalent nitrogen-containing heteroaromatic group having 3 to 26 carbon atoms and consisting only of a 6-membered ring, a substituted or unsubstituted divalent oxygen-containing or sulfur-containing heteroaromatic group having 3 to 26 carbon atoms, or a divalent cycloaliphatic hydrocarbon group having 10 to 16 carbon atoms; ４ , q ４ and r ４ each independently represents an integer of 0 to 2; ４１ , Ar ４２ , L ４１ , L４２ , and L ４３ At least one of the groups has a cyano group.

[0439] Aspect 15: In the formula (4), the L ４１ , L ４２ , and L ４３ A compound according to embodiment 14, wherein each independently represents a phenyl group optionally substituted with a cyano group, or a pyridyl group optionally substituted with a cyano group.

[0440] Aspect 16: In the formula (4), the Ar ４１ , Ar ４２ , L ４１ , L ４２ , and L ４３ 16. The compound according to embodiment 14 or 15, wherein the sum of the number of cyano groups contained in these groups and the number of nitrogen-containing heteroaromatic rings constituted by 6-membered rings is 2 or more.

[0441] Aspect 17: In the formula (4), the Ar ４１ , Ar ４２ , L ４１ , L ４２ , and L ４３ The compound according to any one of Aspects 14 to 16, wherein the sum of the number of cyano groups and the number of pyridyl groups contained in these groups is 2 or more.

[0442] Aspect 18: A material for a photoelectric conversion element for an imaging element, comprising the compound according to any one of Aspects 14 to 17.

[0443] Aspect 19: The material for a photoelectric conversion element for an imaging element according to Aspect 18, which is a hole-blocking material.

[0444] Aspect 20: An imaging device comprising a layer containing the material for a photoelectric conversion element for an imaging device according to Aspect 18 or 19.

[0445] <Additional Notes> The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention.

[0446] The present invention will be described in more detail below based on examples, but the present invention should not be construed as being limited to these examples.

[0447] <Example of Material (1) for Photoelectric Conversion Element of Image Sensor> <Synthesis Example 101> 2,2′-(9,9-diphenyl-9H-fluorene-2,7-diyl)bis(4,6-bis(3-pyridyl)-1,3,5-triazine) (CA31-GA2)

[0448]

[0449] (Step 1) N,N'-(9H-fluorene-2,7-dimethylidine)bis-4-pyridylamine (X12) In a flask equipped with a Dean-Stark tube and a reflux condenser, 9,9-diphenyl-9H-fluorene-2,7-dicarboxaldehyde (X11) (2.2 g, 5.8 mmol) and 3-aminopyridine (1.1 g, 12 mmol) were dissolved in dehydrated chloroform (12 mL) and heated under reflux for 4 hours. After confirming the completion of the reaction by NMR, low-boiling fractions were removed under reduced pressure to obtain N,N'-(9H-fluorene-2,7-dimethylidine)bis-4-pyridylamine (X12). The resulting crude product was used in the next reaction without purification (crude yield 3.0 g, crude yield 98%).

[0450] １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 8.45-8.47 (m, 6H), 8.01-7.93 (m, 6H), 7.50 (m, 2H), 7.31 (t, J = 2.7Hz, 2H), 7.29-7.23 (m, 10H).

[0451] ​(Step 2) Under an argon atmosphere, N,N'-(9H-fluorene-2,7-dimethylidine)bis-4-pyridylamine (X12) (3.0 g, 5.7 mmol) was added to a suspension of pyridine-3-carboximidamide hydrochloride (3.7 g, 23 mmol) and potassium carbonate (4.0 g, 29 mmol) in DMF (20 mL) in a two-neck flask, and the mixture was stirred at 100°C for 17 hours. After cooling to room temperature, water and methanol were added, and the solid was collected by filtration. The resulting solid was subjected to alumina column chromatography (chloroform) to give 2,2'-(9,9-diphenyl-9H-fluorene-2.7-diyl)bis(4.6-bis(3-pyridyl)-1,3,5-triazine) (CA31-GA2) (yield: 1.5 g, 33%).

[0452] １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 9.91 (dd, J = 2.1, 0.7Hz, 4H), 8.95 (ddd, J = 8.3, 3.9, 3.9H z, 4H), 8.87 (dd, J = 5.0, 1.8Hz, 4H), 8.86 (s, 2H), 8.11 (d, J = 7.8Hz , 2H), 8.10 (d, J=7.8Hz, 2H), 7.54 (ddd, J=7.2, 4.8, 0.8Hz, 4H), 7. 42 (d, J = 7.0 Hz, 4H), 7.34 (t, J = 7.4 Hz, 4H), 7.30 (d, J = 7.2 Hz, 2H).

[0453] Synthesis Example 102: 2,2'-(9,9-diphenyl-9H-fluorene-2,7-diyl)bis[4,6-bis{4-pyridyl}-1,3,5-triazine] (CA31-GA1)

[0454]

[0455] ​(Step 1) 2,2'-(9,9-diphenyl-9H-fluorene-2,7-diyl)bis[4,6-bis{4-pyridyl}-1,3,5-triazine] (CA31-GA1) In a recovery flask, a suspension of N,N'-(9H-fluorene-2,7-dimethylidine)bis-4-pyridylamine (X12) (2.1 g, 4.0 mmol), pyridine-4-carboximidamide hydrochloride (5.0 g, 32 mmol), and sodium hydroxide (2.6 g, 64 mmol) in diethylene glycol dimethyl ether (80 mL) was stirred at 150°C for 2 days. After allowing to cool to room temperature, 22 mL of 10% hydrochloric acid was added and the mixture was stirred for 30 minutes. Thereafter, water and methanol were added, and the precipitate was collected by filtration and washed with water, methanol, hexane, and acetone to obtain 2,2′-(9,9-diphenyl-9H-fluorene-2.7-diyl)bis[4.6-bis{4-pyridyl}-1,3,5-triazine (CA31-GA1) (yield: 2.9 g, 93%).

[0456] １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 8.92 (brd, J=6.0Hz, 8H), 8.90 (dd, J=8.0, 1.5Hz, 2H), 8.86 (d, J=1.0Hz, 2H), 8.52 (b rd, J = 6.0Hz, 8H), 8.12 (d, J = 8.0Hz, 2H), 7.44 (brd, J = 6.9Hz, 4H), 7.38-7.29 (m, J = 7.0Hz, 6H).

[0457] Synthesis Example 103: 2-(3-(9,10-dihydro-9,10-[1,2]-benzenoanthracen-2-yl)phenyl)-4,6-bis(pyridin-4-yl)-1,3,5-triazine (CB31-GB49)

[0458]

[0459] ​(Step 1) 2-(3-Bromophenyl)-4,6-bis(pyridin-4-yl)-1,3,5-triazine (X32) Under an argon atmosphere, 3-bromobenzoyl chloride (X31) (3.3 mL, 25 mmol) and isonicotinamide hydrochloride (11.8 g, 75 mmol) were suspended in xylene (250 mL). Triethylamine (11 mL, 75 mmol) was added to this suspension at room temperature, and the mixture was stirred at room temperature for 2 minutes and at 60°C for 20 minutes. 1,1,3,3-tetramethyldisiloxane (13 mL, 75 mmol) was then added, and the mixture was stirred at 150°C for 12 hours, after which the low-boiling fraction was removed under reduced pressure. The obtained solid was washed with water, methanol, hexane and a small amount of acetone to obtain 2-(3-bromophenyl)-4,6-bis(pyridin-4-yl)-1,3,5-triazine (X32) (yield: 3.7 g, 38%).

[0460] １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 8.93 (brdd, J=6.1, 1.6Hz, 4H), 8.89 (brdd, J=1.8, 1.8Hz, 1H), 8.71 (brd, J=8.0Hz, 1H), 8.56 (brdd, J=6.1, 1.6Hz, 4H), 7.80 (brd, J=8.0Hz, 1H), 7.50 (brdd, J=7.9, 7.9Hz, 1H).

[0461] ​(Step 2) 2-(3-(9,10-dihydro-9,10-[1,2]-benzenoanthracen-2-yl)phenyl)-4,6-bis(pyridin-4-yl)-1,3,5-triazine (CB31-GB49) Under an argon atmosphere, 2-(3-bromophenyl)-4,6-bis(pyridin-4-yl)-1,3,5-triazine (X32) (2.7 g, 7.0 mmol), 2-(9,10-dihydro-9,10[1,2]-benzenoanthracen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxoborolane (2.5 g, 6.6 mmol), palladium acetate (79 mg, 0.35 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (334 mg, 0.70 mmol) were suspended in THF (70 mL). 2 M aqueous potassium carbonate solution (14 mL, 28 mmol) was added to the suspension, and the mixture was stirred at 80°C for 2 hours. Further, 2-(9,10-dihydro-9,10[1,2]-benzenoanthracen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxoborolane (692 mg, 1.8 mmol) was added, and the mixture was heated and stirred at 80°C for 13 hours. After cooling to room temperature, chloroform and water were added to the reaction mixture, and the organic layer was extracted. Sodium sulfate and activated carbon were added to the organic layer, and the mixture was stirred, followed by filtration through Celite. Furthermore, the residue was subjected to medium pressure column chromatography using silica gel (100% hexane, then hexane:chloroform=50:50, then 100% chloroform), and further washed with hot toluene, and then washed with hexane, methanol, and a small amount of acetone to obtain 2-(3-(9,10-dihydro-9,10-[1,2]-benzenoanthracen-2-yl)phenyl)-4,6-bis(pyridin-4-yl)-1,3,5-triazine (CB31-GB49) (yield: 1.6 g, 41%).

[0462] １ H-NMR (400MHz, CDCl ３ ​) δ (ppm): 8.91 (brdd, J=6.1, 1.6Hz, 4H), 8.85 (brdd, J=1.6, 1.6Hz, 1H), 8.70 (brd , J=7.8Hz, 1H), 8.54 (brdd, J=6.1, 1.6Hz, 4H), 7.77 (brdd, J=6.1, 1.6Hz, 1H), 7.72 (d, J=1.5Hz, 1H), 7.62 (brdd, J=7.7, 7.7Hz, 1H), 7.54 (d, J=7.6Hz, 1H), 7.48-7.42 (m, 4H), 7.33 (dd, J=7.6, 1.7Hz, 1H), 7.06-7.02 (m, 4H), 5.57 (s, 1H), 5.53 (s, 1H).

[0463] Synthesis Example 104: 2-(3-(6-(9,10-dihydro-9,10-[1,2]-benzenoanthracen-2-yl)-pyridin-3-yl)phenyl)-4,6-bis(pyridin-4-yl)-1,3,5-triazine (CB37-GB49)

[0464]

[0465] (Step 1) 5-chloro-2-(9,10-dihydro-9,10-[1,2]-benzenoanthracen-2-yl)pyridine (X42) Under an argon atmosphere, 2-(9,10-dihydro-9,10[1,2]-benzenoanthracen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxoborolane (12.9 g, 33.8 mmol), 2-bromo-5-chloropyridine (9.83 g, 25.8 mmol), and tetrakis(triphenylphosphine)palladium (2.51 g, 2.2 mmol) were suspended in THF (70 mL). To this suspension was added 2 M aqueous potassium carbonate (50 mL, 100 mmol), and the mixture was stirred at 80°C for 42 hours. After cooling to room temperature, chloroform and water were added to the reaction mixture, and the organic layer was extracted and further washed with saturated brine. Sodium sulfate and activated carbon were added to the organic layer, followed by stirring, followed by filtration through Celite, and the low-boiling fraction was removed under reduced pressure. The resulting solid was purified by column chromatography (hexane:chloroform=100:0 to 50:50) to give 5-chloro-2-(9,10-dihydro-9,10-[1,2]-benzenoanthracen-2-yl)pyridine (X42) (yield: 6.25 g, 66%).

[0466] １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 8.58 (dd, J = 2.5, 0.7Hz, 1H), 8.04 (d, J = 1.7Hz, 1H), 7.66 (dd, J = 8.5, 2.5Hz, 1H), 7.59 (dd, J = 8.6, 0.7Hz, 1H) , 7.54 (dd, J = 7.6, 1.8 Hz, 1H), 7.46 (d, J = 7.7 Hz, 1H), 7.42-7.37 (m, 4H), 7.02-6.98 (m, 4H), 5.51 (s, 1H), 5.47 (s, 1H).

[0467] ​(Step 2) 2-(9,10-dihydro-9,10-[1,2]-benzenoanthracen)-2-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxoborolan-2-yl)pyridine (X43) Under an argon atmosphere, 5-chloro-2-(9,10-dihydro-9,10-[1,2]-benzenoanthracen-2-yl)pyridine (X42) (5.76 g, 15.7 mmol), bis(pinacolato)diboron (4.51 g, 17.7 mmol), palladium acetate (0.18 g, 0.8 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.77 g, 1.6 mmol), and potassium acetate (5.63 g, 57.4 mmol) were suspended in xylene (100 mL) and stirred at 140°C for 23 hours (15.3 g, yield 87%). After cooling to room temperature, chloroform and water were added to the reaction mixture, and the organic layer was extracted and further washed with saturated brine. Sodium sulfate and activated carbon were added to the organic layer, and the mixture was stirred. The mixture was then filtered through Celite, and the low-boiling fraction was removed under reduced pressure to give 2-(9,10-dihydro-9,10-[1,2]-benzenoanthracen)-2-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxoborolan-2-yl)pyridine (X43) (crude yield: 8.21 g, crude yield quant.). This crude product was used in the next reaction without purification.

[0468] １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 8.96 (dd, J = 1.7, 1.0Hz, 1H), 8.12 (d, J = 1.6Hz, 1H), 8.06 (dd, J = 8.0, 1.8Hz, 1H), 7.63 (d, J = 7.8Hz, 1H), 7.60 ( d, J = 7.6 Hz, 1H), 7.46 (d, J = 7.7Hz, 1H), 7.40-7.38 (m, 4H), 7.01-6.97 (m, 4H), 5.52 (s, 1H), 5.47 (s, 1H), 1.35 (s, 12H).

[0469] ​(Step 3) 2-(3-(6-(9,10-dihydro-9,10-[1,2]-benzenoanthracen-2-yl)-pyridin-3-yl)phenyl)-4,6-bis(pyridin-4-yl)-1,3,5-triazine (CB37-GB49) Under an argon atmosphere, 2-(9,10-dihydro-9,10-[1,2]-benzenoanthracen-2-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxoborolan-2-yl)pyridine (X43) (2.51 g, 5.5 mmol), 2-(3-bromophenyl)-4,6-bis(pyridin-4-yl)-1,3,5-triazine (X32) (1.93 g, 4.9 mmol), and tetrakis(triphenylphosphine)palladium (0.32 g, 0.28 mmol) were suspended in xylene (55 mL). A 4 M aqueous potassium phosphate solution (5 mL, 20 mmol) was added to this suspension, and the mixture was stirred at 130°C for 20 hours. After allowing to cool to room temperature, water and methanol were added to the reaction mixture, and the precipitate was collected by filtration. The collected material was suspended in DMF (300 mL), and air was bubbled through it at 140°C for 1.5 hours, followed by filtration through Celite. The low-boiling fraction was removed under reduced pressure, and then water and methanol were added, and the precipitate was collected by filtration. The collected material was suspended in toluene (150 mL), heated to 120°C, and filtered through Celite while hot. The low-boiling fraction was then concentrated under reduced pressure and washed with methanol to give 2-(3-(6-(9,10-dihydro-9,10-[1,2]-benzenoanthracen-2-yl)-pyridin-3-yl)phenyl)-4,6-bis(pyridin-4-yl)-1,3,5-triazine (CB37-GB49) (yield: 1.27 g, 40%).

[0470] １ H-NMR (400MHz, CDCl ３ ​) δ (ppm): 9.06 (brd, J=1.9Hz, 1H), 9.03 (brdd, J=1.6, 1.6Hz, 1H), 8.93 (brdd, J=6.1, 1.6Hz, 4H), 8.80 (brd, J=7.8Hz, 1H), 8.57 (brdd, J=6.1, 1.6Hz, 4H), 8.19 (brd, J=1.6Hz, 1H), 8.06 (dd, J=8.3, 1.6Hz, 1H ), 7.92 (brd, J=7.7Hz, 1H), 7.83 (dd, J=8.3, 0.6Hz, 1H), 7.74 (brdd, J=7.9, 7.9Hz, 1H), 7.69 (brd, J=7 .7, 1.7Hz, 1H) 7.52 (brd, J=7.7Hz, 1H) 7.45-7.41 (m, 4H), 7.04-7.00 (m, 4H), 5.56 (s, 1H), 5.51 (s, 1H).

[0471] Synthesis Example 105: 2-([1,1'-biphenyl]-4-yl)-4,6-bis(2-[9-phenanthryl]pyridin-4-yl)-1,3,5-triazine (CB4-GB2)

[0472]

[0473] (Step 1) 2-(9-Phenanthryl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (X52) Bis(pinacolato)diboron (2.13 g, 8.41 mmol), 4-chloro-2-(9-phenanthryl)pyridine (X51) (2.03 g, 7.01 mmol), potassium acetate (2.08 g, 21.2 mmol), palladium acetate (35.8 mg, 0.159 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (XPhos, 141 mg, 0.296 mmol) were suspended in 30 mL of 1,4-dioxane under a nitrogen stream and reacted at 100°C for 14 hours. A saturated aqueous solution of sodium chloride was added to the reaction solution, and the mixture was extracted with tetrahydrofuran. The organic layer was separated, dehydrated over magnesium sulfate, and concentrated under reduced pressure using a rotary evaporator. Hexane was added to the resulting oil, and the mixture was stirred at room temperature. The resulting solid was collected by filtration to obtain the target compound, 2-(9-phenanthryl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (X52) (yield: 1.80 g, 67%).

[0474] The identification of the obtained compound was １ H-NMR was used.

[0475] １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 1.39 (s, 12H), 7.56-7.73 (m, 5H), 7.87 (s, 1H), 7.93 (d, J = 7.7Hz, 1H), 8.01 (s, 1H) , 8.07 (d, J = 8.3 Hz, 1H), 8.74 (d, J = 8.1 Hz, 1H), 8.78 (d, J = 8.1 Hz, 1H), 8.86 (d, J = 4.8 Hz, 1H).

[0476] ​(Step 2) 2-([1,1'-biphenyl]-4-yl)-4,6-bis(2-[9-phenanthryl]pyridin-4-yl)-1,3,5-triazine (CB4-GB2) Under a nitrogen atmosphere, 2-(9-phenanthryl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (X52) (257 mg, 0.675 mmol) synthesized in Step 1, 2-([1,1'-biphenyl]-4-yl)-4,6-dichloro-1,3,5-triazine (0.102 g, 0.338 mmol), tetrakis(triphenylphosphine)palladium(0) (13 mg, 0.011 mmol), and 2 M aqueous sodium carbonate solution (0.169 mL) were suspended in toluene and reacted at 100°C for 1 hour. Hexane was added to the resulting reaction solution, and the mixture was stirred at room temperature. The resulting solid was collected by filtration to obtain the target compound, 2-([1,1'-biphenyl]-4-yl)-4,6-bis(2-[9-phenanthryl]pyridin-4-yl)-1,3,5-triazine (CB4-GB2) (yield: 0.20 g, 80%).

[0477] The compound obtained was identified by FD-MS measurement using an M-80B manufactured by Hitachi, Ltd. FD-MS: 739.

[0478] Synthesis Example 106: 2,4-bis(3,5-di(pyridin-4-yl)phenyl)-6-(4-(naphthalen-1-yl)phenyl)-1,3,5-triazine (CD1-GB28)

[0479]

[0480] (Step 1) 2-chloro-4,6-bis(3,5-dichlorophenyl)-1,3,5-triazine (X62) Under an argon atmosphere, 1-bromo-3,5-dichlorobenzene (X61) (21 g, 95 mmol) was suspended in THF (260 mL) in a two-neck flask and cooled to 0°C. To this suspension was added 2 M isopropylmagnesium chloride THF solution (50 mL, 100 mmol), and the mixture was stirred at 0°C for 2 hours. Cyanuric chloride (6.2 g, 33 mmol) was then added, and the mixture was warmed to room temperature and stirred overnight. The reaction mixture was concentrated, and water and methanol were added. The precipitate was collected by filtration and washed with water, methanol, and hexane to give crude 2-chloro-4,6-bis(3,5-dichlorophenyl)-1,3,5-triazine (X62) (crude yield: 4.7 g, 69%).

[0481] １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 8.49 (d, J = 2.0 Hz, 4H), 7.64 (t, J = 1.9 Hz, 2H).

[0482] (Step 2) 2,4-bis(3,5-dichlorophenyl)-6-(4-(naphthalen-1-yl)phenyl)-1,3,5-triazine (X63) Under an argon atmosphere, 2-chloro-4,6-bis(3,5-dichlorophenyl)-1,3,5-triazine (X62) (2.8 g, 5.4 mmol), 4-(1-naphthyl)phenylboronic acid (1.6 g, 6.5 mmol), tetrakistriphenylphosphine palladium (0.3 g, 0.3 mmol), and 2 M aqueous sodium carbonate solution (9.7 mL, 19 mmol) were suspended in xylene (100 mL) in a two-necked flask equipped with a reflux condenser, and the suspension was stirred at 140° C. overnight. After allowing to cool to room temperature, water and methanol were added, and the precipitate was collected by filtration and washed with water and methanol. The residue was dissolved in toluene at 120°C, activated carbon was added, and the mixture was stirred. The mixture was then filtered while still warm, and the resulting liquid was concentrated to give 2,4-bis(3,5-dichlorophenyl)-6-(4-(naphthalen-1-yl)phenyl)-1,3,5-triazine (X63) (yield: 2.6 g, 84%).

[0483] １ ​​H-NMR (400MHz, CDCl ３ ) δ (ppm): 8.87 (d, J = 8.4 Hz, 2H), 8.65 (d, J = 2.0 Hz, 4H), 7.95 (dd, J = 9.0, 9.0 Hz, 3H), 7.76 (d, J = 8.4 Hz) , 2H), 7.64 (dd, J = 2.0, 2.0Hz, 2H), 7.59 (dd, J = 8.0, 8.0Hz, 1H), 7.56-7.52 (m, 2H), 7.50-7.46 (m, 1H).

[0484] (Step 3) 2,4-bis(3,5-bis(4,4,5,5-tetramethyl-1,3,2-yl)phenyl)-6-(4-(naphthalen-1-yl)phenyl)-1,3,5-triazine (X64) Under an argon atmosphere, in a two-necked flask equipped with a reflux condenser, 2,4-bis(3,5-dichlorophenyl)-6-(4-(naphthalen-1-yl)phenyl)-1,3,5-triazine (X63) (1.9 g, 3.4 mmol), bis(pinacolato)diboron (3.8 g, 15 mmol), palladium acetate (38 mg, 0.2 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.2 g, 0.3 mmol), and potassium acetate (4.4 g, 45 mmol) were suspended in xylene (70 mL) and stirred at 140°C overnight. After allowing to cool to room temperature, water was added and the organic layer was extracted. The resulting organic layer was heated to 120°C, and activated carbon and magnesium sulfate were added. After stirring, the mixture was filtered through Celite while still warm. The obtained liquid was concentrated to obtain 2,4-bis(3,5-bis(4,4,5,5-tetramethyl-1,3,2-yl)phenyl)-6-(4-(naphthalen-1-yl)phenyl)-1,3,5-triazine (X64) (yield: 3.1 g, 97%).

[0485] １ H-NMR (400MHz, CDCl ３ ​) δ (ppm): 9.30 (d, J = 1.3 Hz, 4H), 8.97 (brd, J = 8.5 Hz, 2H), 8.52 (dd, J = 1.3, 1.3 Hz, 2H), 8.00 (dd, J = 8.2, 0.7 Hz, 1 H), 7.94 (brd, J=7.9Hz, 1H), 7.92 (brd, J=7.9Hz, 1H), 7.76 (brd, J=8.4Hz, 2H), 7.60-7.47 (m, 4H), 1.41 (s, 48H).

[0486] (Step 4) 2,4-bis(3,5-di(pyridin-4-yl)phenyl)-6-(4-(naphthalen-1-yl)phenyl)-1,3,5-triazine (CD1-GB28) Under an argon atmosphere, in a two-necked flask equipped with a reflux condenser, 2,4-bis(3,5-bis(4,4,5,5-tetramethyl-1,3,2-yl)phenyl)-6-(4-(naphthalen-1-yl)phenyl)-1,3,5-triazine (X64) (3.2 g, 3.5 mmol), 4-bromopyridine hydrochloride (3.0 g, 15 mmol), tetrakistriphenylphosphine palladium (0.2 g, 0.2 mmol), and a 4 M aqueous potassium phosphate solution (13 mL, 50 mmol) were suspended in xylene (120 mL) and stirred at 140° C. overnight. After cooling to room temperature, the precipitate was collected by filtration and washed with water, methanol, and hexane. The resulting solid was suspended in 500 mL of toluene and heated with stirring at 120°C. The hot solid was collected by filtration to obtain 2,4-bis(3,5-di(pyridin-4-yl)phenyl)-6-(4-(naphthalen-1-yl)phenyl)-1,3,5-triazine (CD1-GB28) (yield: 2.5 g, 96%).

[0487] １ H-NMR (400MHz, CDCl ３ ​) δ (ppm): 9.13 (d, J = 1.8 Hz, 4H), 8.94 (brd, J = 8.4 Hz, 2H), 8.81 (dd, J = 6.1, 4.4H z, 8H), 8.14 (dd, J=1.8, 1.8Hz, 2H), 7.98 (brd, J=9.0Hz, 2H), 7.95 (brd, J=8.1Hz , 2H), 7.80 (brd, J = 8.4Hz, 2H), 7.74 (dd, J = 6.1, 4.4Hz, 8H), 7.61 (d, J = 7.0Hz, 1 H), 7.59 (d, J = 7.2 Hz, 1H), 7.57-7.52 (m, 2H), 7.48 (ddd, J = 8.3, 6.8, 1.4 Hz, 1H).

[0488] Synthesis Example 107: 4,6-bis(biphenyl-4-yl)-2-[4'-(1-adamantyl)-5-(3-pyridyl)biphenyl-3-yl]-1,3,5-triazine (E-22)

[0489]

[0490] Under an argon atmosphere, 4,6-bis(biphenyl-4-yl)-2-[3-(3-pyridyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1,3,5-triazine (1.50 g, 2.26 mmol), 4-(1-adamantyl)phenyl triflate (1.22 g, 3.39 mmol), palladium acetate (5.07 mg, 0.0226 mmol), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (21.6 mg, 0.0452 mmol), and potassium carbonate (0.810 g, 5.87 mmol) were suspended in a mixed solvent of tetrahydrofuran (75 mL) and water (6 mL), heated to 70° C., and stirred for 17 hours. After cooling to room temperature, water (50 mL) was added to the reaction mixture, and the precipitate was collected by filtration. The resulting precipitate was purified by silica gel chromatography (developing solvent: a 1:2 mixed solvent of chloroform and hexane) and recrystallization with toluene to obtain the target compound, 4,6-bis(biphenyl-4-yl)-2-[4'-(1-adamantyl)-5-(3-pyridyl)biphenyl-3-yl]-1,3,5-triazine (E-22), as a white solid (yield: 0.97 g, 57%). The T ｇThe temperature was 155°C.

[0491] １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 9.07 (d, J = 1.7 Hz, 1H), 9.05 (t, J = 1.6 Hz, 1H), 8.95 (t, J = 1.6 Hz, 1H), 8.86 (d, J =8.6Hz, 4H), 8.68 (dd, J=4.9Hz, 1.6Hz, 1H), 8.08 (ddd, J=1.7Hz, 2.3Hz, 7.9Hz, 1H) 8.00 (t, J=1.8Hz, 1H), 7.81 (d, J=8.5Hz, 4H), 7.76 (d, J=8.5Hz, 2H), 7.71 (d, J=7.0Hz, 4H), 7 .55 (d, J=8.5Hz, 2H), 7.52-7.39 (m, 7H), 2.14 (brs, 3H), 2.01 (brs, 6H), 1.81 (brs, 6H).

[0492] Synthesis Example 108: 4,6-bis(biphenyl-4-yl)-2-[3-(4-pyridyl)-5-(9-phenanthryl)phenyl]-1,3,5-triazine (E-21)

[0493]

[0494] By the same procedure as in Synthesis Example 107, the target product, 4,6-bis(biphenyl-4-yl)-2-[3-(4-pyridyl)-5-(9-phenanthryl)phenyl]-1,3,5-triazine (E-21), was obtained as a white solid.

[0495] Synthesis Example 109: 4,6-bis(biphenyl-4-yl)-2-[4'-(3-pyridyl)-5-(9-phenanthryl)biphenyl-3-yl]-1,3,5-triazine (E-18)

[0496]

[0497] By the same procedure as in Synthesis Example 107, the target product, 4,6-bis(biphenyl-4-yl)-2-[4'-(3-pyridyl)-5-(9-phenanthryl)biphenyl-3-yl]-1,3,5-triazine (E-18), was obtained as a white solid.

[0498] ​Synthesis Example 110: 4,6-bis(biphenyl-4-yl)-2-[3-(2-phenyl-4-pyridyl)-5-(9-phenanthryl)phenyl]-1,3,5-triazine (E-19)

[0499]

[0500] The same procedure as in Synthesis Example 107 was carried out to obtain the target product, 4,6-bis(biphenyl-4-yl)-2-[3-(2-phenyl-4-pyridyl)-5-(9-phenanthryl)phenyl]-1,3,5-triazine (E-19), as a white solid.

[0501] Synthesis Example 111: 4,6-bis(biphenyl-4-yl)-2-[4'-(4-pyridyl)-5-(9-phenanthryl)biphenyl-3-yl]-1,3,5-triazine (E-17)

[0502]

[0503] By the same procedure as in Synthesis Example 107, the target product, 4,6-bis(biphenyl-4-yl)-2-[4'-(4-pyridyl)-5-(9-phenanthryl)biphenyl-3-yl]-1,3,5-triazine (E-17), was obtained as a white solid.

[0504] Synthesis Example 112: 4,6-bis(biphenyl-4-yl)-2-[3-(2-phenyl-3-pyridyl)-5-(9-phenanthryl)phenyl]-1,3,5-triazine (E-20)

[0505]

[0506] The same procedure as in Synthesis Example 107 was carried out to obtain the target product, 4,6-bis(biphenyl-4-yl)-2-[3-(2-phenyl-3-pyridyl)-5-(9-phenanthryl)phenyl]-1,3,5-triazine (E-20), as a white solid.

[0507] Synthesis Example 113: 4,6-bis(biphenyl-4-yl)-2-{4-[6-(biphenyl-4-yl)pyridin-3-yl]phenyl]-1,3,5-triazine (E-29)

[0508]

[0509] The same procedure as in Synthesis Example 107 was carried out to obtain the target product, 4,6-bis(biphenyl-4-yl)-2-{4-[6-(biphenyl-4-yl)pyridin-3-yl]phenyl}-1,3,5-triazine (E-29), as a white solid.

[0510] Synthesis Example 114: 2,4-di([1,1′-biphenyl]-4-yl)-6-(4′-(adamantan-1-yl)-5-(2-phenylpyridin-3)-yl)-[1,1′-biphenyl]-3-yl)-1,3,5-triazine (E-33)

[0511]

[0512] Under an argon atmosphere, 2,4-di([1,1'-biphenyl]-4-yl)-6-chloro-1,3,5-triazine (1.4 g, 3.3 mmol), 3-(4'-(-adamantan-1-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1'-biphenyl]-3-yl)-2-phenylpyridine (2.0 g, 3.5 mmol), and tetrakis(triphenylphosphine)palladium (0.12 g, 0.010 mmol) were suspended in THF (33 mL). To this suspension was added 2 M aqueous potassium carbonate solution (5.4 mL, 11 mmol), and the mixture was refluxed for 17 hours. Water was added to the reaction solution, and the solid was collected by filtration and washed with water, methanol, and hexane. The obtained solid was dissolved in hot toluene, activated carbon was added, and the mixture was stirred, followed by hot filtration using Celite. The filtrate was allowed to stand at room temperature, and the precipitated solid was collected by filtration to give 2,4-di([1,1'-biphenyl]-4-yl)-6-(4'-(adamantan-1-yl)-5-(2-phenylpyridin-3)-yl)-[1,1'-biphenyl]-3-yl)-1,3,5-triazine (E-33) (1.8 g, 65%).

[0513] １ H-NMR (400MHz, CDCl ３ ​) δ (ppm): 8.92 (dd, J=1.6, 1.6Hz, 1H), 8.83 (brd, J=8.5Hz, 4H), 8.79 (dd, J=4.8, 1.7H z, 1H), 8.68 (dd, J = 1.6, 1.6Hz, 1H), 8.00 (dd, J = 7.9, 1.7Hz, 1H), 7.83 (brd, J = 8.5Hz, 4 H), 7.73 (brd, J=7.4Hz, 4H), 7.58 (dd, J=1.6.1.6Hz, 1H), 7.55-7.49 (m, 6H), 7.49-7.4 0 (m, 7H), 7.37-7.29 (m, 3H), 2.17-2.11 (m, 3H), 2.00-1.96 (m, 6H), 1.87-1.74 (m, 6H).

[0514] Synthesis Example 115: 2-(4-(adamantan-1-yl)phenyl)-4,6-bis(4-(2-phenylpyridin-3-yl)phenyl)-1,3,5-triazine (E-39)

[0515]

[0516] Under an argon atmosphere, 2-(4-(adamantan-1-yl)phenyl)-4,6-bis(4-chlorophenyl)-1,3,5-triazine (1.5 g, 2.9 mmol), 2-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (1.8 g, 6.5 mmol), palladium acetate (33 mg, 0.15 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (140 mg, 0.29 mmol) were suspended in THF (30 mL). To this suspension was added 2M aqueous potassium carbonate solution (10 mL, 20 mmol), and the mixture was refluxed for 17 hours. Water was added to the reaction solution, followed by extraction with toluene, and the organic layer was washed with water. The organic layer was separated, sodium sulfate and activated carbon were added, and the mixture was stirred. After filtration through Celite, the solvent was evaporated. The obtained solid was washed with hot octane and hot ethanol to obtain 2-(4-(adamantan-1-yl)phenyl)-4,6-bis(4-(2-phenylpyridin-3-yl)phenyl)-1,3,5-triazine (E-39) (1.7 g, 77%).

[0517] １ H-NMR (400MHz, CDCl​３ ) δ (ppm): 8.75 (dd, J=4.8, 1.6Hz, 2H), 8.67 (brd, J=8.4Hz, 4H), 8.66 (brd, J=8.6Hz, 2H), 7.82 (dd, J=7.7, 1.7Hz, 2H), 7. 55 (brd.

[0518] <Glass Transition Temperature and LUMO Level> The glass transition temperatures of the compounds (CA31-GA2), (CA31-GA1), (C31-GB49), (CB37-GB49), (CB4-GB2), (CD1-GB28), (E-22), (E-21), (E-18), (E-19), (E-17), (E-20), (E-29), (E-33), and (E-39) of Synthesis Examples 101 to 115, as well as comparative compounds 1 and 2 described in Patent Document 1 and comparative compound 3 described in Patent Document 2 were measured using a differential scanning calorimeter (DSC7020 manufactured by Hitachi High-Technologies) at a sweep rate of 10°C / min using an aluminum pan. Furthermore, for the LUMO level, Gaussian 16 software was used, and density functional theory (DFT) was used under calculation conditions of the B3LYP functional and 6-31G(d) basis set to optimize the molecular structure and calculate the LUMO level. The obtained glass transition temperature and LUMO level (calc.LUMO) results are summarized in the table below. In the table below, "N.D." means "not detected." That is, compounds (CA31-GA2), (CA31-GA1), and comparative compounds 1 and 2 are crystalline, not amorphous. In the table below, "-" means not measured.

[0519]

[0520] The results in the above table show that, as a material for a photoelectric conversion element, the compound represented by formula (1) has excellent thermal stability of the film compared to the comparative compounds 1 to 3, and has a deeper calculated LUMO level (calc. LUMO) than the comparative compounds (values ​​are lower in the positive direction).

[0521] <Element Example 101 (see FIG. 1)> As shown in FIG. 1, an imaging element 100 was fabricated as a photoelectric conversion element having a layered structure including a first electrode 1, a hole blocking layer 2, a photoelectric conversion layer 3, an electron blocking layer 4, a hole transport layer 5, and a second electrode 6, and the dark current, external quantum efficiency, and responsiveness of the imaging element were evaluated.

[0522] (Preparation of First Electrode 1) 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 a first electrode on its surface. The substrate was then washed with isopropyl alcohol and then subjected to surface treatment by ozone ultraviolet cleaning.

[0523] (Preparation for Vacuum Deposition) Each layer was vacuum-deposited on the cleaned and surface-treated substrate by a vacuum deposition method, and each layer was laminated.

[0524] First, the glass substrate was placed in a vacuum deposition chamber. －５ The pressure was reduced to Pa. Then, each layer was formed in the following order according to the film formation conditions.

[0525] (Preparation of Hole Blocking Layer 2) The sublimation-purified compound (CA31-GA2) was formed into a film having a thickness of 10 nm at a rate of 0.03 nm / second to prepare a hole blocking layer 2.

[0526] (Preparation of Photoelectric Conversion Layer (Light Receiving Layer) 3) A 120 nm thick film was formed by mixing N,N-dimethylquinacridone and C60 in a ratio of 4:1 (mass ratio) to prepare photoelectric conversion layer 3. The film formation rate was 0.15 nm / sec.

[0527] (Preparation of Electron Blocking Layer 4) Compound (ic-3) was deposited at a rate of 0.10 nm / second to a thickness of 10 nm to prepare electron blocking layer 4. Note that (ic-3) was synthesized by the method described in JP-A-2018-193371.

[0528] (Preparation of Hole Transport Layer 5) A compound 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN) was deposited at a rate of 0.10 nm / second to form a film of 10 nm, thereby preparing a hole transport layer 5.

[0529] (Fabrication of Second Electrode 6) Finally, a metal mask was placed perpendicular to the ITO stripes on the substrate, and the second electrode 6 serving as the upper electrode was formed. Specifically, a silver film was formed to a thickness of 80 nm at a rate of 0.1 nm / sec, thereby fabricating the second electrode 6 serving as the upper electrode.

[0530] As a result, the area of ​​4 mm as shown in FIG. ２ The thickness of each film was measured using a stylus film thickness meter (DEKTAK, manufactured by Bruker).

[0531] The device was then sealed in a nitrogen atmosphere glove box with oxygen and moisture concentrations of 1 ppm or less by sealing the glass sealing cap and the film-formed substrate (device) with bisphenol F epoxy resin (manufactured by Nagase ChemteX Corporation).

[0532] The image sensor fabricated as described above was evaluated for the current in the dark (dark current), external quantum efficiency, and response time when a voltage of 2.6 V was applied. The dark current was measured using a Keithley Source Measure Unit 2636B. The external quantum efficiency was measured using a solar cell spectral response measurement device (Soma Optical Co., Ltd.). The wavelength of the irradiated light was 560 nm, and the intensity was 50 μW / cm. ２ The response time was measured by irradiating a light pulse and measuring the time it took for the current value to return to the value before irradiation.

[0533] The dark current, external quantum efficiency, and response time are relative values, with the result for Comparative Example Element 101 set as the reference value (1.0). The lower the dark current value, the better the performance, the higher the external quantum efficiency value, and the shorter the response time, the better the performance. The measurement results obtained are shown in the table below.

[0534] <Element Examples 102 to 115, Element Comparative Examples 101 to 103> In Element Example 101, instead of compound (CA31-GA2), compounds (CA31-GA1), (CB31-GB49), (CB37-GB49), (CB4-GB2), (CD1-GB28), (E-22), (E-21), (E-18), (E-19), (E-17), (E-20), (E-29), (E-33), and (E-39), and comparative compounds 1, 2, and 3 were used, respectively, in that order. An imaging photoelectric conversion element was prepared and evaluated in the same manner as in Element Example 101. The measurement results obtained are shown in the table below. In the table below, "-" means "not measured."

[0535]

[0536] The results in the above table show that by forming a layer using the compound represented by formula (1) as a material for a photoelectric conversion element for an imaging device, an imaging photoelectric conversion element having improved at least one of the characteristics of responsiveness, external quantum efficiency, and dark current can be realized, compared to when a layer is formed using a comparative example compound.

[0537] Furthermore, the results of Device Examples 107 to 115 show that, even if the calculated LUMO level (calc. LUMO) of a compound represented by formula (1) is shallower (higher in the positive direction) than that of the comparative compound, the compound contributes to an imaging photoelectric conversion element having excellent response, high external quantum efficiency, and reduced dark current. This is thought to be due to the coordination ability of the pyridyl group and the uniform film quality due to the amorphous nature.

[0538] <Example of Material (1′) for Photoelectric Conversion Element of Image Sensor> <Synthesis Example-201> 4′,4″″,4′″″″-(1,3,5-triazine-2,4,6-triyl)tris(([1,1′:2′,1″-terphenyl]-4,4″-dicarbonitrile)) (D′-16)

[0539] Under an argon atmosphere, 2,4,6-tris(3-bromo-4-iodophenyl)-1,3,5-triazine (2.0 g, 2.2 mmol), 4-cyanophenylboronic acid (3.2 g, 22 mmol), palladium acetate (49 mg, 0.22 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.21 g, 0.43 mmol) were suspended in 1,4-dioxane (43 mL). To this suspension was added 2 M aqueous sodium carbonate solution (11 mL, 22 mmol), and the mixture was refluxed for 17 hours. The reaction solution was filtered and then washed with water, methanol, and hexane. The resulting solid was dried under vacuum and then purified by sublimation to obtain 4',4'''',4'''''''-(1,3,5-triazine-2,4,6-triyl)tris(([1,1':2',1''-terphenyl]-4,4''-dicarbonitrile)) (D'-16) (yield: 0.40 g, 20%).

[0540] １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 8.88 (dd, J = 8.0, 1.7 Hz, 3H), 8.78 (d, J = 1.7 Hz, 3H), 7.67 (d, J = 8.0 Hz, 3H), 7.63 (br d, J=8.4Hz, 6H), 7.60 (brd, J=8.4Hz, 6H), 7.35 (brd, J=8.4Hz, 6H), 7.29 (brd, J=8.4Hz, 6H).

[0541] Synthesis Example 202: 4',4''''-(6-phenyl-1,3,5-triazine-2,4-diyl)bis(([1,1':2',1''-terphenyl]-4,4''-dicarbonitrile)) (D'-08)

[0542] ​Under an argon atmosphere, 2,4-bis(3,4-dichlorophenyl)-6-phenyl-1,3,5-triazine (1.7 g, 3.8 mmol), 4-cyanophenylboronic acid (3.4 g, 23 mmol), palladium acetate (85 mg, 0.38 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.36 g, 0.76 mmol) were suspended in THF (19 mL). To this suspension was added 2 M aqueous sodium carbonate solution (11 mL, 23 mmol), and the mixture was refluxed for 18 hours. The reaction solution was filtered and then washed with water, methanol, and hexane. The resulting solid was dissolved in toluene heated to 110°C, activated carbon was added, and the mixture was stirred, followed by hot filtration through Celite. The filtrate was allowed to stand at room temperature, and the precipitated solid was collected by filtration to obtain 4',4''''-(6-phenyl-1,3,5-triazine-2,4-diyl)bis(([1,1':2',1''-terphenyl]-4,4''-dicarbonitrile)) (D'-08) (yield: 2.1 g, 77%).

[0543] １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 8.90 (dd, J=8.1, 1.7Hz, 2H), 8.81 (d, J=1.7Hz, 2H), 8.76 (brd, J=7.0 Hz, 2H), 7.69-7.57 (m, 13H), 7.37 (brd, J=8.4Hz, 4H), 7.30 (brd, J=8.4Hz, 4H).

[0544] Synthesis Example 203: 4'-(4-(3',4'-dicyano-[1,1'-biphenyl]-4-yl)-6-phenyl-1,3,5-triazin-2-yl)-[1,1:2',1''-terphenyl]-4,4''-dicarbonitrile (CC'105-GC'1)

[0545] ​Under an argon atmosphere, 4'-(4-(4-chlorophenyl)-6-phenyl-1,3,5-triazin-2-yl)-[1,1':2',1''-terphenyl]-4,4''-dicarbonitrile (1.8 g, 3.3 mmol), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phthalonitrile (0.92 g, 3.6 mmol), palladium acetate (22 mg, 99 μmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (94 mg, 0.20 mmol) were suspended in THF (33 mL). A 2M aqueous solution of potassium carbonate (5.5 mL, 11 mmol) was added to this suspension, and the mixture was refluxed for 17 hours. Water was added to the reaction solution, and the solid was collected by filtration and washed with water, methanol, and hexane. The obtained solid was dissolved in toluene heated to 110°C, activated carbon was added, and the mixture was stirred, followed by hot filtration using Celite. The filtrate was allowed to stand at room temperature, and the precipitated solid was collected by filtration to obtain 4'-(4-(3',4'-dicyano-[1,1'-biphenyl]-4-yl)-6-phenyl-1,3,5-triazin-2-yl)-[1,1:2',1"-terphenyl]-4,4"-dicarbonitrile (CC'105-GC'1) (yield: 1.4 g, 69%).

[0546] １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 8.93 (brd, J=8.7Hz, 2H), 8.92 (dd, J=8.1, 1.8Hz, 1H), 8.81( d, J=1.8Hz, 1H), 8.78 (brd, J=6.7Hz, 2H), 8.12 (d, J=1.7Hz, 1H), 8.04( dd, J=8.2, 1.7Hz, 1H), 7.95 (d, J=8.2Hz, 1H), 7.81 (brd, J=8.4Hz, 2H) , 7.70-7.58 (m, 8H), 7.38 (brd, J=8.4Hz, 2H), 7.31 (brd, J=8.4Hz, 2H).

[0547] ​Synthesis Example 204: 4'-(4-([1,1'-biphenyl]-4-yl)-6-(4'-cyano-[1,1'-biphenyl]-4-yl)-1,3,5-triazin-2-yl)-[1,1':2',1''-terphenyl]-4,4''-dicarbonitrile (CC'94-GC'1)

[0548] Under an argon atmosphere, 4'-(4-([1,1'-biphenyl]-4-yl)-6-(4-chlorophenyl)-1,3,5-triazin-2-yl)-[1,1':2',1''-terphenyl]-4,4''-dicarbonitrile (2.5 g, 4.0 mmol), 4-cyanophenylboronic acid (0.71 g, 4.8 mmol), palladium acetate (27 mg, 0.12 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.12 g, 0.24 mmol) were suspended in THF (40 mL). To this suspension was added 2 M aqueous potassium carbonate solution (2.8 mL, 5.6 mmol), and the mixture was refluxed for 17 hours. Water was added to the reaction solution, and the solid was collected by filtration and washed with water, methanol, and hexane. The obtained solid was dissolved in toluene heated to 110°C, activated carbon was added, and the mixture was stirred, followed by hot filtration using Celite. The filtrate was allowed to stand at room temperature, and the precipitated solid was collected by filtration to give 4'-(4-([1,1'-biphenyl]-4-yl)-6-(4'-cyano-[1,1'-biphenyl]-4-yl)-1,3,5-triazin-2-yl)-[1,1':2',1"-terphenyl]-4,4"-dicarbonitrile (CC'94-GC'1) (yield: 1.5 g, 54%).

[0549] １ H-NMR (400MHz, CDCl ３ ​) δ (ppm): 8.94 (dd, J = 8.2, 1.7 Hz, 1H) 8.90 (brd, J = 8.5 Hz, 2H), 8.86 (brd, J = 8.5 Hz, 2H), 8.83 (d , J=1.7Hz, 1H), 7.84 (brd, J=8.5Hz, 2H), 7.83 (brd, J=8.5Hz, 2H), 7.81 (brs, 4H), 7.72 (brd, J=7 .. 0Hz, 2H), 7.68 (d, J = 8.2Hz, 1H), 7.65 (brd, J = 8.5Hz, 2H), 7.61 (brd, J = 8.5Hz, 2H), 7.52 (brdd, J=7.3, 7.0Hz, 2H), 7.44 (brt, J=7.3Hz, 1H), 7.38 (brd, J=8.5Hz, 2H), 7.32 (brd, J=8.5Hz, 2H).

[0550] Synthesis Example 205: 4'-(4-([1,1'-biphenyl]-4-yl)-6-(3',5'-dicyano-[1,1'-biphenyl]-4-yl)-1,3,5-triazin-2-yl)-[1,1':2',1''-terphenyl]-4,4''-dicarbonitrile (CC'112-GC'1)

[0551] Under an argon atmosphere, 4'-(4-([1,1'-biphenyl]-4-yl)-6-(4-chlorophenyl)-1,3,5-triazin-2-yl)-[1,1':2',1''-terphenyl]-4,4''-dicarbonitrile (2.5 g, 4.0 mmol), 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)isophthalonitrile (1.2 g, 4.8 mmol), palladium acetate (27 mg, 0.12 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.12 g, 0.24 mmol) were suspended in THF (40 mL). 2 M aqueous potassium carbonate solution (7.3 mL, 15 mmol) was added to this suspension, and the mixture was refluxed for 17 hours. Water was added to the reaction solution, and the solid was collected by filtration and washed with water, methanol, and hexane. The obtained solid was washed with toluene heated to 110°C to obtain 4'-(4-([1,1'-biphenyl]-4-yl)-6-(3',5'-dicyano-[1,1'-biphenyl]-4-yl)-1,3,5-triazin-2-yl)-[1,1':2',1"-terphenyl]-4,4"-dicarbonitrile (CC'112-GC'1) (yield: 2.0 g, 70%).

[0552] １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 8.94 (brd, J=8.5Hz, 2H), 8.93 (dd, J=8.1, 1.6Hz, 1H), 8.86 (brd, J=8.5Hz, 2H), 8.82 (d, J=1.6 Hz, 1H), 8.19 (d, J = 1.5Hz, 2H), 7.98 (t, J = 1.5Hz, 1H), 7.85 (brd, J = 8.5Hz, 2H), 7.79 (brd, J = 8.5Hz, 2H) , 7.73 (brd, J=7.0Hz, 2H), 7.69 (d, J=8.1Hz, 1H), 7.65 (brd, J=8.4Hz, 2H), 7.60 (brd, J=8.4Hz, 2H), 7.5 3 (brdd, J=7.3, 7.0Hz, 2H), 7.44 (brt, J=7.3Hz, 1H), 7.38 (brd, J=8.4Hz, 2H), 7.32 (brd, J=8.4Hz, 2H).

[0553] ​Synthesis Example 206: 4'-(4-(4-([1,1'-biphenyl]-4-yl)-6-(4-cyanophenyl)-1,3,5-triazin-2-yl)phenyl)-[1,1':2',1''-terphenyl]-4,4''-dicarbonitrile (CC'119-GC'1)

[0554] Under an argon atmosphere, 4-(4-([1,1'-biphenyl]-4-yl)-6-(4-chlorophenyl)-1,3,5-triazin-2-yl)benzonitrile (2.0 g, 4.5 mmol), 4'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1':2',1''-terphenyl]-4,4''-dicarbonitrile (2.0 g, 5.0 mmol), palladium acetate (30 mg, 0.14 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.13 g, 0.27 mmol) were suspended in THF (45 mL). 2M aqueous potassium carbonate solution (7.5 mL, 15 mmol) was added to this suspension, and the mixture was refluxed for 17 hours. Water was added to the reaction solution, and the solid was collected by filtration and washed with water, methanol, and hexane. The obtained solid was dissolved in toluene heated to 110°C, activated carbon was added, and the mixture was stirred, followed by hot filtration using Celite. The filtrate was allowed to stand at room temperature, and the precipitated solid was collected by filtration to obtain 4'-(4-(4-([1,1'-biphenyl]-4-yl)-6-(4-cyanophenyl)-1,3,5-triazin-2-yl)phenyl)-[1,1':2',1"-terphenyl]-4,4"-dicarbonitrile (CC'119-GC'1) (yield: 1.6 g, 52%).

[0555] １ H-NMR (400MHz, CDCl ３ ​) δ (ppm): 8.93 (brd, J = 8.5Hz, 2H), 8.89 (brd, J = 8.5Hz, 2H), 8.85 (brd , J = 8.5Hz, 2H), 7.93-7.82 (m, 7H), 7.76 (d, J = 1.8Hz, 1H), 7.73 (brd, J =7.1Hz, 2H), 7.63-7.57(m, 5H), 7.52(brdd, J=7.3, 7.3Hz, 2H), 7.44( brt, J=7.3Hz, 1H), 7.32 (brd, J=8.5Hz, 2H), 7.29 (brd, J=8.5Hz, 2H).

[0556] Synthesis Example 207: 2'-(4-(4-([1,1'-biphenyl]-4-yl)-6-(4-cyanophenyl)-1,3,5-triazin-2-yl)phenyl)-[1,1':4',1''-terphenyl]-4,4''-dicarbonitrile (CC'119-GC'21)

[0557] Under an argon atmosphere, 4-(4-([1,1'-biphenyl]-4-yl)-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3,5-triazin-2-yl)benzonitrile (1.6 g, 2.9 mmol), 2'-chloro-[1,1':4',1''-terphenyl]-4,4''-dicarbonitrile (0.97 g, 3.1 mmol), palladium acetate (66 mg, 0.29 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.28 g, 0.57 mmol) were suspended in THF (29 mL). 2M aqueous potassium carbonate solution (4.6 mL, 9.2 mmol) was added to this suspension, and the mixture was refluxed for 17 hours. Water was added to the reaction solution, and then the solid was collected by filtration and washed with water, methanol, and hexane. The obtained solid was washed with toluene heated to 110°C, dissolved in chloroform, and then filtered using Celite. Low boiling points were removed from the filtrate by solvent distillation to obtain 2'-(4-(4-([1,1'-biphenyl]-4-yl)-6-(4-cyanophenyl)-1,3,5-triazin-2-yl)phenyl)-[1,1':4',1''-terphenyl]-4,4''-dicarbonitrile (CC'119-GC'21) (yield: 0.28 g, 14%).

[0558] １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 8.90 (brd, J=8.6Hz, 2H) 8.83 (brd, J=8.6Hz, 2H), 8.71 (brd, J=8.6Hz, 2 H), 7.89 (brd, J=8.6Hz, 2H), 7.83 (brd, J=8.6Hz, 2H), 7.80 (brs, 4H), 7.78-7.69 ( m, 4H), 7.60 (d, J = 8.1Hz, 1H), 7.57 (brd, J = 8.5Hz, 2H), 7.52 (brdd, J = 7.5, 7.5Hz , 2H), 7.44 (brt, J=7.5Hz, 1H), 7.39 (brd, J=8.5Hz, 2H), 7.35 (brd, J=8.5Hz, 2H).

[0559] Synthesis Example 208: 4'-(4-([1,1'-biphenyl]-4-yl)-6-(3'-cyano-[1,1'-biphenyl]-4-yl)-1,3,5-triazin-2-yl)-[1,1':2',1''-terphenyl]-4,4''-dicarbonitrile (CC'98-GC'1)

[0560] ​Under an argon atmosphere, 4'-(4-([1,1'-biphenyl]-4-yl)-6-(4-chlorophenyl)-1,3,5-triazin-2-yl)-[1,1':2',1''-terphenyl]-4,4''-dicarbonitrile (2.5 g, 4.0 mmol), 3-cyanophenylboronic acid (0.71 g, 4.8 mmol), palladium acetate (27 mg, 0.12 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.12 g, 0.24 mmol) were suspended in THF (40 mL). To this suspension was added 2 M aqueous potassium carbonate solution (2.8 mL, 5.6 mmol), and the mixture was refluxed for 17 hours. Water was added to the reaction solution, and the solid was collected by filtration and washed with water, methanol, and hexane. The obtained solid was dissolved in toluene heated to 110°C, activated carbon was added, and the mixture was stirred, followed by hot filtration using Celite. The filtrate was allowed to stand at room temperature, and the precipitated solid was collected by filtration to give 4'-(4-([1,1'-biphenyl]-4-yl)-6-(3'-cyano-[1,1'-biphenyl]-4-yl)-1,3,5-triazin-2-yl)-[1,1':2',1"-terphenyl]-4,4"-dicarbonitrile (CC'98-GC'1) (yield: 1.5 g, 54%).

[0561] １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 8.94 (dd, J=8.0, 1.6Hz, 1H), 8.90 (brd, J=8.3Hz, 2H), 8.86 (brd, J=8.3Hz, 2H), 8. 84 (d, J = 1.6 Hz, 1H), 7.99 (dd, J = 1.6, 1.6 Hz, 1H), 7.94 (ddd, J = 7.8, 1.6, 1.6 Hz, 1H), 7.85 (b rd, J=8.3Hz, 2H), 7.80 (brd, J=8.3Hz, 2H), 7.74-7.59 (m, 8H), 7.52 (brdd, J=7.8, 7.3Hz, 2H ), 7.44 (brt, J=7.3Hz, 1H), 7.38 (brd, J=8.1Hz, 2H), 7.32 (brd, J=8.1Hz, 2H), 7.27 (m, 1H).

[0562] ​Synthesis Example 209: 4-(4-([1,1'-biphenyl]-4-yl)-6-(3,4-bis(4-pyridyl))phenyl)-1,3,5-triazin-2-yl)benzonitrile (CC'119-GC'5)

[0563] Under an argon atmosphere, 4-(4-([1,1'-biphenyl]-4-yl)-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3,5-triazin-2-yl)benzonitrile (2.4 g, 4.5 mmol), 3,4-bis(4-pyridyl))phenyl chloride (1.4 g, 5.4 mmol), palladium acetate (50 mg, 0.2 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.2 g, 0.4 mmol) were suspended in THF (45 mL). To this suspension was added 2 M aqueous potassium carbonate solution (8.1 mL, 16 mmol), and the mixture was refluxed for 19 hours. After cooling to room temperature, water and methanol were added to the reaction solution, and the solid was then collected by filtration and washed with water and methanol to obtain 4-(4-([1,1'-biphenyl]-4-yl)-6-(3,4-bis(4-pyridyl))phenyl)-1,3,5-triazin-2-yl)benzonitrile (CC'119-GC'5) (yield: 2.5 g, 88%).

[0564] １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 8.93 (brd, J=8.6Hz, 2H), 8.90 (brd, J=8.5Hz, 2H) 8.86 (brd, J=8.6Hz, 2H), 8.56 (brd, J=6.1Hz, 2H), 8.54 (brd, J=6.1Hz, 2H), 7.87-7.92 (m, 5H), 7.84 (d, J=8.6Hz, 2H), 7.78 (d, J=1.8Hz, 1H), 7.73 (d, J=7.1Hz) , 2H), 7.61 (d, J = 8.0Hz, 1H), 7.50-7.54 (m, 2H), 7.44 (t, J = 7.3Hz, 1H), 7.17 (brd, J = 6.1Hz, 2H), 7.12 (brd, J = 6.1Hz, 2H).

[0565] ​Synthesis Example 210: 4'-(4-([1,1'-biphenyl]-4-yl)-6-(4-(5-cyanopyridin-3-yl)phenyl)-1,3,5-triazin-2-yl)-[1,1':2',1''-terphenyl]-4,4''-dicarbonitrile (CC'109-GC'1)

[0566] Under an argon atmosphere, 4'-(4-([1,1'-biphenyl]-4-yl)-6-(4-chlorophenyl)-1,3,5-triazin-2-yl)-[1,1':2',1''-terphenyl]-4,4''-dicarbonitrile (2.7 g, 4.3 mmol), 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)nicotinonitrile (1.2 g, 5.2 mmol), palladium acetate (29 mg, 0.13 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.12 g, 0.26 mmol) were suspended in THF (43 mL). 2 M aqueous potassium carbonate solution (7.8 mL, 16 mmol) was added to this suspension, and the mixture was refluxed for 17 hours. Water was added to the reaction solution, and then the solid was collected by filtration and washed with water, methanol, and hexane. The obtained solid was dissolved in benzonitrile heated to 120°C, activated carbon was added, and the mixture was stirred, and then hot filtered using Celite. The filtrate was allowed to stand at -20°C, and the precipitated solid was collected by filtration to obtain 4'-(4-([1,1'-biphenyl]-4-yl)-6-(4-(5-cyanopyridin-3-yl)phenyl)-1,3,5-triazin-2-yl)-[1,1':2',1''-terphenyl]-4,4''-dicarbonitrile (CC'109-GC'1) (yield: 2.0 g, 67%).

[0567] １ H-NMR (400MHz, CDCl ３ ​) δ (ppm): 9.15 (d, J = 2.2Hz, 1H), 8.98-8.91 (m, 4H), 8.87 (brd, J = 8.5Hz, 2H), 8.83 (d, J = 1.7Hz, 1 H), 8.25 (dd, J=2.2, 2.2Hz, 1H), 7.86 (brd, J=8.5Hz, 2H), 7.81 (brd, J=8.5Hz, 2H), 7.73 (brd, J= 7.1Hz, 2H), 7.69 (d, J = 8.1Hz, 1H), 7.65 (brd, J = 8.4Hz, 2H), 7.61 (brd, J = 8.4Hz, 2H), 7.53 (brdd , J=7.3, 7.1Hz, 2H), 7.44 (brt, J=7.3Hz, 1H), 7.39 (brd, J=8.4Hz, 2H), 7.32 (brd, J=8.4Hz, 2H).

[0568] Synthesis Example 211: 4'-(4-([1,1'-biphenyl]-4-yl)-6-(4-(pyridin-4-yl)phenyl)-1,3,5-triazin-2-yl)-[1,1':2',1''-terphenyl]-4,4''-dicarbonitrile (CC'129-GC'1)

[0569] Under an argon atmosphere, 4'-(4-([1,1'-biphenyl]-4-yl)-6-(4-chlorophenyl)-1,3,5-triazin-2-yl)-[1,1':2',1''-terphenyl]-4,4''-dicarbonitrile (2.3 g, 3.7 mmol), 4-pyridineboronic acid (0.55 g, 4.4 mmol), palladium acetate (25 mg, 0.11 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.11 g, 0.22 mmol) were suspended in THF (37 mL). To this suspension was added 2 M aqueous potassium carbonate solution (2.6 mL, 5.2 mmol), and the mixture was refluxed for 17 hours. Water was added to the reaction solution, and the solid was collected by filtration and washed with water, methanol, and hexane. The obtained solid was dissolved in toluene heated to 110°C, activated carbon was added, and the mixture was stirred, followed by hot filtration using Celite. The filtrate was allowed to stand at room temperature, and the precipitated solid was collected by filtration to give 4'-(4-([1,1'-biphenyl]-4-yl)-6-(4-(pyridin-4-yl)phenyl)-1,3,5-triazin-2-yl)-[1,1':2',1"-terphenyl]-4,4"-dicarbonitrile (CC'129-GC'1) (yield: 1.5 g, 61%).

[0570] １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 8.94 (dd, J=8.1, 1.7Hz, 1H), 8.90 (brd, J=8.5Hz, 2H), 8.86 (brd, J=8 .5Hz, 2H), 8.83 (d, J=1.7Hz, 1H), 8.75 (brd, J=6.1Hz, 2H), 7.88 (brd, J=8.5Hz) , 2H), 7.84 (brd, J=8.5Hz, 2H), 7.75-7.58 (m, 9H), 7.52 (brdd, J=7.3, 7.0Hz, 2 H), 7.45 (brt, J=7.3Hz, 1H), 7.39 (brd, J=8.5Hz, 2H), 7.32 (brd, J=8.5Hz, 2H).

[0571] ​Synthesis Example 212: 5-(4-(4-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)phenyl)-6-phenyl-1,3,5-triazin-2-yl)picolinonitrile (CA'63-GA'45)

[0572] Under an argon atmosphere, 5-(4-(4-chlorophenyl)-6-phenyl-1,3,5-triazin-2-yl)picolinonitrile (2.0 g, 5.4 mmol), 2-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.3 g, 6.0 mmol), palladium acetate (36 mg, 0.16 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.16 g, 0.33 mmol) were suspended in THF (53 mL). To this suspension was added 2M aqueous potassium carbonate solution (9.0 mL, 18 mmol), and the mixture was refluxed for 17 hours. Water was added to the reaction solution, and the solid was collected by filtration and washed with water, methanol, and hexane. The obtained solid was dissolved in toluene heated to 110°C and filtered using Celite while hot. The filtrate was allowed to stand at room temperature, and the precipitated solid was collected by filtration to obtain 5-(4-(4-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)phenyl)-6-phenyl-1,3,5-triazin-2-yl)picolinonitrile (CA'63-GA'45) (yield: 2.2 g, 69%).

[0573] １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 10.02 (brd, J=2.0Hz, 1H), 9.14 (dd, J=8.0, 2.0Hz, 1H), 8.77 (br d, J=8.5Hz, 4H), 7.92 (brd, J=8.0Hz, 1H), 7.76-7.71 (m, 3H), 7.67 (brt, J= 7.0Hz, 1H), 7.64-7.58 (m, 2H), 7.51 (d, J=7.7Hz, 1H), 7.47-7.40 (m, 4H), 7.34 (dd, J=7.7, 1.8Hz, 1H), 7.06-7.00 (m, 4H), 5.55 (s, 1H), 5.50 (s, 1H).​

[0574] Synthesis Example 213: 5,5'-((6-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)-1,3,5-triazine-2,4-diyl)bis(4,1-phenylene))dipicolinonitrile (CA'11-GA'45)

[0575] Under an argon atmosphere, 2-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)-4,6-bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3,5-triazine (3.5 g, 4.8 mmol), 5-bromopicolinonitrile (2.1 g, 11 mmol), and tetrakis(triphenylphosphine)palladium(0) (0.28 g, 0.24 mmol) were suspended in THF (45 mL). To this suspension was added 2 M aqueous potassium carbonate solution (14 mL, 29 mmol), and the mixture was refluxed for 17 hours. Water was added to the reaction solution, and the solid was collected by filtration and washed with water, methanol, and hexane. The obtained solid was dissolved in pyridine heated to 115°C, activated carbon was added, and the mixture was stirred, followed by hot filtration using Celite. The filtrate was allowed to stand at room temperature, and the precipitated solid was collected by filtration, thereby obtaining 5,5'-((6-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)-1,3,5-triazine-2,4-diyl)bis(4,1-phenylene))dipicolinonitrile (CA'11-GA'45) (yield: 2.0 g, 61%).

[0576] １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 9.07 (dd, J = 2.3, 0.8 Hz, 2H), 8.92 (brd, J = 8.5 Hz, 4H), 8.79 (br d, J=1.5Hz, 1H), 8.51 (dd, J=7.8, 1.5Hz, 1H), 8.13 (dd, J=8.0, 2.3Hz, 2H ), 7.84 (dd, J=8.0, 0.8Hz, 2H), 7.83 (brd, J=8.5Hz, 4H), 7.61 (d, J=7.8H z, 1H), 7.51-7.43 (m, 4H), 7.08-7.02 (m, 4H), 5.67 (s, 1H), 5.57 (s, 1H).​

[0577] Synthesis Example 214: 4',4'''-(6-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)-1,3,5-triazine-2,4-diyl)bis([1,1'-biphenyl]-4-carbonitrile) (CA'4-GA'45)

[0578] Under an argon atmosphere, 2,4-bis(4-chlorophenyl)-6-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)-1,3,5-triazine (2.5 g, 4.5 mmol), 4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)benzonitrile (2.3 g, 11 mmol), palladium acetate (51 mg, 0.23 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.22 g, 0.45 mmol) were suspended in THF (45 mL). To this suspension was added 2M aqueous potassium carbonate solution (16 mL, 33 mmol), and the mixture was refluxed for 17 hours. Water was added to the reaction solution, and the solid was collected by filtration and washed with water, methanol, and hexane. The obtained solid was dissolved in toluene heated to 110°C and filtered using Celite while hot. The filtrate was allowed to stand at room temperature, and the precipitated solid was collected by filtration to obtain 4',4'''-(6-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)-1,3,5-triazine-2,4-diyl)bis([1,1'-biphenyl]-4-carbonitrile) (CA'4-GA'45) (yield: 2.8 g, 90%). １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 8.87 (brd, J=8.6Hz, 4H), 8.78 (d, J=1.6Hz, 1H), 8.50 (dd, J=7.7, 1.6Hz, 1H), 7.84-7.76 (m, 12H), 7.61 (d, J=7.7Hz, 1H), 7.51-7.42 (m, 4H), 7.07-7.01 (m, 4H), 5.67 (s, 1H), 5.57 (s, 1H).

[0579] Synthesis Example 215: 5-(4-(4-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)phenyl)-6-phenyl-1,3,5-triazin-2-yl)isophthalonitrile (CA'75-GA'45)

[0580] Under an argon atmosphere, 5-(4-(4-chlorophenyl)-6-phenyl-1,3,5-triazin-2-yl)isophthalonitrile (1.7 g, 4.3 mmol), 2-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.8 g, 4.8 mmol), palladium acetate (29 mg, 0.13 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.12 g, 0.26 mmol) were suspended in THF (43 mL). To this suspension was added 2M aqueous potassium carbonate solution (7.2 mL, 14 mmol), and the mixture was refluxed for 17 hours. Water was added to the reaction solution, and the solid was collected by filtration and washed with water, methanol, and hexane. The obtained solid was dissolved in toluene heated to 110°C and filtered using Celite while hot. The filtrate was allowed to stand at room temperature, and the precipitated solid was collected by filtration to obtain 5-(4-(4-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)phenyl)-6-phenyl-1,3,5-triazin-2-yl)isophthalonitrile (CA'75-GA'45) (yield: 1.5 g, 56%).

[0581] １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 9.26 (d, J=1.2Hz, 2H), 8.79-8.74 (m, 4H), 8.12 (brt, J=1.2Hz, 1H), 7.77-7.72 (m, 3H), 7.69 (brt, J=7.2Hz, 1H), 7.65-7. 70 (m, 2H), 7.52 (brd, J=7.6Hz, 1H), 7.48-7.41 (m, 4H), 7.35 (dd, J=7.6, 1.7Hz, 1H), 7.06-7.01 (m, 4H), 5.56 (s, 1H), 5.51 (s, 1H).

[0582] ​Synthesis Example 216: 4',4'''-{6-[4-(1-adamantyl)phenyl]-1,3,5-triazine-2,4-diyl}-bis[(1,1'-biphenyl)-4-carbonitrile] (CA'4-GA'43)

[0583] Under a nitrogen atmosphere, 2-[4-(1-adamantyl)phenyl]-4,6-bis(4-chlorophenyl)-1,3,5-triazine (0.63 g, 1.2 mmol), 4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)benzonitrile (0.56 g, 2.6 mmol), palladium acetate (8.5 mg, 0.038 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (35.4 mg, 0.074 mmol) were suspended in THF (12 mL). To this suspension was added 2 M aqueous tripotassium phosphate solution (3.7 mL, 7.4 mmol), and the mixture was refluxed for 3.5 hours. The reaction solution was filtered and then washed with water, methanol, and hexane to obtain a solid, which was then vacuum dried and recrystallized from toluene to obtain 4',4'''-{6-[4-(1-adamantyl)phenyl]-1,3,5-triazine-2,4-diyl}-bis[(1,1'-biphenyl)-4-carbonitrile] (CA'4-GA'43) (yield: 0.51 g, 64%).

[0584] １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 8.89 (d, J = 8.7Hz, 4H), 8.73 (d, J = 8.6Hz, 2H), 7.78-7.83 (m, 12H), 7.60 ( d, J=8.6Hz, 2H), 2.16 (brs, 3H), 2.01 (d, J=2.7Hz, 6H), 1.83 (brt, J=15.2Hz, 6H).

[0585] Synthesis Example 217: 4',4'''-[6-(fluoranthene-3-yl)]-1,3,5-triazine-2,4-diyl}-bis[(1,1'-biphenyl)-4-carbonitrile] (CA'4-GA'29)

[0586] ​Under a nitrogen atmosphere, 2-[4-(1-adamantyl)phenyl]-4,6-bis(4-chlorophenyl)-1,3,5-triazine (1.00 g, 2.0 mmol), 4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)benzonitrile (0.91 g, 4.2 mmol), palladium acetate (13.5 mg, 0.060 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (58.2 mg, 0.122 mmol) were suspended in THF (60 mL). To this suspension was added 2 M aqueous tripotassium phosphate solution (6.0 mL, 11.9 mmol), and the mixture was refluxed for 1 hour. The reaction solution was filtered and then washed with water, methanol, and hexane to obtain a solid, which was then vacuum dried and recrystallized from toluene to obtain {4',4'''-[6-(fluoranthene-3-yl)]-1,3,5-triazine-2,4-diyl}-bis[(1,1'-biphenyl)-4-carbonitrile] (CA'4-GA'29) (yield: 1.06 g, 84%).

[0587] １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 9.32 (d, J = 8.6Hz, 1H), 9.03 (d, J = 7.5Hz, 1H), 8.90 (d, J = 8.5Hz, 4H), 8.11 (d, J = 7.3Hz, 1H), 8.00 ( d, J=6.8Hz, 1H), 7.96-7.98 (m, 1H), 7.92-7.94 (m, 1H), 7.78-7.84 (m, 13H), 7.43 (quind, J=7.4, 1.4Hz, 2H).

[0588] Synthesis Example 218: 4-(4-[(1,1'-biphenyl)-4-yl]-6-{4'-[6-(4-cyanophenyl)-4-phenylpyridin-2-yl]-[(1,1'-biphenyl)-4-yl]}-1,3,5-triazin-2-yl)benzonitrile (CB'152-GB'39)

[0589] ​Under a nitrogen atmosphere, 4-[6-(4-bromophenyl)-4-phenylpyridin-2-yl]benzonitrile (1.06 g, 2.58 mmol), 4-{4-[(1,1'-biphenyl)-4-yl]-6-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1,3,5-triazin-2-yl}benzonitrile (1.42 g, 2.65 mmol), and tetrakis(triphenylphosphine)palladium(0) (97.0 mg, 0.084 mmol) were dissolved in THF (26 mL). 2 M aqueous potassium phosphate solution (3.9 mL, 7.7 mmol) was added to this solution, and the mixture was refluxed for 11 hours. The reaction solution was filtered and then washed with THF, water, ethanol, and hexane. The resulting solid was dried in vacuo to obtain 4-(4-[(1,1'-biphenyl)-4-yl]-6-{4'-[6-(4-cyanophenyl)-4-phenylpyridin-2-yl]-[(1,1'-biphenyl)-4-yl]}-1,3,5-triazin-2-yl)benzonitrile (CB'152-GB'39) (yield: 1.36 g, 71%).

[0590] １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 8.93 (dt, J = 8.7, 1.9 Hz, 2H), 8.89 (dt, J = 8.6, 2.0 Hz, 2H), 8.86 (d t, J=8.5, 1.9Hz, 2H), 8.36 (tt, J=8.3, 1.9Hz, 4H), 8.04 (d, J=1.5Hz, 1H), 7 96 (d, J=1.3Hz, 1H), 7.88-7.93 (m, 6H), 7.84 (d, J=8.1Hz, 4H), 7.77-7.80 (m, 2H), 7.72-7.75 (m, 2H), 7.51-7.61 (m, 5H), 7.45 (tt, J=7.3, 1.3Hz, 1H).

[0591] Synthesis Example 219: 4-(3-(4-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)pyridine-2,6-dicarbonitrile (CA'127-GA'45)

[0592] ​

[0593] Under a nitrogen atmosphere, 2-((9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)-4-phenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3,5-triazine (1.50 g, 2.45 mmol), 4-chloropyridine-2,6-dicarbonitrile (0.531 g, 3.25 mmol), palladium acetate (12.0 mg, 0.0534 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (5 The resulting solid was dissolved in a mixed solvent of 25 mL of toluene and 25 mL of pyridine, and the resulting solution was heated to 110°C. 0.17 g of activated carbon was added to the solution, and the mixture was filtered using Celite. The filtrate was allowed to stand at room temperature, and the precipitated solid was collected by filtration. 4-(3-(4-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)pyridine-2,6-dicarbonitrile (CA'127-GA'45) was obtained (yield: 1.3 g, 87%).

[0594] １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 8.97-8.94 (m, 2H), 8.75 (m, 1H), 8.73 (t, J = 1.8Hz, 2H), 8.46 (dd, J = 7.8, 1.7Hz, 1H), 8.19 (s, 2H) ), 7.82-7.76 (m, 2H), 7.67-7.58 (m, 4H), 7.49-7.44 (m, 4H), 7.07-7.02 (m, 4H), 5.66 (s, 1H), 5.57 (s, 1H).

[0595] ​Synthesis Example 220: 4,4'-(4'-(4-([1,1'-biphenyl]-4-yl)-6-(4-cyanophenyl)-1,3,5-triazin-2-yl)-[1,1'-biphenyl]-3,4-diyl)bis(1-naphthonitrile) (CC'119-GC'51)

[0596]

[0597] Under an argon atmosphere, 4-(4-([1,1'-biphenyl]-4-yl)-6-(4-chlorophenyl)-1,3,5-triazin-2-yl)benzonitrile (0.10 g, 0.23 mmol), 4,4'-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2-phenylene)bis(1-naphthonitrile) (0.12 g, 0.24 mmol), palladium acetate (1.5 mg, 6.8 μmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (6.4 mg, 0.014 mmol) were suspended in THF (2.3 mL). To this suspension was added 2 M aqueous potassium carbonate solution (0.36 mL, 0.72 mmol), and the mixture was refluxed for 17 hours. Water was added to the reaction solution, and then the solid was collected by filtration and washed with water, methanol, and hexane. The obtained solid was dissolved in hot toluene, activated carbon was added, and the mixture was stirred, and then the mixture was filtered while hot using Celite. The filtrate was allowed to stand at room temperature, and the precipitated solid was collected by filtration to obtain 4,4'-(4'-(4-([1,1'-biphenyl]-4-yl)-6-(4-cyanophenyl)-1,3,5-triazin-2-yl)-[1,1'-biphenyl]-3,4-diyl)bis(1-naphthonitrile) (CC'119-GC'51) (yield: 70 mg, 39%).

[0598] １ H-NMR (400MHz, CDCl ３ ​) δ (ppm): 8.95-8.83 (m, 6H), 8.27-8.22 (m, 1.2H), 8.11 (brd, J=9.0Hz, 0.6H), 8.03-7.82 (m, 9.8H), 7.76-7 .62 (m, 6.2H), 7.55-7.39 (m, 5.2H), 7.32-7.23 (m, 1.8H), 7.03 (d, J = 7.4Hz, 0.6H), 7.00 (d, J = 7.4Hz, 0.6H).

[0599] Synthesis Example 221: 4,4'-(4-(4,6-di([1,1'-biphenyl]-4-yl)-1,3,5-triazin-2-yl)-1,2-phenylene)bis(1-naphthonitrile) (CC'135-GC'51)

[0600]

[0601] Under an argon atmosphere, 2,4-di([1,1'-biphenyl]-4-yl)-6-chloro-1,3,5-triazine (1.1 g, 2.6 mmol), 4,4'-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2-phenylene)bis(1-naphthonitrile) (1.4 g, 2.8 mmol), and tetrakis(triphenylphosphine)palladium (0.091 g, 0.079 mmol) were suspended in THF (26 mL). To this suspension was added 2 M aqueous potassium carbonate solution (4.3 mL, 8.7 mmol), and the mixture was refluxed for 17 hours. Water was added to the reaction solution, and then activated carbon and sodium sulfate were added to the solution extracted with toluene, stirred, and then filtered through Celite. The solvent was distilled off from the obtained solution, and methanol and hexane were added and ultrasonically treated. The resulting solid was recrystallized from hot toluene to obtain 4,4'-(4-(4,6-di([1,1'-biphenyl]-4-yl)-1,3,5-triazin-2-yl)-1,2-phenylene)bis(1-naphthonitrile) (CC'135-GC'51) (yield: 1.5 g, 75%).

[0602] １ H-NMR (400MHz, CDCl ３ ​) δ (ppm): 9.10-9.05 (m, 1H), 8.96 (d, J = 1.5Hz, 0.4H), 8.90 (d, J = 1.5Hz, 0 .6H), 8.88-8.81 (m, 4H), 8.29-8.22 (m, 1.2H), 7.97 (m, 0.8H), 7.91 (brd, J =8.2Hz, 0.8H), 7.91 (m, 1.2H), 7.87-7.60 (m, 12.2H), 7.57-7.39 (m, 8.8H) ), 7.36-7.30 (m, 0.8H), 7.08 (d, J=7.3Hz, 0.6H), 7.03 (d, J=7.3Hz, 0.6H).

[0603] Synthesis Example 222: 4,4'-(4'-(4-([1,1'-biphenyl]-4-yl)-6-phenyl-1,3,5-triazin-2-yl)-[1,1'-biphenyl]-3,4-diyl)bis(1-naphthonitrile) (CC'137-GC'51)

[0604]

[0605] Under an argon atmosphere, 2-([1,1'-biphenyl]-4-yl)-4-(4-bromophenyl)-6-phenyl-1,3,5-triazine (1.5 g, 3.2 mmol), 4,4'-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2-phenylene)bis(1-naphthonitrile) (1.7 g, 3.4 mmol), and tetrakis(triphenylphosphine)palladium (0.11 g, 0.097 mmol) were suspended in THF (32 mL). To this suspension was added 2 M aqueous potassium carbonate solution (5.4 mL, 11 mmol), and the mixture was refluxed for 17 hours. Water was added to the reaction solution, and then activated carbon and sodium sulfate were added to the solution extracted with toluene, followed by stirring and filtration through a silica pad. The solvent was distilled off from the obtained solution, and methanol and hexane were added. The resulting solid was subjected to ultrasonic treatment and washed with hot octane to obtain 4,4'-(4'-(4-([1,1'-biphenyl]-4-yl)-6-phenyl-1,3,5-triazin-2-yl)-[1,1'-biphenyl]-3,4-diyl)bis(1-naphthonitrile) (CC'137-GC'51) (yield: 1.3 g, 53%).

[0606] １ ​H-NMR (400MHz, CDCl ３ ) δ (ppm): 8.95-8.90 (m, 2H), 8.90-8.85 (m, 2H), 8.84-8.80 (m, 2H), 8.27-8.23 (m, 1.2H), 8.1 (brd, J = 8.9Hz, 0.8H), 8.03-7.80 (m, 8H), 7.76-7.58 (m, 9H), 7.54-7.48 (m, 4.4H), 7.45-7.39 (m, 1.2H), 7.37 -7.27 (m, 1.2H), 7.03 (d, J=7.4Hz, 0.6H), 6.99 (d, J=7.4Hz, 0.6H).

[0607] Synthesis Example 223: 4'-(4,6-bis(4-(6-cyanopyridin-3-yl)phenyl)-1,3,5-triazin-2-yl)-[1,1':2',1''-terphenyl]-4,4''-dicarbonitrile (CC'7-GC'1)

[0608]

[0609] Under an argon atmosphere, 4'-(4,6-bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3,5-triazin-2-yl)-[1,1':2',1"-terphenyl]-4,4"-dicarbonitrile (3.3 g, 4.3 mmol), 5-bromopicolinonitrile (1.9 g, 10.4 mmol), and tetrakis(triphenylphosphine)palladium (0.25 g, 0.22 mmol) were suspended in THF (43 mL). To this suspension was added 2 M aqueous potassium carbonate solution (14 mL, 29 mmol), and the mixture was refluxed for 17 hours. Water was added to the reaction solution, which was then filtered and washed with water, methanol, hexane, and hot toluene. The resulting solid was dissolved in hot pyridine, activated carbon was added, and the mixture was stirred, followed by hot filtration using Celite. The filtrate was allowed to stand at room temperature, and the precipitated solid was collected by filtration to obtain 4'-(4,6-bis(4-(6-cyanopyridin-3-yl)phenyl)-1,3,5-triazin-2-yl)-[1,1':2',1''-terphenyl]-4,4''-dicarbonitrile (CC'7-GC'1) (yield: 2.5 g, 81%).

[0610] １ ​H-NMR (400MHz, CDCl ３ ) δ (ppm): 9.07 (d, J = 2.2Hz, 2H), 8.97-8.91 (m, 5H), 8.83 (d, J = 1.5Hz , 1H), 8.14 (dd, J = 8.1, 2.2Hz, 2H), 7.86 (brd, J = 8.4Hz, 4H), 7.86 (d, J=8.1Hz, 2H), 7.69(d, J=8.1Hz, 1H), 7.65(brd, J=8.3Hz, 2H), 7.61( brd, J=8.3Hz, 2H), 7.38 (brd, J=8.3Hz, 2H), 7.32 (brd, J=8.3Hz, 2H).

[0611] <Glass transition temperature / LUMO level> Compounds of Synthesis Examples-201 to 223 (D'-16), (D'-08), (CC'105-GC'1), (CC'94-GC'1), (CC'112-GC'1), (CC'119-GC'1), (CC'119-GC'21), (CC' 98-GC'1), (CC'119-GC'5), (CC'109-GC'1), (CC'129-GC'1), (CA'63-GA'45), (CA'11-GA'45), (CA'4-GA'45), (CA'75-GA'45), ( CA'4-GA'43), (CA'4-GA'29), (CB'152-GB'39), (CA'127-GA'45), (CC'119-GC'51), (CC'135-GC'51), (CC'137-GC'51), and (CC'7-GC'1), as well as comparative compound 1 described in Patent Document 1 and comparative compound 3 described in Patent Document 2, were measured for glass transition temperature using a differential scanning calorimeter (Hitachi High-Tech DSC7020) at a sweep rate of 10 ° C / min using an aluminum pan. In addition, for the LUMO level, the molecular structure was optimized and the LUMO level was calculated using density functional theory (DFT) under calculation conditions of the B3LYP functional and 6-31G(d) basis set using GA'ussian16 software. The obtained results of glass transition temperature and LUMO level (calc.LUMO) are summarized in the table below. In the table below, "ND" means "not detected." That is, compound (D'-16) and comparative compound 1 are crystalline, not amorphous. In the table below, "-" means not measured.

[0612]

[0613]

[0614]

[0615]

[0616]

[0617] The results in the above table show that, as a material for a photoelectric conversion element, the compound represented by formula (1′) has excellent thermal stability of the film compared to the comparative compounds 1 and 3, and has a deeper calculated LUMO level (calc. LUMO) than the comparative compounds (values ​​in the positive direction are lower).

[0618] <Element Example 201 (see FIG. 1)> As shown in FIG. 1, an imaging element 100 was fabricated as a photoelectric conversion element having a layered structure including a first electrode 1, a hole blocking layer 2, a photoelectric conversion layer 3, an electron blocking layer 4, a hole transport layer 5, and a second electrode 6, and the dark current, external quantum efficiency, and responsiveness of the imaging element were evaluated.

[0619] (Preparation of First Electrode 1) 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 a first electrode on its surface. The substrate was then washed with isopropyl alcohol and then subjected to surface treatment by ozone ultraviolet cleaning.

[0620] (Preparation for Vacuum Deposition) Each layer was vacuum-deposited on the cleaned and surface-treated substrate by a vacuum deposition method, and each layer was laminated.

[0621] First, the glass substrate was placed in a vacuum deposition chamber. －５ The pressure was reduced to Pa. Then, each layer was formed in the following order according to the film formation conditions.

[0622] (Preparation of Hole Blocking Layer 2) The sublimation-purified compound (D'-16) was formed into a film having a thickness of 10 nm at a rate of 0.03 nm / second to prepare a hole blocking layer 2.

[0623] (Preparation of Photoelectric Conversion Layer (Light Receiving Layer) 3) A 120 nm thick film was formed by mixing N,N-dimethylquinacridone and C60 in a ratio of 4:1 (mass ratio) to prepare photoelectric conversion layer 3. The film formation rate was 0.15 nm / sec.

[0624] (Preparation of Electron Blocking Layer 4) Compound (ic-3) was deposited at a rate of 0.10 nm / second to a thickness of 10 nm to prepare electron blocking layer 4. Note that (ic-3) was synthesized by the method described in JP-A-2018-193371.

[0625] (Preparation of Hole Transport Layer 5) A compound 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN) was deposited at a rate of 0.10 nm / second to form a film of 10 nm, thereby preparing a hole transport layer 5.

[0626] (Fabrication of Second Electrode 6) Finally, a metal mask was placed perpendicular to the ITO stripes on the substrate, and the second electrode 6 serving as the upper electrode was formed. Specifically, a silver film was formed to a thickness of 80 nm at a rate of 0.1 nm / sec, thereby fabricating the second electrode 6 serving as the upper electrode.

[0627] As a result, the area of ​​4 mm as shown in FIG. ２ The thickness of each film was measured using a stylus film thickness meter (DEKTAK, manufactured by Bruker).

[0628] The device was then sealed in a nitrogen atmosphere glove box with oxygen and moisture concentrations of 1 ppm or less by sealing the glass sealing cap and the film-formed substrate (device) with bisphenol F epoxy resin (manufactured by Nagase ChemteX Corporation).

[0629] The image sensor fabricated as described above was evaluated for the current in the dark (dark current), external quantum efficiency, and response time when a voltage of 2.6 V was applied. The dark current was measured using a Keithley Source Measure Unit 2636B. The external quantum efficiency was measured using a solar cell spectral response measurement device (Soma Optical Co., Ltd.). The wavelength of the irradiated light was 560 nm, and the intensity was 50 μW / cm. ２ The response time was measured by irradiating a light pulse and measuring the time it took for the current value to return to the value before irradiation.

[0630] The dark current, external quantum efficiency, and response time are relative values, with the result for Comparative Example Element 201 set as the reference value (1.0). A lower dark current value indicates better performance, a higher external quantum efficiency value indicates better performance, and a shorter response time indicates better performance. The measurement results obtained are shown in the table below.

[0631] <Element Examples 202 to 206, 211, 214, 215, 219, 222, 223, Element Comparative Examples 21, 22> In Element Example 201, instead of compound (D'-16), compounds (D'-08), (CC'105-GC'1), (CC'94-GC'1), (CC'112-GC'1), (CC'119-GC'1), (CC'129-GC'1), (CA'4-GA'45), (CA'75-GA'45), (CA'127-GA'45), (CC'137-GC'51), and (CC'7-GC'1), as well as comparative compound 1 described in Patent Document 1, and comparative compound 3 described in Patent Document 2, were used, respectively, in that order, and an imaging photoelectric conversion element was produced and evaluated in the same manner as in Element Example 201. The measurement results obtained are shown in the table below.

[0632]

[0633] The results in the above table show that by forming a layer using the compound represented by formula (1') as a material for a photoelectric conversion element for an imaging device, an imaging photoelectric conversion element can be realized that has improved at least one of the characteristics of responsiveness, external quantum efficiency, and dark current compared to when a layer is formed using a comparative compound.

[0634] An imaging element including a photoelectric conversion element according to one embodiment of the present invention can be applied to, for example, an imaging element of a digital camera or a digital video camera, an imaging element built into a mobile phone, and an image input device of a driving assistance system.

[0635] REFERENCE SIGNS LIST 1 First electrode 2 Hole blocking layer 3 Photoelectric conversion layer (light receiving layer) 4 Electron blocking layer 5 Hole transport layer 6 Second electrode 10 Organic layer 100 Imaging element

Claims

1. An imaging device comprising a layer containing a material for a photoelectric conversion element for an imaging device, the material for a photoelectric conversion element for an imaging device being represented by the following formula (1) or formula (1'): In the formula (1), CA is represented by the following formula (1a): Ar １ , and Ar ２ each independently represents a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent heteroaromatic group, or a substituted or unsubstituted divalent cyclic aliphatic hydrocarbon group; ３ each independently represents a substituted or unsubstituted mono- to pentavalent aromatic hydrocarbon group, a substituted or unsubstituted mono- to pentavalent heteroaromatic group, or a substituted or unsubstituted mono- to pentavalent cyclic aliphatic hydrocarbon group; L １ ~L ３ each independently represents a substituted or unsubstituted di- to tetra-valent aromatic hydrocarbon group, a substituted or unsubstituted di- to tetra-valent heteroaromatic group, or a substituted or unsubstituted di- to tetra-valent cyclic aliphatic hydrocarbon group; R １ and R ２ Each independently represents hydrogen or Ar ３ represents; １ , a ２ , b １ , b ２ and c each independently represent an integer of 1 to 3; d and e each independently represent an integer of 1 or 2; and c+d+e represents an integer of 1 to 3; p, q and r each independently represent an integer of 0 to 3; n represents an integer of 1 to 3; Ar １ , Ar ２ , Ar ３ , L １ , L ２ and L ３ at least one of the heteroaromatic monocyclic groups is selected from the group consisting of a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, and a tetrazinyl group, or a fused ring group consisting of 2 to 4 aromatic monocyclic groups and partially containing at least one selected from the heteroaromatic monocyclic groups; with regard to the material for a photoelectric conversion element for an imaging element represented by the following formula (1'): In the formula (1'), Ar １１ ~Ar ３１ each independently represents a substituted or unsubstituted di- or trivalent aromatic hydrocarbon group, a substituted or unsubstituted di- or trivalent heteroaromatic group, or a substituted or unsubstituted di- or trivalent cyclic aliphatic hydrocarbon group; L １１ ~L ３１ each independently represents a substituted or unsubstituted di- to tetra-valent aromatic hydrocarbon group, a substituted or unsubstituted di- to tetra-valent heteroaromatic group, or a substituted or unsubstituted di- to tetra-valent cyclic aliphatic hydrocarbon group; １１ , a ２１ , b １１ , b ２１ , c １１ , and c ２１ each independently represents an integer of 1 to 3; １ , q １ and r １ each independently represents an integer of 0 to 3; １１ , Ar ２１ , Ar ３１ , L １１ , L ２１ , and L ３１ At least one of Ar has a cyano group; １１ , Ar ２１ , Ar ３１ , L １１ , L ２１ , and L ３１ wherein the sum of the number of cyano groups contained in these groups and the number of nitrogen-containing heteroaromatic rings each consisting of a 6-membered ring is 2 or more.

2. The imaging element according to claim 1, wherein in formula (1), n ​​is 1 or 2.

3. In the formula (1), １ , a ２ , b １ , b ２ 3. The imaging element according to claim 1, wherein p, q and r each independently represent an integer of 0 to 2.

4. In the formula (1), the Ar １ , Ar ２ , Ar ３ , L １ , L ２ and L ３ 4. The imaging device according to claim 1, wherein at least one of the groups is a pyridyl group or a pyrimidinyl group.

5. In the formula (1), the Ar １ , Ar ２ , Ar ３ , L １ , L ２ and L ３ 5. The imaging element according to claim 1, wherein at least two of the groups are pyridyl groups or pyrimidinyl groups.

6. In the formula (1'), the Ar １１ , Ar ２１ , Ar ３１ , L １１ , L ２１ , and L ３１ 2. The image sensor according to claim 1, wherein the sum of the number of cyano groups and the number of pyridyl groups contained in these groups is 2 or more.

7. An imaging device comprising a layer containing a material for a photoelectric conversion element for an imaging device, the material for a photoelectric conversion element for an imaging device being represented by the following formula (2): In the formula (2), L ２１Ａ represents a phenylene group; １Ａ represents an integer of 0 or 1; ２１ is represented by any one of formulas (21a) to (24a); In the formulas (21a) to (24a), Ar ２１Ａ R are the same or different and each represents a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heteroaromatic group; ２２ , and R ２３ are each independently represented by any one of formulas (21b) to (25b); In the formulas (21b) to (25b), Ar ２２Ａ are the same or different and each represents a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heteroaromatic group; ２２Ａ represents a phenylene group or a single bond; * represents a bonding site; Ar ２１Ａ and Ar in the formulas (21b) to (25b). ２２Ａ At least one of the Ar groups has a cyano group; ２１Ａ and Ar in the formulas (21b) to (25b). ２２Ａ In the above, the sum of the number of cyano groups and the number of pyridyl rings contained in these groups is 2 or more; ２１ is represented by the formula (21a), and / or R ２２ and R ２３ When at least one of the above is represented by the formula (21b), Ar in the formula (21a) ２１Ａ and Ar in the formula (21b) ２２Ａ 2. The image sensor according to claim 1, wherein, being the same or different, each is an aromatic hydrocarbon group substituted with one or more cyano groups or a heteroaromatic group substituted with one or more cyano groups.

8. In the formula (2), the L ２１Ａ 8. The imaging element according to claim 7, wherein is an o-phenylene group, a p-phenylene group, or a single bond.

9. In the formula (2), the Ar ２１Ａ and are the same or different and each is an aromatic hydrocarbon group substituted with a cyano group, or a substituted or unsubstituted heteroaromatic group.

10. In the formula (2), the Ar ２２Ａ and are the same or different and are an aromatic hydrocarbon group substituted with a cyano group, or a substituted or unsubstituted heteroaromatic group.

11. In the formula (2), Ar in the formulas (21a) to (24a) ２１Ａ and Ar in the formulas (21b) to (25b). ２２Ａ 11. The imaging element according to claim 7, wherein at least two of the above have a cyano group.

12. The image sensor according to any one of claims 1 to 11, wherein the material for the photoelectric conversion element for the image sensor has a molecular weight of 550 or more.

13. The image sensor according to any one of claims 1 to 12, wherein the layer containing the material for a photoelectric conversion element for an image sensor is a hole blocking layer.

14. A compound represented by formula (11), formula (12), formula (13), formula (14), formula (3) or formula (4), wherein the compound represented by the following formula (11) is: In the formula (11), Ar １１１ and Ar ２１１ each independently represents a 3-pyridyl group or a 4-pyridyl group; Ar ３１１ represents a mono- or divalent phenanthryl group, a mono- or divalent dimethylfluorenyl group, a mono- or divalent diphenylfluorenyl group, a mono- or divalent spirobifluorenyl group, a mono- or divalent triptycenyl group, an aromatic group having 6 to 26 carbon atoms and at least one sulfone group, or a cyclic aliphatic hydrocarbon group having 10 to 16 carbon atoms; L ３１１ represents a divalent phenyl group or a divalent pyridyl group; L ３１１ When multiple are present, they may be the same or different; １１ represents an integer of 0 to 2; １１ represents an integer of 1 or 2; A compound having a triazine ring represented by the following formula (12) is: In the formula (12), L １１２ and L ２１２ represents a divalent pyridyl group; the divalent pyridyl group is bonded to the triazine ring at the 3-position or the 4-position; when the divalent pyridyl group is bonded to the triazine ring at the 4-position, Ar １１２ and Ar ２１２ each independently represents an aromatic hydrocarbon group having 10 to 26 carbon atoms, a nitrogen-containing heteroaromatic group having 6 to 26 carbon atoms composed only of a 6-membered ring, an aromatic group having 6 to 26 carbon atoms and having at least one sulfone group, or a cyclic aliphatic hydrocarbon group having 10 to 16 carbon atoms; when the divalent pyridyl group has a bond to the triazine ring at the 3-position, Ar １１２ and Ar ２１２ each independently represents a biphenylyl group, a terphenylyl group, a phenanthryl group, a dimethylfluorenyl group, a diphenylfluorenyl group, a spirobifluorenyl group, a triptycenyl group, an aromatic group having 6 to 26 carbon atoms and at least one sulfone group, or a cyclic aliphatic hydrocarbon group having 10 to 16 carbon atoms; ３１２ represents an aromatic hydrocarbon group having 6 to 26 carbon atoms, a nitrogen-containing heteroaromatic group having 6 to 26 carbon atoms composed only of a 6-membered ring, an oxygen- or sulfur-containing heteroaromatic group having 4 to 26 carbon atoms, an aromatic group having 6 to 26 carbon atoms and having at least one sulfone group, or a cyclic aliphatic hydrocarbon group having 10 to 16 carbon atoms; ３１２ represents a single bond, a divalent or trivalent phenyl group, or a divalent or trivalent pyridyl group; ４１２ represents a divalent phenyl group or a divalent pyridyl group; L ４１２ When multiple are present, they may be the same or different; １２ represents an integer of 1 or 2; A compound represented by the following formula (13): In the formula (13), Ar １１３ and Ar ２１３ each independently represents a 3-pyridyl group or a 4-pyridyl group; Ar ３１３ represents an aromatic hydrocarbon group having 10 to 26 carbon atoms, a nitrogen-containing heteroaromatic group having 2 to 26 carbon atoms composed only of a 6-membered ring, an oxygen- or sulfur-containing heteroaromatic group having 4 to 26 carbon atoms, an aromatic group having 6 to 26 carbon atoms and having at least one sulfone group, or a cyclic aliphatic hydrocarbon group having 10 to 16 carbon atoms; ３１３ represents a single bond, a divalent or trivalent phenyl group, or a divalent or trivalent pyridyl group; ４１３ represents a divalent phenyl group or a divalent pyridyl group; L ４１３ When multiple are present, they may be the same or different; １３ represents an integer of 1 or 2; A compound represented by the following formula (14): In the formula (14), Ar １１４ and Ar ２１４ each independently represents a 3-pyridyl group or a 4-pyridyl group; Ar ３１４ represents an aromatic hydrocarbon group having 10 to 24 carbon atoms, a nitrogen-containing heteroaromatic group having 6 to 26 carbon atoms composed only of a 6-membered ring, an oxygen- or sulfur-containing heteroaromatic group having 4 to 26 carbon atoms, an aromatic group having 6 to 26 carbon atoms and having at least one sulfone group, or a cyclic aliphatic hydrocarbon group having 10 to 16 carbon atoms; ３１４ represents a single bond, a divalent or trivalent phenyl group, or a divalent or trivalent pyridyl group; ４１４ represents a divalent phenyl group or a divalent pyridyl group; L ４１４ When multiple are present, they may be the same or different; １４ represents an integer of 1 or 2; A compound represented by the following formula (3): In the formula (3), L ３１Ａ represents a phenylene group; １Ａ represents an integer of 0 or 1; ３１ is represented by any one of formulas (31a) to (34a); In the formulas (31a) to (34a), Ar ３１Ａ are the same or different and each represents a phenyl group substituted with one or more cyano groups, a pyridyl group, a pyridyl group substituted with one or more alkyl groups having 1 to 6 carbon atoms, a pyridyl group substituted with one or more cyano groups, or an optionally substituted naphthyl group; R ３２ , and R ３３ are each independently represented by any one of formulas (31b) to (35b); In the formulas (31b) to (35b), Ar ３２Ａ are the same or different and represent a phenyl group, a phenyl group substituted with one or more alkyl groups having 1 to 6 carbon atoms, a phenyl group substituted with one or more cyano groups, a pyridyl group, a pyridyl group substituted with one or more alkyl groups having 1 to 6 carbon atoms, a pyridyl group substituted with one or more cyano groups, or a biphenylyl group; L ３２Ａ represents a phenylene group or a single bond; * represents a bonding site; Ar ３１Ａ and Ar in the formulas (31b) to (35b). ３２Ａ At least one of R has a cyano group; ３１ is represented by the formula (31a), and / or R ３２ and R ３３ When at least one of the above is represented by the formula (31b), Ar in the formula (31a) ３１Ａ and Ar in the formula (31b). ３２Ａ are the same or different and are a phenyl group substituted with one or more cyano groups, or a pyridyl group substituted with one or more cyano groups, and the compound represented by the following formula (4) is: In the formula (4), Ar ４１ , and Ar ４２ each independently represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 26 carbon atoms, a substituted or unsubstituted nitrogen-containing heteroaromatic group having 3 to 26 carbon atoms composed only of a 6-membered ring, a substituted or unsubstituted oxygen-containing or sulfur-containing heteroaromatic group having 3 to 26 carbon atoms, or a cyclic aliphatic hydrocarbon group having 10 to 16 carbon atoms; ４１ ~L ４３ each independently represents a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 26 carbon atoms, a substituted or unsubstituted divalent nitrogen-containing heteroaromatic group having 3 to 26 carbon atoms and consisting only of a 6-membered ring, a substituted or unsubstituted divalent oxygen-containing or sulfur-containing heteroaromatic group having 3 to 26 carbon atoms, or a divalent cyclic aliphatic hydrocarbon group having 10 to 16 carbon atoms; ４ , q ４ and r ４ each independently represents an integer of 0 to 2; ４１ , Ar ４２ , L ４１ , L ４２ , and L ４３ At least one of the groups has a cyano group.

15. In the formula (4), the L ４１ , L ４２ , and L ４３ The compound according to claim 14 , wherein each of the groups independently represents a phenyl group which may be substituted with a cyano group, or a pyridyl group which may be substituted with a cyano group.

16. In the formula (4), the Ar ４１ , Ar ４２ , L ４１ , L ４２ , and L ４３ 16. The compound according to claim 14 or 15, wherein the sum of the number of cyano groups contained in these groups and the number of nitrogen-containing heteroaromatic rings constituted by 6-membered rings is 2 or more.

17. In the formula (4), the Ar ４１ , Ar ４２ , L ４１ , L ４２ , and L ４３ The compound according to any one of claims 14 to 16, wherein the sum of the number of cyano groups and the number of pyridyl groups contained in these groups is 2 or more.

18. A material for a photoelectric conversion element for an imaging element, comprising the compound according to any one of claims 14 to 17.

19. The material for a photoelectric conversion element for an imaging element according to claim 18, which is a hole-blocking material.

20. An imaging device comprising a layer containing the material for a photoelectric conversion element for an imaging device according to claim 18 or 19.

Images