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

Abstract

The purpose of the present disclosure is to provide a material for a photoelectric conversion element for an imaging element, which has high thermal stability, while achieving an imaging element in which at least one characteristic among responsiveness, external quantum efficiency, and dark current is improved. An image pickup element according to one embodiment of the present invention is provided with a layer containing a material for a photoelectric conversion element for an image pickup element, the material being represented by formula (1) or formula (1 ').

Description

Materials for photoelectric conversion elements used in camera components and camera components Technical Field

[0001] This invention relates to materials for photoelectric conversion elements used in camera elements and to camera elements. Background Technology

[0002] Photoelectric conversion elements are widely used in solar cells, optical sensors, image sensors, etc., and their applications and markets are constantly expanding, with their development being actively underway.

[0003] For example, Patent Document 1 discloses a photoelectric conversion element that includes 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] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2022-17302

[0008] Patent Document 2: Korean Patent Publication No. 10-2021-053141 Summary of the Invention

[0009] The technical problem that the invention aims to solve

[0010] In photoelectric conversion devices used in applications such as imaging components, it is desirable to improve external quantum efficiency to increase sensitivity, reduce dark current to decrease noise, and improve susceptibility to reduce image retention. In addition, depending on applications such as automotive, very high heat resistance is sometimes required, necessitating materials with high glass transition temperatures (Tg).

[0011] One objective of this invention is to obtain an imaging element in which at least one of the following characteristics—responsiveness, external quantum efficiency, and dark current—is improved, and to realize a novel compound with very high heat resistance.

[0012] Technical solutions for solving technical problems

[0013] To solve the above-mentioned technical problems, a camera element is provided, which includes a layer comprising a material for a photoelectric conversion element for a camera element, wherein the material for the photoelectric conversion element for a camera element is represented by the following formula (1) or formula (1′): Regarding the material for the photoelectric conversion element for a camera element shown in the following formula (1): [Chemical 1]

[0014] In equation (1), CA is represented by the following equation (1a), [Chemistry 2]

[0015] 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; Ar 3 Each independently represents a substituted or unsubstituted aromatic hydrocarbon group in the 1-5 valent range, a substituted or unsubstituted heteroaromatic group in the 1-5 valent range, or a substituted or unsubstituted cyclic aliphatic hydrocarbon group in the 1-5 valent range; L 1 ~L 3 Each independently represents a substituted or unsubstituted divalent to tetravalent aromatic hydrocarbon group, a substituted or unsubstituted divalent to tetravalent heteroaromatic group, or a substituted or unsubstituted divalent to tetravalent cyclic aliphatic hydrocarbon group; R 1 and R 2 Each can be independently represented as hydrogen or Ar. 3 ;a 1 a 2 b 1 b 2 c and d independently represent integers from 1 to 3; d and e independently represent integers from 1 to 2; and c + d + e represent integers from 1 to 3; p, q, and r independently represent integers from 0 to 3; n represents integers from 1 to 3; Ar 1 Ar 2 Ar 3 L 1 L 2 and L 3 At least one of the groups is selected from: heteroaromatic monocyclic groups selected from pyridyl, pyridinyl, pyrimidinyl, pyrazinyl, and tetraazinyl, or a fused-ring group composed of 2 to 4 aromatic monocyclic groups, a portion of which contains at least one selected from the heteroaromatic monocyclic groups; with respect to the material for the photoelectric conversion element for the imaging element shown in the following formula (1′); [Chemical 3]

[0016] In the aforementioned formula (1′), Ar 11 ~Ar 31 Each independently represents a substituted or unsubstituted divalent or trivalent aromatic hydrocarbon group, a substituted or unsubstituted divalent or trivalent heteroaromatic group, or a substituted or unsubstituted divalent or trivalent cyclic aliphatic hydrocarbon group; L 11 ~L 31Each independently represents a substituted or unsubstituted divalent to tetravalent aromatic hydrocarbon group, a substituted or unsubstituted divalent to tetravalent heteroaromatic group, or a substituted or unsubstituted divalent to tetravalent cyclic aliphatic hydrocarbon group; a 11 a 21 b 11 b 21 c 11 and c 21 Each can independently represent an integer from 1 to 3; p 1 q 1 and r 1 Each represents an integer from 0 to 3 independently; Ar 11 Ar 21 Ar 31 L 11 L 21 and L 31 At least one of them has a cyano group; in Ar 11 Ar 21 Ar 31 L 11 L 21 and L 31 In these groups, the sum of the number of cyano groups and the number of nitrogen-containing heteroaromatic rings composed of 6-membered rings is more than 2.

[0017] Alternatively, according to another aspect of the invention, compounds represented by formula (11), (12), (13), (14), (3), or (4) are provided, wherein the compound represented by formula (11) is: [Chemical 4]

[0018] In the aforementioned formula (11), Ar 111 and Ar 211 Each independently represents 3-pyridinyl or 4-pyridinyl; Ar 311 This refers to a phenanthrene group (monovalent or divalent), a dimethylfluorenyl group (monovalent or divalent), a diphenylfluorenyl group (monovalent or divalent), a spirodifluorenyl group (monovalent or divalent), a triterpenyl group (monovalent or divalent), an aromatic group having at least one sulfone group and 6 to 26 carbon atoms, or a cyclic aliphatic hydrocarbon group having 10 to 16 carbon atoms; L 311 This indicates a divalent phenyl or a divalent pyridyl group, in L... 311 In the case of multiple Ls, multiple Ls 311 They can be the same or different; r 11 n represents an integer from 0 to 2; 11 Representing an integer of 1 or 2, the compound with a triazine ring shown in the following formula (12) is: [Chemistry 5]

[0019] In the above formula (12), L 112 and L 212 The divalent pyridinyl group represents a pyridinyl group; the divalent pyridinyl group has a bond with the triazine ring at the 3- or 4-position; when the divalent pyridinyl group has a bond with the triazine ring at the 4-position, Ar 112 and Ar 212 Each of these groups independently represents an aromatic hydrocarbon group with 10 to 26 carbon atoms, a nitrogen-containing heteroaromatic group with 6 to 26 carbon atoms consisting only of a 6-membered ring, an aromatic group with 6 to 26 carbon atoms having at least one sulfone group, or a cyclic aliphatic hydrocarbon group with 10 to 16 carbon atoms; when the divalent pyridinium group has a bond with the triazine ring at the 3-position, Ar 112 and Ar 212 Each can independently represent biphenyl, terphenyl, phenanthrene, dimethylfluorenyl, diphenylfluorenyl, spirodifluorenyl, triphenylenyl, an aromatic group having at least one sulfone group and 6 to 26 carbon atoms, or a cyclic aliphatic hydrocarbon group having 10 to 16 carbon atoms; Ar 312 The following groups represent aromatic hydrocarbon groups with 6 to 26 carbon atoms, nitrogen-containing heteroaromatic groups with 6 to 26 carbon atoms consisting only of a 6-membered ring, oxygen-containing or sulfur-containing heteroaromatic groups with 4 to 26 carbon atoms, aromatic groups with 6 to 26 carbon atoms having at least one sulfone group, or cyclic aliphatic hydrocarbon groups with 10 to 16 carbon atoms; L 312 Indicates a single bond, a divalent or trivalent phenyl group, or a divalent or trivalent pyridyl group; L 412 This indicates a divalent phenyl or a divalent pyridyl group, in L... 412 In the case of multiple Ls, multiple Ls 412 They can be the same or different; c 12 Representing an integer of 1 or 2, the compound shown in equation (13) below is: [Chemical Engineering 6]

[0020] In the aforementioned formula (13), Ar 113 and Ar 213 Each independently represents 3-pyridinyl or 4-pyridinyl; Ar 313 The following groups represent aromatic hydrocarbon groups with 10 to 26 carbon atoms, nitrogen-containing heteroaromatic groups with 2 to 26 carbon atoms consisting only of a 6-membered ring, oxygen-containing or sulfur-containing heteroaromatic groups with 4 to 26 carbon atoms, aromatic groups with 6 to 26 carbon atoms having at least one sulfone group, or cyclic aliphatic hydrocarbon groups with 10 to 16 carbon atoms; L 313 Indicates a single bond, a divalent or trivalent phenyl group, or a divalent or trivalent pyridyl group; L 413 This indicates a divalent phenyl or a divalent pyridyl group, in L... 413 In the case of multiple Ls, multiple Ls 413 They can be the same or different; c13 Representing an integer of 1 or 2, the compound shown in equation (14) below is: [Chemistry 7]

[0021] In the aforementioned formula (14), Ar 114 and Ar 214 Each independently represents 3-pyridinyl or 4-pyridinyl; Ar 314 The following groups represent aromatic hydrocarbon groups with 10 to 24 carbon atoms, nitrogen-containing heteroaromatic groups with 6 to 26 carbon atoms consisting only of a 6-membered ring, oxygen-containing or sulfur-containing heteroaromatic groups with 4 to 26 carbon atoms, aromatic groups with 6 to 26 carbon atoms having at least one sulfone group, or cyclic aliphatic hydrocarbon groups with 10 to 16 carbon atoms; L 314 Indicates a single bond, a divalent or trivalent phenyl group, or a divalent or trivalent pyridyl group; L 414 This indicates a divalent phenyl or a divalent pyridyl group, in L... 414 In the case of multiple Ls, multiple Ls 414 They can be the same or different; c 14 Representing an integer of 1 or 2, the compound shown in equation (3) below is: [Chemical Engineering 8]

[0022] In the above formula (3), L 31A Indicates phenylene; r 1A R represents an integer that is either 0 or 1; 31 Any one of equations (31a) to (34a) can be used to represent: [Chemistry 9]

[0023] In equations (31a) to (34a), Ar 31A Same or different, indicating phenyl, pyridyl, pyridyl substituted with one or more cyano groups, pyridyl substituted with one or more alkyl groups having 1 to 6 carbon atoms, pyridyl substituted with one or more cyano groups, or naphthyl that can be substituted; R 32 and R 33 Each can be independently represented by any one of equations (31b) to (35b): [Chemistry 10]

[0024] In equations (31b) to (35b), Ar 32A Same or different, indicating phenyl, phenyl substituted with one or more alkyl groups having 1 to 6 carbon atoms, phenyl substituted with one or more cyano groups, pyridyl, pyridyl substituted with one or more alkyl groups having 1 to 6 carbon atoms, pyridyl substituted with one or more cyano groups, or biphenyl; L 32A Indicates a phenylene oxide or a single bond; Indicates the bonding site; Ar in formulas (31a) to (34a) 31A And Ar in equations (31b) to (35b) 32A At least one of them has a cyano group; in R 31 The expression (31a) and / or R 32 and R 33 When at least one of them is represented by the formula (31b), Ar in the formula (31a) 31A And Ar in equation (31b) 32A Whether identical or different, a phenyl group substituted with one or more cyano groups or a pyridyl group substituted with one or more cyano groups, the compound represented by formula (4) below is: [Chemical 11]

[0025] In equation (4), Ar 41 and Ar 42 Each can independently represent an aromatic hydrocarbon group with 6 to 26 carbon atoms (substituted or unsubstituted), a nitrogen-containing heteroaromatic group with 3 to 26 carbon atoms (substituted or unsubstituted) consisting only of a 6-membered ring, an oxygen-containing or sulfur-containing heteroaromatic group with 3 to 26 carbon atoms (substituted or unsubstituted), or a cyclic aliphatic hydrocarbon group with 10 to 16 carbon atoms; L 41 ~L 43 Each can independently represent a divalent aromatic hydrocarbon group with 6 to 26 carbon atoms (substituted or unsubstituted), a divalent nitrogen-containing heteroaromatic group with 3 to 26 carbon atoms (substituted or unsubstituted) consisting only of a 6-membered ring, a divalent heteroaromatic group with 3 to 26 carbon atoms (substituted or unsubstituted), or a divalent cyclic aliphatic hydrocarbon group with 10 to 16 carbon atoms; p 4 q 4 and r 4 Each independently represents an integer from 0 to 2; Ar 41 Ar 42 L 41 L 42 and L 43 At least one of them has a cyano group.

[0026] Invention Effects

[0027] According to one aspect of the present invention, it is possible to obtain a photoelectric conversion element material for a camera element with improved responsiveness, external quantum efficiency and dark current, and to realize a novel compound with very high heat resistance. Attached Figure Description

[0028] Figure 1 is a schematic cross-sectional view showing a stacked structure of a photoelectric conversion element for a camera element, including materials for a photoelectric conversion element for a camera element according to one aspect of the present invention. Detailed Implementation

[0029] The following is a detailed description of the material included in the layer of a camera element according to one aspect of the present invention for a photoelectric conversion element.

[0030] A "photoelectric conversion element" comprising a layer of photoelectric conversion element material, such as material used in a photoelectric conversion element for an image sensor, refers to a light-receiving element that utilizes the photoelectric effect or photovoltaic effect. Examples of light-receiving elements include photodiodes, phototransistors, image sensors (image sensors), and solar cells, with image sensors being preferred. A typical light-receiving element is one that converts incident light into an electric current. In this case, the light-receiving element operates on a different principle than a light-emitting element that converts applied current into light. Therefore, the "photoelectric conversion element material" used in "photoelectric conversion element" refers to the "photoelectric conversion element material" used in the "light-receiving element," and the "photoelectric conversion element material" used in an image sensor is referred to as "material for a photoelectric conversion element for an image sensor."

[0031] The definitions of each group in the formulas described below and their preferred examples are as follows. It should be noted that in this specification, functional groups such as aromatic hydrocarbon groups, heteroaromatic groups, and cyclic aliphatic hydrocarbon groups are not distinguished according to their valence. For example, in the context of 1- to 3-valent aromatic hydrocarbon groups, "phenyl" includes not only a 1-valent benzene ring (i.e., phenyl in the narrow sense) but also a 2-valent benzene ring (i.e., phenylene) and a 3-valent benzene ring (i.e., triphenyl). Furthermore, "pyridyl" includes both "pyridylene" and "pyridyltrimethylpyridyl".

[0032] Furthermore, the triazine ring specifically shown in each formula is distinguished from the alternatively stated "triazine" and "triazinyl" by being written as "triazine ring".

[0033] <Materials for photoelectric conversion elements used in camera components>

[0034] One aspect of the present invention relates to an imaging element comprising a layer containing a material for a photoelectric conversion element for an imaging element. This material for the photoelectric conversion element for an imaging element is represented by formula (1) or formula (1′) described later. Hereinafter, the material for the photoelectric conversion element for an imaging element represented by formula (1) will be referred to as "material (1) for a photoelectric conversion element for an imaging element," and the material for the photoelectric conversion element for an imaging element represented by formula (1′) will be referred to as "material (1′) for a photoelectric conversion element for an imaging element."

[0035] <Materials for photoelectric conversion elements used in camera components (1)>

[0036] One aspect of the present invention relates to an imaging element having a layer comprising a material for a photoelectric conversion element of an imaging element, which is represented by the following formula (1).

[0037] [Chemistry 12]

[0038] Here, in equation (1), CA is represented by the following equation (1a).

[0039] [Chemistry 13]

[0040] The material shown in Equation (1) for the photoelectric conversion element of the camera element is an electron transport material with excellent charge transport properties (i.e., electrons) and a hole blocking material with excellent blocking properties (i.e., holes) of the opposite charge. It is suitable for use as a material for the photoelectric conversion element of the camera element.

[0041] <Ar 1 Ar 2 Ar 3 >

[0042] In equation (1), Ar 1 and Ar 2 Each can independently represent a divalent aromatic hydrocarbon group, a divalent heteroaromatic group, or a divalent cyclic aliphatic hydrocarbon group. Ar 3 Each of these groups independently represents a substituted or unsubstituted aromatic hydrocarbon group with a 1-5 valence, a substituted or unsubstituted heteroaromatic group with a 1-5 valence, or a substituted or unsubstituted cyclic aliphatic hydrocarbon group with a 1-5 valence. In formula (1) representing CA, R 1 and R 2 Indicates hydrogen or Ar 3 .

[0043] Ar 1 ~Ar 3 The number of carbon atoms in each is preferably 5 to 50, more preferably 5 to 30, and even more preferably 6 to 26. By making Ar... 1 ~Ar 3 A higher number of carbon atoms within the aforementioned range improves the thermal stability of the layers in the imaging element. By making Ar... 1 ~Ar 3The smaller number of carbon atoms within the aforementioned range improves the solubility of the material used in the photoelectric conversion element for the camera element, and also improves the ease of manufacturing the material. Furthermore, it improves the layer formation in the material used in the photoelectric conversion element for the camera element, i.e., the film-forming properties in the coating process of the material used in the photoelectric conversion element for the camera element.

[0044] Ar 1 ~Ar 3 The aromatic hydrocarbon group represented can be a monocyclic ring, or a fused or compound ring containing multiple rings. There are no particular limitations on the aromatic hydrocarbon group; examples include phenyl, naphthyl, phenanthryl, anthraceneyl, fluorenyl, dimethylfluorenyl, diphenylfluorenyl, spirofluorenyl, pyrene, fluoranyl, triphenylene, tetraphenyl, and phenylyl.

[0045] Ar 1 ~Ar 3 The heteroaromatic group referred to is not particularly limited, and may be, for example, a functional group that includes nitrogen, oxygen, sulfur, phosphorus, silicon, and / or germanium atoms as heteroatoms on an aromatic ring, and can be a monocyclic ring, or a fused ring containing multiple rings. The heteroatom contained on the aromatic ring in the heteroaromatic group may be one or more. When there are two or more heteroatoms on the aromatic ring, these heteroatoms may be the same or different from each other.

[0046] Examples of nitrogen-containing heteroaromatic groups include: pyridinyl, pyrimidinyl, pyrazinyl, triazinyl, tetraazinyl, imidazolyl, and other heteroaromatic monocyclic compounds; quinolinyl, isoquinolinyl, quinoxalinyl, azathanel, diazathanel, triazathanel, tetraazathanel, azaphenyl, diazaphenyl, triazaphenyl, tetraazaphenyl, azapyrene, diazapyrene, triazapyrene, tetraazapyrene, and azapyrene. Fused rings of heteroaromatic monocyclic rings, including fluoranthyl, diazafluoranthyl, triazafluoranthyl, tetraazafluoranthyl, azitriaphenylene, diazaphenylene, triazaphenylene, tetraazaphenylene, pentaazaphenylene, hexaphenylene, oxazolyl, pyrroleyl, imidazolyl, triazolyl, thiadiazolyl, oxadiazolyl, benzothiazolyl, benzoxazolyl, benzoxazolyl, benzothiazolyl, and benzoxadiazolyl.

[0047] Examples of oxygen-containing heteroaromatic groups include: fused rings of heteroaromatic monocyclic rings such as furanyl, benzofuranyl, dibenzofuranyl, benzonaphthofuranyl, xanthonyl, dibenzodioxinyl, fluorenonyl group, and benzoxadiazolyl.

[0048] Examples of sulfur-containing heteroaromatic groups include thienyl and other heteroaromatic monocyclic rings; fused rings of heteroaromatic monocyclic rings such as benzothienyl, dibenzothienyl, thioxanthyl, and thianthyl.

[0049] As Ar 1 ~Ar 3 Examples of the cyclic aliphatic hydrocarbon groups represented include adamantyl, diadamantyl, norbornyl, cyclopentyl, and cyclohexyl. From the viewpoint of improving the thermal stability of the layer in a photoelectric conversion element used in a camera element, adamantyl or diadamantyl with 10 or more carbon atoms is preferred.

[0050] In Ar 1 ~Ar 3 In this context, aromatic hydrocarbon groups, heteroaromatic groups, and cyclic aliphatic hydrocarbon groups can each independently have substituents or not. In other words, aromatic hydrocarbon groups, heteroaromatic groups, and cyclic aliphatic hydrocarbon groups are substituted or unsubstituted. Examples of substituents that these functional groups can have include: deuterium atoms, cyano groups, halogen atoms, haloalkyl groups, acyl groups, nitro groups, sulfonyl groups, phosphoryl groups, alkyl groups with 1 to 20 carbon atoms, alkenyl groups and cycloalkyl groups, alkoxy groups with 1 to 10 carbon atoms, groups represented by -P(=O)(Ar′)2, groups represented by -S(=O)2Ar′, groups represented by -S(=O)Ar′, groups represented by -B(Ar′)2, groups represented by -B(OAr′)2, groups represented by -Si(Ar′)3, aromatic hydrocarbon groups with 6 to 30 carbon atoms, and heteroaryl groups with 3 to 30 carbon atoms (Ar′ represents aryl or heteroaryl).

[0051] As Ar 1 ~Ar 3 Examples of substitution by -P(=O)(Ar′)2 include: triphenylphosphine oxide, diphenylnaphthylphosphine oxide, diphenylphenanthrenephosphine oxide, diphenyl(dimethylfluorenyl)phosphine oxide, diphenyl(diphenylfluorenyl)phosphine oxide, and diphenylspirodifluorenylphosphine oxide.

[0052] In addition, as Ar 1 ~Ar 3 Groups substituted with -S(=O)2Ar′, for example, include diphenyl sulfone and dibenzothiophene-5,5-dioxide, which can be a form of an aromatic group having at least one sulfone group and 6 to 26 carbon atoms.

[0053] a 1 a 2 b 1 b 2c and 'c' each independently represent an integer from 1 to 3, preferably an integer of 1 or 2. The material for the photoelectric conversion element used in the camera element shown in equation (1) is obtained by using a... 1 a 2 b 1 b 2 Optimizing c within such a range can suppress the glass transition temperature (T0) of the material used in the photoelectric conversion element for the camera element. g The lowering of the LUMO energy level can deepen the LUMO energy level of the material used in the photoelectric conversion element for camera components, thereby improving the response speed in the photoelectric conversion element for camera components.

[0054] In equation (1a) representing CA, d and e each independently represent an integer of 1 or 2, and c+d+e represents an integer from 1 to 3.

[0055] The compounds shown in formula (1), which are used as materials for photoelectric conversion elements in imaging elements, each have multiple Ar... 1 Ar 2 and Ar 3 In the case of Ar 1 Each, Ar 2 Each, Ar 3 They can be the same or different, but from the point of view of ease of manufacturing, the same is preferred.

[0056] <L 1 L 2 L 3 >

[0057] In equation (1), L 1 L 2 and L 3 Each can independently represent a 2-4 valent aromatic hydrocarbon group, a 2-4 valent heteroaromatic group, or a 2-4 valent cyclic aliphatic hydrocarbon group.

[0058] L 1 ~L 3 The aromatic hydrocarbon group represented can be a monocyclic ring, or a fused or compound ring containing multiple rings. There are no particular limitations on the aromatic hydrocarbon group, and examples include phenyl, naphthyl, phenanthryl, anthraceneyl, fluorenyl, dimethylfluorenyl, spirofluorenyl, pyrene, fluoranyl, triphenylene, tetraphenyl, and alkyl.

[0059] L 1 ~L 3 The heteroaromatic group referred to is not particularly limited, and can be, for example, a functional group that includes nitrogen, oxygen, sulfur, phosphorus, silicon, and / or germanium atoms as heteroatoms on an aromatic ring, and can be a monocyclic ring, or a fused ring containing multiple rings. Examples of heteroaromatic groups include Ar mentioned above. 1~Ar 3 The nitrogen-containing heteroaromatic groups, oxygen-containing heteroaromatic groups, and sulfur-containing heteroaromatic groups exemplified herein are preferably pyridyl, pyrimidinyl, pyrazinyl, triazine, and the nitrogen-containing heteroaromatic groups exemplified herein.

[0060] As L 1 ~L 3 The cyclic aliphatic hydrocarbon group represented, for example, with Ar 1 ~Ar 3 Similarly, examples of cyclic aliphatic hydrocarbon groups with 10 or more carbon atoms, such as the adamantyl group mentioned above, can be cited.

[0061] In L 1 ~L 3 In this context, aromatic hydrocarbon groups, heteroaromatic groups, and cyclic aliphatic hydrocarbon groups can each independently have substituents or not. In other words, aromatic hydrocarbon groups, heteroaromatic groups, and cyclic aliphatic hydrocarbon groups are substituted or unsubstituted. Specific examples of substituents that these functional groups can have are related to Ar. 1 ~Ar 3 The specific examples of substituents that can be present are the same.

[0062] p, q, and r each independently represent an integer from 0 to 3, preferably an integer from 0 to 2. The material for the photoelectric conversion element of the image sensor shown in equation (1) can suppress the T-value of the material by optimizing p, q, and r within such ranges. g Lowering the p level deepens the LUMO energy level of the material used in the photoelectric conversion element for imaging sensors, thereby improving the response speed in the imaging sensor. It should be noted that when p is 0, L... 1 Representing a single bond, therefore in equation (1), Ar 1 It is directly bonded to the triazine ring via a single bond. Similarly, when q and r are both 0, L 2 and L 3 These represent single bonds.

[0063] The compounds shown in formula (1), which are used as materials for photoelectric conversion elements in imaging elements, each have multiple L... 1 L 2 and L 3 In the case of L 1 Each, L 2 Each, L 3 They can be the same or different.

[0064] <Characteristics of Ar, L and triazine rings>

[0065] In equation (1), Ar 1 Ar 2 Ar3 L 1 L 2 and L 3 At least one of the following is selected from (1) a heteroaromatic monocyclic ring selected from pyridine, pyridazine, pyrimidine, pyrazine, and tetrazine rings, or (2) a fused ring consisting of 2 to 4 aromatic monocyclic rings, wherein a portion of the fused ring group contains at least one heteroaromatic monocyclic ring selected from the heteroaromatic monocyclic ring. The heteroaromatic monocyclic rings of pyridine, pyridazine, pyrimidine, pyrazine, and tetrazine rings contain a nitrogen atom as a cyclizing atom in a fully conjugated aromatic ring, wherein no hydrogen atom is covalently bonded to the nitrogen atom. It should be noted that, unless otherwise specified, "aromatic monocyclic ring" in this specification refers to both "heteroaromatic monocyclic rings" and "aromatic hydrocarbon monocyclic rings".

[0066] via Ar 1 Ar 2 Ar 3 L 1 L 2 and L 3 At least one of the aromatic rings is a heteroaromatic ring, or a polycyclic aromatic ring containing the heteroaromatic ring, which can deepen the LUMO energy level of the material used in the photoelectric conversion element for the camera element and improve the response speed in the camera element.

[0067] That is, in equation (1), Ar 1 Ar 2 Ar 3 L 1 L 2 and L 3 At least one of them is preferably selected from heteroaromatic monocyclic rings exemplified above, such as pyridyl, pyrimidinyl, and pyrazinyl, as well as fused rings of aromatics that contain heteroaromatic monocyclic rings in a portion.

[0068] Furthermore, regarding the material for the photoelectric conversion element for the imaging element shown in formula (1) and the compounds shown in the formulas described later, Ar is directly or indirectly bonded to the triazine ring. 1 Ar 2 Ar 3 L 1 L 2 and L 3 At least one of them is a heteroaromatic monocyclic ring selected from pyridyl, pyridinyl, pyrimidinyl, pyrazinyl and tetraazinyl. Thus, as described above, it can not only deepen the LUMO energy level and improve the response speed in the imaging element, but also be used as a photoelectric conversion material for imaging elements that can achieve, for example, lower dark current and higher external quantum efficiency.

[0069] Among them, Ar 1 ~Ar 3and L 1 ~L 3 At least one of the rings is preferably a heteroaromatic ring as described above, more preferably pyridyl or pyrimidinyl, and even more preferably pyridyl. With this configuration, the LUMO of the material used in the photoelectric conversion element for the camera element can be deepened, thereby improving the response speed in the camera element.

[0070] The functional group selected from (1) the above-mentioned heteroaromatic monocyclic ring, or (2) the fused ring of an aromatic monocyclic ring containing at least one of the heteroaromatic monocyclic rings in a portion thereof, is preferably Ar. 1 ~Ar 3 and L 1 ~L 3 At least two of them. Especially Ar 1 Ar 2 Ar 3 L 1 L 2 and L 3 Preferably, at least two of the groups are pyridyl or pyrimidinyl groups. With this configuration, the LUMO of the material used in the photoelectric conversion element for the camera element can be further enhanced, thereby improving the response speed in the camera element.

[0071] <n>

[0072] In equation (1), n ​​represents an integer from 1 to 3, preferably an integer of 1 or 2. The material for the photoelectric conversion element used in the camera element shown in equation (1), by optimizing n within such a range, can suppress the T-value of the material used in the photoelectric conversion element for the camera element. g Lowering the LUMO energy level can deepen the LUMO energy level of the material used in the photoelectric conversion element of the camera element, thereby improving the response speed in the camera element.

[0073] <Compound(11)>

[0074] In one aspect of the present invention, the material (1) for the photoelectric conversion element of the imaging element described above can be a compound represented by the following formula (11). The compound represented by formula (11) also falls within the scope of the present invention.

[0075] [Chemistry 14]

[0076] <Ar 111 Ar 211 Ar 311 >

[0077] In equation (11), Ar 111 and Ar 211Each can be independently represented as 3-pyridyl or 4-pyridyl, and from the viewpoint of deepening the LUMO energy level, 4-pyridyl is preferred. 111 and Ar 211 They can be the same or different.

[0078] In equation (11), Ar 311 This refers to a phenanthrene group (monovalent or divalent), a dimethylfluorenyl group (monovalent or divalent), a diphenylfluorenyl group (monovalent or divalent), a spirodifluorenyl group (monovalent or divalent), a triterpenyl group (monovalent or divalent), an aromatic group having at least one sulfone group and having 6 to 26 carbon atoms, or a cyclic aliphatic hydrocarbon group having 10 to 16 carbon atoms. Ar 311 Preferred components include 2-phenanthrene, 3-phenanthrene, 9-phenanthrene, 9,9-dimethylfluorene-1-yl, 9,9-dimethylfluorene-2-yl, 9,9-dimethylfluorene-3-yl, 9,9-dimethylfluorene-4-yl, 9,9-diphenylfluorene-1-yl, 9,9-diphenylfluorene-2-yl, 9,9-diphenylfluorene-3-yl, 9,9-diphenylfluorene-4-yl, 1-spirodifluorene, and 2-spirodifluorene. 3-Spirodifluorenyl, 4-Spirodifluorenyl, 1-Tripteroyl, 2-Tripteroyl, 2-Phenylenyl, 3-Phenylenylsulfonyl, 4-Phenylenylsulfonyl, Dibenzothiophene-5,5-dioxide-1-yl, Dibenzothiophene-5,5-dioxide-2-yl, Dibenzothiophene-5,5-dioxide-3-yl, Dibenzothiophene-5,5-dioxide-4-yl, 1-Adamantane yl, 2-adamantyl, phenanthrene-9,10-diyl, 9,9-dimethylfluorene-2,7-diyl, 9,9-diphenylfluorene-2,7-diyl, spirodifluorene-2,7-diyl, triptene-2,6-diyl; more preferably, 9-phenanthrene, 9,9-dimethylfluorene-2-yl, 9,9-dimethylfluorene-4-yl, 9,9-diphenylfluorene-2-yl, 9,9-diphenylfluorene-4-yl, 2- Spirodifluorenyl, 4-spirodifluorenyl, 2-tripteroyl, 4-phenylphenylsulfonyl, dibenzothiophene-5,5-dioxide-2-yl, dibenzothiophene-5,5-dioxide-3-yl, 1-adamantyl, phenanthrene-9,10-diyl, 9,9-dimethylfluorene-2,7-diyl, 9,9-diphenylfluorene-2,7-diyl, spirodifluoren-2,7-diyl, tripteroyl-2,6-diyl.

[0079] <L 311 r 11 >

[0080] In equation (11), L 311 This indicates a divalent phenyl or a divalent pyridyl group, in L... 311 In the case of multiple Ls, multiple Ls 311 They can be the same or different.

[0081] r11 Represents integers from 0 to 2. It should be noted that in r... 11 When L is 0, 311 Representing a single bond, therefore in equation (11), Ar 311 It is directly bonded to the triazine ring via a single bond.

[0082] <n 11 >

[0083] In equation (11), n 11 An integer representing 1 or 2.

[0084] Preferred examples of compounds represented by formula (11) are shown in the table below, but are not limited to these. The table below shows compounds having skeletons of (CA1) to (CA33) as shown below, and groups of (GA1) to (GA29) as shown below having a # at the site of the group and a plurality of groups on the skeleton. (CAx) is represented by bonding 1 -GAy 1 Compounds containing (CA1) to (CA33) skeletons. It is bonded to the same groups shown in (GA1) to (GA29). Here, x 1 y represents any integer from 1 to 33. 1 Represents any integer from 1 to 29. That is, (CAx) 1 -GAy 1 The compounds referred to are those with the structure (CA1-GA1) to (CA33-GA29). However, these compounds do not include: compounds having any one of the (CA1) to (CA17) skeletons and a (GA3) group, or compounds having any one of the (CA25) to (CA33) skeletons and a (GA3) group. Therefore, for example, in x 1 =31, y 1 In the case of a compound such as (CA31-GA1) = 1, it indicates that the (CA31) skeleton and the (GA1) group are located at the # site of the group and at the two sites of the skeleton. The following (CA31-GA1) compounds are represented by bonding.

[0085] [Chemistry 15]

[0086] [Table 1]

[0087]

[0088] [Table 2]

[0089]

[0090] [Table 3]

[0091]

[0092] [Table 4]

[0093]

[0094] [Table 5]

[0095]

[0096] [Table 6]

[0097]

[0098] [Table 7]

[0099]

[0100] [Table 8]

[0101]

[0102] [Table 9]

[0103]

[0104] [Table 10]

[0105]

[0106] [Table 11]

[0107]

[0108] [Table 12]

[0109]

[0110] [Chemistry 16]

[0111] [Chemistry 17]

[0112] (Continued)

[0113] [Chemistry 18]

[0114] (Continued)

[0115] [Chemistry 19]

[0116] (Continued)

[0117] [Chemistry 20]

[0118] (Continued)

[0119] <Compound(12)>

[0120] In one aspect of the present invention, the material (1) for the photoelectric conversion element of the imaging element described above can be a compound represented by the following formula (12). The compound represented by formula (12) also falls within the scope of the present invention.

[0121] [Chemistry 21]

[0122] <L 112 L 212 Ar 112 Ar 212 >

[0123] In equation (12), L 112 and L 212 This indicates a divalent pyridinyl group, which has a bond with the triazine ring at the 3- or 4-position. Additionally, c 12 An integer representing 1 or 2, preferably 1.

[0124] The compound shown in formula (12) above in L 112 and L 212 When the divalent pyridyl group in the triazine ring has a bond with the triazine ring at the 4 position, it is represented by the following formula (12A).

[0125] [Chemistry 22]

[0126] In equation (12A), Ar 112A and Ar 212A Each can independently represent an aromatic hydrocarbon group with 10 to 26 carbon atoms, a nitrogen-containing heteroaromatic group with 6 to 26 carbon atoms consisting only of a 6-membered ring, an aromatic group with 6 to 26 carbon atoms having at least one sulfone group, or a cyclic aliphatic hydrocarbon group with 10 to 16 carbon atoms.

[0127] In equation (12A), in Ar 112A and Ar 212A In the case of aromatic hydrocarbon groups with 10 to 26 carbon atoms, Ar 112A and Ar 212A Each of the following is preferably naphthyl, biphenyl, terphenyl, phenanthrene, dimethylfluorenyl, diphenylfluorenyl, spirodifluorenyl, or triphenylenyl.

[0128] In equation (12A), in Ar 112A and Ar 212A In the case of Ar being a nitrogen-containing heteroaromatic group consisting only of a 6-membered ring with 6 to 26 carbon atoms, 112A and Ar 212A Each of the following is preferably quinolinyl, isoquinolinyl, quinoxalinyl, azirthaneyl, diazirthaneyl, triazirthaneyl, tetraazirthaneyl, aziphenanthryl, diaziphenanthryl, triaziphenanthryl, tetraaziphenanthryl, azipyrene, diazipyrene, triazipyrene, tetraazipyrene, azitrimethylene, diazitrimethylene, triazitrimethylene, tetraazitrimethylene, pentaazitrimethylene, hexaazitrimethylene.

[0129] In equation (12A), in Ar 112A and Ar 212A In the case of an aromatic group having at least one sulfone group and 6 to 26 carbon atoms, this Ar 112A and Ar 212A Examples of aromatic groups with sulfone groups include diphenyl sulfone and dibenzothiophene-5,5-dioxide.

[0130] Additionally, in equation (12A), in Ar 112A and Ar 212A In the case of cyclic aliphatic hydrocarbon groups with 10 to 16 carbon atoms, this Ar 112A and Ar 212A Examples of cyclic aliphatic hydrocarbon groups include the aforementioned adamantyl group.

[0131] The compound shown in formula (12) above in L 112 and L 212 When the divalent pyridine ring has a bond with the triazine ring at position 3, it is represented by the following formula (12B).

[0132] [Chemistry 23]

[0133] In equation (12B), Ar 112B and Ar 212BEach can independently represent biphenyl, terphenyl, phenanthrene, dimethylfluorenyl, diphenylfluorenyl, spirodifluorenyl, triphenylenyl, an aromatic group having at least one sulfone group and 6 to 26 carbon atoms, or a cyclic aliphatic hydrocarbon group having 10 to 16 carbon atoms.

[0134] In equation (12B), in Ar 112B and Ar 212B In the case of an aromatic group having at least one sulfone group and having 6 to 26 carbon atoms, or a cyclic aliphatic hydrocarbon group having 10 to 16 carbon atoms, Ar 112B and Ar 212B Able to select with Ar 112A and Ar 212A The same aromatic groups with sulfone groups and carbon atoms numbering 6 to 26, or cyclic aliphatic hydrocarbon groups with carbon atoms numbering 10 to 16, are therefore omitted from the description.

[0135] <Ar 312 >

[0136] In equation (12), Ar 312 The terms "aromatic hydrocarbon group with 6 to 26 carbon atoms," "nitrogen-containing heteroaromatic group with 6 to 26 carbon atoms consisting only of a 6-membered ring," "oxygen-containing or sulfur-containing heteroaromatic group with 4 to 26 carbon atoms," "aromatic group with 6 to 26 carbon atoms having at least one sulfone group," or "cyclic aliphatic hydrocarbon group with 10 to 16 carbon atoms" can be selected from Ar as shown in formula (12A) above. 112A and Ar 212A Since they are the same functional groups, their descriptions are omitted.

[0137] In equation (12), in Ar 312 When the aromatic hydrocarbon group has 6 to 26 carbon atoms, it is preferably phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, dimethylfluorenyl, diphenylfluorenyl, spirodifluorenyl, or tripteneyl.

[0138] In equation (12), in Ar 312 In the case of oxygen-containing heteroaromatic groups having 4 to 26 carbon atoms, examples include: heteroaromatic monocyclic rings such as furanyl, benzofuranyl, dibenzofuranyl, benzonaphthofuranyl, xanthanyl, dibenzodioxinyl, benzoxadiazolyl, etc., which are fused rings of heteroaromatic monocyclic rings.

[0139] In equation (12), in Ar 312In the case of sulfur-containing heteroaromatic groups with 4 to 26 carbon atoms, examples include heteroaromatic monocyclic rings such as thienyl; and fused rings of heteroaromatic monocyclic rings such as benzothienyl, dibenzothienyl, thioxanthyl, and thianthyl.

[0140] <L 312 L 412 c 12 >

[0141] In equation (12), L 312 This indicates a single bond, a divalent or trivalent phenyl group, or a divalent or trivalent pyridyl group. 12 An integer representing 1 or 2.

[0142] L 412 This indicates a divalent phenyl or a divalent pyridyl group, in L... 412 In the case of multiple Ls, multiple Ls 412 They can be the same or different.

[0143] Preferred examples of compounds represented by formula (12) are shown in the table below, but are not limited thereto. The table below shows compounds having skeletons as shown below (CB1) to (CB38), and groups as shown below (GB1) to (GB50) having a # at the site of the group and a # at the site of the skeleton. The bonded representation of (CBx) 2 -GBy 2 Compounds of ). Here, x 2 y represents any integer from 1 to 38. 2 Represents any integer from 1 to 50. That is, (CBx) 2 -GBy 2 The compounds referred to are those of (CB1-GB1) to (CB38-GB50). However, these compounds do not include compounds having a (CB3) skeleton and any of the groups of (GB1) to (GB7), (GB9) to (GB15), (GB23) to (GB26), (GB28) to (GB38), and (GB47) to (GB50), that is, compounds not including (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). Therefore, for example, in x 2 =4, y 2 In the case of a compound such as (CB4-GB2) = 2, it indicates that the (CB4) skeleton and the (GB2) group are located at the # site of the group and the skeleton. The following (CB4-GB2) compounds are represented by bonding.

[0144] [Chemistry 24]

[0145] [Table 13]

[0146]

[0147] [Table 14]

[0148]

[0149] [Table 15]

[0150]

[0151] [Table 16]

[0152]

[0153] [Table 17]

[0154]

[0155] [Table 18]

[0156]

[0157] [Table 19]

[0158]

[0159] [Table 20]

[0160]

[0161] [Table 21]

[0162]

[0163] [Table 22]

[0164]

[0165] [Table 23]

[0166]

[0167] [Table 24]

[0168]

[0169] [Table 25]

[0170]

[0171] [Chemistry 25]

[0172] [Chemistry 26]

[0173] (Continued)

[0174] [Chemistry 27]

[0175] (Continued)

[0176] [Chemistry 28]

[0177] (Continued)

[0178] [Chemistry 29]

[0179] (Continued)

[0180] [Chemistry 30]

[0181] (Continued)

[0182] [Chemistry 31]

[0183] (Continued)

[0184] <Compound(13)>

[0185] In one aspect of the present invention, the material (1) for the photoelectric conversion element of the imaging element described above can be a compound represented by the following formula (13). The compound represented by formula (13) also falls within the scope of the present invention.

[0186] [Chemistry 32]

[0187] In equation (13), Ar 113 and Ar 213Each can be independently represented as 3-pyridyl or 4-pyridyl, preferably 4-pyridyl.

[0188] In equation (13), Ar 313 It refers to an aromatic hydrocarbon group with 10 to 26 carbon atoms, a nitrogen-containing heteroaromatic group with 2 to 26 carbon atoms consisting only of a 6-membered ring, an oxygen-containing or sulfur-containing heteroaromatic group with 4 to 26 carbon atoms, an aromatic group with 6 to 26 carbon atoms having at least one sulfone group, or a cyclic aliphatic hydrocarbon group with 10 to 16 carbon atoms.

[0189] In equation (13), in Ar 313 In the case of aromatic hydrocarbon groups with 10 to 26 carbon atoms, Ar 313 Each of the following is preferably naphthyl, biphenyl, terphenyl, phenanthrene, dimethylfluorenyl, diphenylfluorenyl, spirodifluorenyl, or triphenylenyl.

[0190] In equation (13), in Ar 313 In the case of Ar being a nitrogen-containing heteroaromatic group consisting only of a 6-membered ring with 2 to 26 carbon atoms, 313 Each of the following is preferably pyridyl, pyrazinyl, triazinyl, tetraazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, azirthaneyl, diazaanthrayl, triazaanthrayl, tetraazaanthrayl, aziphenanthrayl, diazaanthrayl, triazaanthrayl, tetraazaanthrayl, azipyrene, diazapyrene, triazapyrene, tetraazapyrene, azitrimethylene, diazatrimethylene, triazatrimethylene, tetraazatrimethylene, pentaazatrimethylene, hexaazatrimethylene.

[0191] In equation (13), in Ar 313 In the case of an oxygen-containing heteroaromatic group with 4 to 26 carbon atoms, Ar 313 Each can be independently cited as an example: fused rings of heteroaromatic monocyclic rings such as furanyl, benzofuranyl, dibenzofuranyl, benzonaphthofuranyl, xanthanyl, dibenzodioxinyl, benzoxadiazolyl, etc.

[0192] In equation (13), in Ar 313 In the case of sulfur-containing heteroaromatic groups with 4 to 26 carbon atoms, Ar 313 Examples of heteroaromatic monocyclic rings include thienyl and others; fused rings of heteroaromatic monocyclic rings include benzothienyl, dibenzothienyl, thioxanthyl, and thianthyl.

[0193] In equation (13), in Ar 313 In the case of an aromatic group having at least one sulfone group and 6 to 26 carbon atoms, this Ar 313 Examples of aromatic groups with sulfone groups include diphenyl sulfone and dibenzothiophene-5,5-dioxide.

[0194] Additionally, in equation (13), in Ar 313 In the case of cyclic aliphatic hydrocarbon groups with 10 to 16 carbon atoms, this Ar 313 Examples of cyclic aliphatic hydrocarbon groups include the aforementioned adamantyl group.

[0195] In equation (13), L 313 This indicates a single bond, a divalent or trivalent phenyl group, or a divalent or trivalent pyridyl group. L 413 This indicates a divalent phenyl or a divalent pyridyl group, in L... 413 In the case of multiple Ls, multiple Ls 413 They can be the same or different. 13 An integer representing 1 or 2.

[0196] Preferred examples of compounds represented by formula (13) are shown in the table below, but are not limited to these. The table below shows compounds having a skeleton of (CC1) or (CC2) as shown below, and the groups of (GB1) to (GB50) described above having a # at the site of the group and a # at the site of the skeleton. (CCx) is represented by bonding 3 -GBy 2 Compounds of ). Here, x 3 y represents any integer, either 1 or 2. 2 Represents any integer from 1 to 50. That is, (CCx) 3 -GBy 2 The compounds in (CC1-GB1) to (CC2-GB50) are represented. Therefore, for example, in x 3 =1, y 2 In the case of a compound such as (CC1-GB39) = 39, it indicates that the (CC1) skeleton and the (GB39) group are located at the # site of the group and the skeleton. The following compounds (CC1-GB39) are represented by bonding.

[0197] [Chemistry 33]

[0198] [Table 26]

[0199]

[0200] [Chemistry 34]

[0201] <Compound(14)>

[0202] In one aspect of the present invention, the material (1) for the photoelectric conversion element of the imaging element described above can be a compound represented by the following formula (14). The compound represented by formula (14) also falls within the scope of the present invention.

[0203] [Chemistry 35]

[0204] In equation (14), Ar 114 and Ar 214 Each can be independently represented as 3-pyridyl or 4-pyridyl, preferably 4-pyridyl.

[0205] In equation (14), Ar 314 It refers to an aromatic hydrocarbon group with 10 to 24 carbon atoms, a nitrogen-containing heteroaromatic group with 6 to 26 carbon atoms consisting only of a 6-membered ring, an oxygen-containing or sulfur-containing heteroaromatic group with 4 to 26 carbon atoms, an aromatic group with 6 to 26 carbon atoms having at least one sulfone group, or a cyclic aliphatic hydrocarbon group with 10 to 16 carbon atoms.

[0206] In equation (14), in Ar 314 In the case of aromatic hydrocarbon groups with 10 to 24 carbon atoms, Ar 314 Each of the following is preferably naphthyl, biphenyl, terphenyl, phenanthryl, dimethylfluorenyl, or triphenylenyl.

[0207] In equation (14), in Ar 314 In the case of Ar being a nitrogen-containing heteroaromatic group consisting only of a 6-membered ring with 6 to 26 carbon atoms, 314 Each of the following is preferably quinolinyl, isoquinolinyl, quinoxalinyl, azirthaneyl, diazirthaneyl, triazirthaneyl, tetraazirthaneyl, aziphenanthryl, diaziphenanthryl, triaziphenanthryl, tetraaziphenanthryl, azipyrene, diazipyrene, triazipyrene, tetraazipyrene, azitrimethylene, diazitrimethylene, triazitrimethylene, tetraazitrimethylene, pentaazitrimethylene, hexaazitrimethylene.

[0208] In equation (14), in Ar 314 In the case of an oxygen-containing heteroaromatic group with 4 to 26 carbon atoms, Ar 314 Each can be independently cited as an example: fused rings of heteroaromatic monocyclic rings such as furanyl, benzofuranyl, dibenzofuranyl, benzonaphthofuranyl, xanthanyl, dibenzodioxinyl, benzoxadiazolyl, etc.

[0209] In equation (14), in Ar 314 In the case of sulfur-containing heteroaromatic groups with 4 to 26 carbon atoms, Ar 314Examples of heteroaromatic monocyclic rings include thienyl and others; fused rings of heteroaromatic monocyclic rings include benzothienyl, dibenzothienyl, thioxanthyl, and thianthyl.

[0210] In equation (14), in Ar 314 In the case of an aromatic group having at least one sulfone group and 6 to 26 carbon atoms, this Ar 314 Examples of aromatic groups with sulfone groups include diphenyl sulfone and dibenzothiophene-5,5-dioxide.

[0211] Additionally, in equation (14), in Ar 314 In the case of cyclic aliphatic hydrocarbon groups with 10 to 16 carbon atoms, this Ar 314 Examples of cyclic aliphatic hydrocarbon groups include the aforementioned adamantyl group.

[0212] L 314 This indicates a single bond, a divalent or trivalent phenyl group, or a divalent or trivalent pyridyl group. L 414 This indicates a divalent phenyl or a divalent pyridyl group, in L... 414 In the case of multiple Ls, multiple Ls 414 They can be the same or different. 14 An integer representing 1 or 2.

[0213] Preferred examples of compounds represented by formula (14) are shown in the table below, but are not limited to these. The table below shows compounds having a skeleton of (CD1) or (CD2) as shown below, and the groups of (GB1) to (GB50) described above having a # at the site of the group and a # at the site of the skeleton. (CDx) is represented by bonding 3 -GBy 2 Compounds of ). Here, x 3 y represents any integer, either 1 or 2. 2 Represents any integer from 1 to 50. That is, (CDx) 3 -GBy 2 The compounds in (CD1-GB1) to (CD2-GB50) are represented. Therefore, for example, in x 3 =1, y 2 In the case of a compound such as (CD1-GB28) = 28, it indicates that the (CD1) skeleton and the (GB28) group are located at the # site of the group and the skeleton. The following (CD1-GB28) compounds are represented by bonding.

[0214] [Chemistry 36]

[0215] [Table 27]

[0216]

[0217] [Chemistry 37]

[0218] <Other materials used in photoelectric conversion elements for camera components>

[0219] In one aspect of the invention, the material (1) used for the photoelectric conversion element of the imaging element is not limited to the compounds shown in formulas (11), (12), (13) or (14) above. Other preferred examples of the material (1) used for the photoelectric conversion element of the imaging element are shown below, but are not limited to these.

[0220] [Chemistry 38]

[0221] [Chemistry 39]

[0222] [Chemistry 40]

[0223] [Chemistry 41]

[0224] [Chemistry 42]

[0225] [Chemistry 43]

[0226] [Chemistry 44]

[0227] [Chemistry 45]

[0228] [Chemistry 46]

[0229] [Chemistry 47]

[0230] [Chemistry 48]

[0231] [Chemistry 49]

[0232] [Transformation 50]

[0233] [Chemistry 51]

[0234] [Chemistry 52]

[0235] [Chemistry 53]

[0236] [Chemistry 54]

[0237] [Chemistry 55]

[0238] [Chemistry 56]

[0239] [Chemistry 57]

[0240] [Chem.58]

[0241] [Chemistry 59]

[0242] [Transformation 60]

[0243] [Chemistry 61]

[0244] [Chemistry 62]

[0245] <Materials for photoelectric conversion elements used in camera components (1')>

[0246] One aspect of the present invention relates to an imaging element having a layer comprising a material for a photoelectric conversion element for an imaging element, the material for the photoelectric conversion element for an imaging element being represented by the following formula (1′).

[0247] [Chemistry 63]

[0248] In the aforementioned formula (1′), Ar 11 ~Ar 31Each independently represents a substituted or unsubstituted divalent or trivalent aromatic hydrocarbon group, a substituted or unsubstituted divalent or trivalent heteroaromatic group, or a substituted or unsubstituted divalent or trivalent cyclic aliphatic hydrocarbon group; L 11 ~L 31 Each independently represents a substituted or unsubstituted divalent to tetravalent aromatic hydrocarbon group, a substituted or unsubstituted divalent to tetravalent heteroaromatic group, or a substituted or unsubstituted divalent to tetravalent cyclic aliphatic hydrocarbon group; a 11 a 21 b 11 b 21 c 11 and c 21 Each can independently represent an integer from 1 to 3; p 1 q 1 and r 1 Each represents an integer from 0 to 3 independently; Ar 11 Ar 21 Ar 31 L 11 L 21 and L 31 At least one of them has a cyano group; in Ar 11 Ar 21 Ar 31 L 11 L 21 and L 31 In these groups, the sum of the number of cyano groups and the number of nitrogen-containing heteroaromatic rings composed of 6-membered rings is more than 2.

[0249] Ar 11 ~Ar 31 The number of carbon atoms in each is preferably 5 to 50, more preferably 5 to 30, and even more preferably 6 to 26. By making Ar... 11 ~Ar 31 A higher number of carbon atoms within the aforementioned range improves the thermal stability of the layers in the imaging element. By making Ar... 11 ~Ar 31 The smaller number of carbon atoms within the aforementioned range improves the solubility of the material used in the photoelectric conversion element for the camera element, and also improves the ease of manufacturing the material. Furthermore, it improves the layer formation in the material used in the photoelectric conversion element for the camera element, i.e., the film-forming properties in the coating process of the material used in the photoelectric conversion element for the camera element.

[0250] Ar 11 ~Ar 31The aromatic hydrocarbon group represented can be a monocyclic ring, or a fused or compound ring containing multiple rings. There are no particular limitations on the aromatic hydrocarbon group; examples include phenyl, naphthyl, phenanthryl, anthraceneyl, fluorenyl, dimethylfluorenyl, diphenylfluorenyl, spirofluorenyl, pyrene, fluoranyl, triphenylene, tetraphenyl, tripteneyl, and phenylyl.

[0251] Ar 11 ~Ar 31 The heteroaromatic group referred to is not particularly limited, and may be, for example, a functional group containing nitrogen, oxygen, sulfur, phosphorus, silicon, and / or germanium atoms as heteroatoms within an aromatic ring. It can be a monocyclic ring, or a fused or chained ring containing multiple rings. The heteroaromatic group may contain one or more heteroatoms within the aromatic ring. When there are two or more heteroatoms within the aromatic ring, these heteroatoms may be the same or different from each other.

[0252] Examples of nitrogen-containing heteroaromatic groups include: pyridinyl, pyrimidinyl, pyrazinyl, triazinyl, tetraazinyl, imidazolyl, and other heteroaromatic monocyclic compounds; quinolinyl, isoquinolinyl, quinoxalinyl, azathanel, diazathanel, triazathanel, tetraazathanel, azaphenyl, diazaphenyl, triazaphenyl, tetraazaphenyl, azapyrene, diazapyrene, triazapyrene, tetraazapyrene, and azapyrene. Fused rings of heteroaromatic monocyclic rings, including fluoranthyl, diazafluoranthyl, triazafluoranthyl, tetraazafluoranthyl, azitriaphenylene, diazaphenylene, triazaphenylene, tetraazaphenylene, pentaazaphenylene, hexaphenylene, oxazolyl, pyrroleyl, imidazolyl, triazolyl, thiadiazolyl, oxadiazolyl, benzothiazolyl, benzoxazolyl, benzoxazolyl, benzothiazolyl, and benzoxadiazolyl.

[0253] Examples of oxygen-containing heteroaromatic groups include: fused rings of heteroaromatic monocyclic rings such as furanyl, benzofuranyl, dibenzofuranyl, benzonaphthofuranyl, xanthonyl, dibenzodioxinyl, fluorenone, and benzoxadiazolyl.

[0254] Examples of sulfur-containing heteroaromatic groups include thienyl and other heteroaromatic monocyclic rings; fused rings of heteroaromatic monocyclic rings such as benzothienyl, dibenzothienyl, thioxanthyl, and thianthyl.

[0255] As Ar 11 ~Ar 31 Examples of the cyclic aliphatic hydrocarbon groups represented include adamantyl, diadamantyl, norbornyl, cyclopentyl, and cyclohexyl. From the viewpoint of improving the thermal stability of the layer possessed by the photoelectric conversion element, adamantyl or diadamantyl with 10 or more carbon atoms is preferred.

[0256] In Ar 11~Ar 31 In this context, aromatic hydrocarbon groups, heteroaromatic groups, and cyclic aliphatic hydrocarbon groups can each independently have substituents or not. In other words, aromatic hydrocarbon groups, heteroaromatic groups, and cyclic aliphatic hydrocarbon groups are substituted or unsubstituted. Examples of substituents that these functional groups can have include: deuterium atoms, cyano groups, halogen atoms, haloalkyl groups, acyl groups, nitro groups, sulfonyl groups, phosphoryl groups, alkyl groups with 1 to 20 carbon atoms, alkenyl groups and cycloalkyl groups, alkoxy groups with 1 to 10 carbon atoms, groups represented by -P(=O)(Ar′)2, groups represented by -S(=O)2Ar′, groups represented by -S(=O)Ar′, groups represented by -B(Ar′)2, groups represented by -B(OAr′)2, groups represented by -Si(Ar′)3, aromatic hydrocarbon groups with 6 to 30 carbon atoms, and heteroaryl groups with 3 to 30 carbon atoms (Ar′ represents aryl or heteroaryl).

[0257] As Ar 11 ~Ar 31 Examples of substitution by -P(=O)(Ar′)2 include: triphenylphosphine oxide, diphenylnaphthylphosphine oxide, diphenylphenanthrenephosphine oxide, diphenyl(dimethylfluorenyl)phosphine oxide, diphenyl(diphenylfluorenyl)phosphine oxide, and diphenylspirodifluorenylphosphine oxide.

[0258] In addition, as Ar 11 ~Ar 31 Groups substituted with -S(=O)2Ar′, for example, include diphenyl sulfone and dibenzothiophene-5,5-dioxide, which can be a form of an aromatic group having at least one sulfone group and 6 to 26 carbon atoms.

[0259] a 11 a 21 b 11 b 21 c 11 and c 21 Each element independently represents an integer from 1 to 3, preferably an integer of 1 or 2. The material for the photoelectric conversion element used in the camera element, as shown in equation (1′), is obtained by using a... 11 a 21 b 11 b 21 c 11 and c 21 Optimization within these ranges can suppress the glass transition temperature (T0) of the material used in the photoelectric conversion element for the camera element. g The lowering of the LUMO energy level can deepen the LUMO energy level of the material used in the photoelectric conversion element for camera components, thereby improving the response speed in the photoelectric conversion element for camera components.

[0260] The compounds shown in formula (1′) that serve as materials for photoelectric conversion elements used in imaging sensors each have multiple Ar... 11 Ar 21 and Ar 31 In the case of Ar 11 Each, Ar 21 Each, Ar 31 They can be the same or different, but from the point of view of ease of manufacturing, the same is preferred.

[0261] <L 11 L 21 L 31 >

[0262] In equation (1′), L 11 L 21 and L 31 Each can independently represent a 2-4 valent aromatic hydrocarbon group, a 2-4 valent heteroaromatic group, or a 2-4 valent cyclic aliphatic hydrocarbon group.

[0263] L 11 ~L 31 The aromatic hydrocarbon group represented can be a monocyclic ring, or a fused or compound ring containing multiple rings. There are no particular limitations on the aromatic hydrocarbon group, and examples include phenyl, naphthyl, phenanthryl, anthraceneyl, fluorenyl, dimethylfluorenyl, spirofluorenyl, pyrene, fluoranyl, triphenylene, tetraphenyl, and alkyl.

[0264] L 11 ~L 31 The heteroaromatic group referred to is not particularly limited, and can be, for example, a functional group that includes nitrogen, oxygen, sulfur, phosphorus, silicon, and / or germanium atoms as heteroatoms on an aromatic ring, and can be a monocyclic ring, or a fused ring containing multiple rings. Examples of heteroaromatic groups include Ar mentioned above. 11 ~Ar 31 The nitrogen-containing heteroaromatic groups, oxygen-containing heteroaromatic groups, and sulfur-containing heteroaromatic groups exemplified herein are preferably pyridyl, pyrimidinyl, pyrazinyl, triazine, and the nitrogen-containing heteroaromatic groups exemplified herein.

[0265] As L 11 ~L 31 The cyclic aliphatic hydrocarbon group represented, for example, with Ar 11 ~Ar 31 Similarly, examples of cyclic aliphatic hydrocarbon groups with 10 or more carbon atoms, such as the adamantyl group mentioned above, can be cited.

[0266] In L 11 ~L 31In this context, aromatic hydrocarbon groups, heteroaromatic groups, and cyclic aliphatic hydrocarbon groups can each independently have substituents or not. In other words, aromatic hydrocarbon groups, heteroaromatic groups, and hydrocarbon groups can be substituted or unsubstituted. Specific examples of substituents that these functional groups can have are related to Ar. 11 ~Ar 31 The specific examples of substituents that can be present are the same.

[0267] p 1 q 1 and r 1 Each element independently represents an integer from 0 to 3, preferably an integer from 0 to 2. The material for the photoelectric conversion element used in the camera element, as shown in equation (1′), is obtained by using p... 1 q 1 and r 1 Optimization within these ranges can suppress the T-value of the material used in the photoelectric conversion element for the camera element. g Lowering the LUMO energy level can deepen the LUMO level of the material used in the photoelectric conversion element of the camera, thereby improving the response speed in the camera element. It should be noted that at p... 1 When L is 0, 11 Representing a single bond, therefore in equation (1′), Ar 11 It is directly bonded to the triazine ring via a single bond. Similarly, in q... 1 and r 1 When L is 0, 21 and L 31 These represent single bonds.

[0268] The compounds shown in formula (1′) that serve as materials for photoelectric conversion elements used in imaging elements each have multiple L... 11 L 21 and L 31 In the case of L 11 Each, L 21 Each, L 31 They can be the same or different.

[0269] <Characteristics of Ar, L and triazine rings>

[0270] In equation (1′), Ar 11 Ar 21 Ar 31 L 11 L 21 and L 31 At least one of them has a cyano group. In other words, Ar 11 Ar 21 Ar 31 L 11 L 21 and L31 At least one of them is substituted with a cyano group or is substituted with a group having a cyano group.

[0271] In equation (1′), in Ar 11 Ar 21 Ar 31 L 11 L 21 and L 31 In these groups, the sum of the number of cyano groups and the number of nitrogen-containing heteroaromatic rings composed of 6-membered rings is more than 2. In formula (1′), in Ar 11 Ar 21 Ar 31 L 11 L 21 and L 31 In this specification, the sum of the number of cyano groups and the number of pyridinium groups in these groups is preferably 2 or more. The nitrogen-containing heteroaromatic ring composed of a 6-membered ring is selected from (1) heteroaromatic monocyclic rings selected from pyridine rings, pyridazine rings, pyrimidine rings, pyrazine rings, triazine rings, and tetraazine rings, or (2) a fused ring composed of 2 to 4 aromatic monocyclic rings, a portion of which contains at least one heteroaromatic monocyclic ring selected from the heteroaromatic monocyclic ring. The heteroaromatic monocyclic rings of pyridine rings, pyridazine rings, pyrimidine rings, pyrazine rings, triazine rings, and tetraazine rings contain a nitrogen atom as a cyclizing atom in a fully conjugated aromatic ring, and no hydrogen atom is covalently bonded to the nitrogen atom. It should be noted that, unless otherwise specified, "aromatic monocyclic ring" in this specification refers to both "heteroaromatic monocyclic ring" and "aromatic hydrocarbon monocyclic ring". In formula (1′), the -[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 bonded central triazine ring is not contained in the Ar 11 Ar 21 Ar 31 L 11 L21 and L 31 In the case of a nitrogen-containing heteroaromatic ring consisting of a 6-membered ring. In other words, preferably, the sum of the number of cyano groups among the three substituents of the central triazine ring and the number of nitrogen-containing heteroaromatic rings consisting of a 6-membered ring is 2 or more.

[0272] That is, for example, in the compound CC′119-GC′5, the sum of the number of cyano groups in the substituents of the central triazine ring and the number of nitrogen-containing heteroaromatic rings composed of 6-membered rings is 3.

[0273] [Chemistry 64]

[0274] Furthermore, for example, in the compound CA′11-GA′45, the sum of the number of cyano groups in the substituents of the central triazine ring and the number of nitrogen-containing heteroaromatic rings composed of 6-membered rings is 4. That is, in the 2-cyanopyridin-5-yl group of compound CA′11-GA′45, the sum of the number of cyano groups and the number of nitrogen-containing heteroaromatic rings composed of 6-membered rings is 2 in each group.

[0275] [Chemistry 65]

[0276] via Ar 11 Ar 21 Ar 31 L 11 L 21 and L 31 At least one of them has such a feature that it can deepen the LUMO energy level of the material used in the photoelectric conversion element for the camera element, thereby improving the response speed in the camera element.

[0277] That is, in equation (1′), Ar is preferred. 11 Ar 21 Ar 31 L 11 L 21 and L 31 At least one of them has a cyano group, and the sum of the number of cyano groups contained in these groups and the number of heteroaromatic monocyclic rings exemplified by the above-mentioned pyridyl, pyrimidinyl, pyrazinyl, triazine, etc., and the number of nitrogen-containing heteroaromatic rings composed of 6-membered rings that contain heteroaromatic monocyclic rings in a portion is 2 or more.

[0278] Furthermore, in the materials for photoelectric conversion elements for camera elements shown in Formula (1′), and the materials for photoelectric conversion elements for camera elements shown in the following formulas, and in the compounds, at least one of the three groups of the central triazine ring has at least one cyano group, and the sum of the number of cyano groups contained in the three groups and the number of nitrogen-containing heteroaromatic rings composed of 6-membered rings is 2 or more. Thus, as described above, the LUMO energy level can be deepened, and it can be used as a material for photoelectric conversion elements for camera elements that can achieve at least one of faster response speed, lower dark current and higher external quantum efficiency in camera elements.

[0279] In equation (1′), it is preferred to use Ar 11 Ar 21 Ar 31 L 11 L 21 and L 31 In this context, the cyano groups are arranged in sequences of 1–10, 1–8, 1–6, or 1–4.

[0280] The nitrogen-containing heteroaromatic rings composed of the aforementioned six-membered rings are preferably pyridine rings, pyridazine rings, pyrimidine rings, pyrazine rings, triazine rings, and tetraazine rings, more preferably pyridyl or pyrimidinyl, and even more preferably pyridyl. With this configuration, the LUMO of the material used in the photoelectric conversion element for the camera element can be deepened, thereby improving the response speed in the camera element.

[0281] Preferred examples of compounds represented by formula (1′) are shown in the table below, but are not limited to these. The table below shows compounds having skeletons as shown below (CA′1) to (CA′163), and groups as shown below (GA′1) to (GA′50) bonded to R groups at the # sites of the groups to the R groups of the skeleton. 11 -GA′y 11 Compounds of ). Here, x 11 y represents any integer from 1 to 163. 11 Represents any integer from 1 to 50. That is, (CA′x 11 -GA′y 11 The compounds represented by ) indicate compounds ranging from (CA′1-GA′1) to (CA′163-GA′50). Therefore, for example, in x 11 =4, y 11 In the case of a compound such as (CA′4-GA′43) = 43, the following (CA′4-GA′43) compound is represented by having a (CA′4) skeleton and a (GA′43) group bonded to an R group at the # site of the group and the skeleton.

[0282] [Chemistry 66]

[0283] [Table 28]

[0284]

[0285] [Table 29]

[0286]

[0287] [Table 30]

[0288]

[0289] [Table 31]

[0290]

[0291] [Table 32]

[0292]

[0293] [Table 33]

[0294]

[0295] [Table 34]

[0296]

[0297] [Table 35]

[0298]

[0299] [Table 36]

[0300]

[0301] [Table 37]

[0302]

[0303] [Table 38]

[0304]

[0305] [Table 39]

[0306]

[0307] [Table 40]

[0308]

[0309] [Table 41]

[0310]

[0311] [Table 42]

[0312]

[0313] [Table 43]

[0314]

[0315] [Table 44]

[0316]

[0317] [Table 45]

[0318]

[0319] [Table 46]

[0320]

[0321] [Table 47]

[0322]

[0323] [Table 48]

[0324]

[0325] [Table 49]

[0326]

[0327] [Table 50]

[0328]

[0329] [Table 51]

[0330]

[0331] [Table 52]

[0332]

[0333] [Table 53]

[0334]

[0335] [Table 54]

[0336]

[0337] [Table 55]

[0338]

[0339] [Table 56]

[0340]

[0341] [Table 57]

[0342]

[0343] [Table 58]

[0344]

[0345] [Table 59]

[0346]

[0347] [Table 60]

[0348]

[0349] [Table 61]

[0350]

[0351] [Table 62]

[0352]

[0353] [Table 63]

[0354]

[0355] [Table 64]

[0356]

[0357] [Table 65]

[0358]

[0359] [Table 66]

[0360]

[0361] [Table 67]

[0362]

[0363] [Table 68]

[0364]

[0365] [Table 69]

[0366]

[0367] [Table 70]

[0368]

[0369] [Table 71]

[0370]

[0371] [Table 72]

[0372]

[0373] [Chemistry 67]

[0374] [Chemistry 68]

[0375] [Chemistry 69]

[0376] [Chemistry 70]

[0377] [Chemistry 71]

[0378] [Chemistry 72]

[0379] [Chemistry 73]

[0380] [Chemistry 74]

[0381] [Chemistry 75]

[0382] [Chemistry 76]

[0383] [Chemistry 77]

[0384] Furthermore, preferred examples of compounds represented by formula (1′) are specifically illustrated in the table below, but are not limited to these. The table below shows compounds having skeletons as shown below (CB′1) to (CB′160), and groups as shown below (GB′1) to (GB′50) bonded to R groups at the # sites of the groups to the R sites of the skeletons, representing (CB′x). 21 ~GB′y 21 Compounds of ). Here, x 21 y represents any integer from 1 to 160. 21 Represents any integer from 1 to 50. That is, (CB′x 21 -GB′y 21 The compounds in (CB′1-GB′1) to (CB′160-GB′50) are represented. Therefore, for example, in x 21 =95, y 21 In the case of a compound such as (CB′95-GB′1) = 1, the following (CB′95-GB′1) compound is represented by having a (CB′95) skeleton and a (GB′1) group bonded to an R group at the # site of the group and the skeleton.

[0385] [Chemistry 78]

[0386] [Table 73]

[0387]

[0388] [Table 74]

[0389]

[0390] [Table 75]

[0391]

[0392] [Table 76]

[0393]

[0394] [Table 77]

[0395]

[0396] [Table 78]

[0397]

[0398] [Table 79]

[0399]

[0400] [Table 80]

[0401]

[0402] [Table 81]

[0403]

[0404] [Table 82]

[0405]

[0406] [Table 83]

[0407]

[0408] [Table 84]

[0409]

[0410] [Table 85]

[0411]

[0412] [Table 86]

[0413]

[0414] [Table 87]

[0415]

[0416] [Table 88]

[0417]

[0418] [Table 89]

[0419]

[0420] [Table 90]

[0421]

[0422] [Table 91]

[0423]

[0424] [Table 92]

[0425]

[0426] [Table 93]

[0427]

[0428] [Table 94]

[0429]

[0430] [Table 95]

[0431]

[0432] [Table 96]

[0433]

[0434] [Table 97]

[0435]

[0436] [Table 98]

[0437]

[0438] [Table 99]

[0439]

[0440] [Table 100]

[0441]

[0442] [Table 101]

[0443]

[0444] [Table 102]

[0445]

[0446] [Table 103]

[0447]

[0448] [Table 104]

[0449]

[0450] [Table 105]

[0451]

[0452] [Table 106]

[0453]

[0454] [Table 107]

[0455]

[0456] [Table 108]

[0457]

[0458] [Table 109]

[0459]

[0460] [Table 110]

[0461]

[0462] [Table 111]

[0463]

[0464] [Table 112]

[0465]

[0466] [Table 113]

[0467]

[0468] [Table 114]

[0469]

[0470] [Table 115]

[0471]

[0472] [Table 116]

[0473]

[0474] [Table 117]

[0475]

[0476] [Table 118]

[0477]

[0478] [Table 119]

[0479]

[0480] [Table 120]

[0481]

[0482] [Table 121]

[0483]

[0484] [Table 122]

[0485]

[0486] [Table 123]

[0487]

[0488] [Table 124]

[0489]

[0490] [Table 125]

[0491]

[0492] [Table 126]

[0493]

[0494] [Chemistry 79]

[0495] [Chemistry 80]

[0496] [Chemistry 81]

[0497] [Chemistry 82]

[0498] [Chemistry 83]

[0499] [Chemistry 84]

[0500] [Chemistry 85]

[0501] [Chemistry 86]

[0502] [Chemistry 87]

[0503] [Chemistry 88]

[0504] [Chemistry 89]

[0505] [Chemistry 90]

[0506] [Chemistry 91]

[0507] <Compound(2)>

[0508] In one embodiment of the present invention, the material (1′) for the photoelectric conversion element of the imaging element described above can be a compound represented by the following formula (2). The compound represented by formula (2) also falls within the scope of the present invention.

[0509] [Chemistry 92]

[0510] In equation (2), L 21A Indicates phenylene; q 1A R represents an integer that is either 0 or 1; 21 Any one of equations (21a) to (24a) can be used to represent: [Chemistry 93]

[0511] In equations (21a) to (24a), Ar 21A Same or different indicates substituted or unsubstituted aromatic hydrocarbon groups, or substituted or unsubstituted heteroaromatic groups; R 22 and R 23 Each can be independently represented by any one of equations (21b) to (25b): [Chemistry 94]

[0512] In equations (21b) to (25b), Ar 22A "Same" or "different" indicates substituted or unsubstituted aromatic hydrocarbon groups, or substituted or unsubstituted heteroaromatic groups; L 22A Indicates a phenylene oxide or a single bond; Indicates the bonding site; Ar in formulas (21a) to (24a) 21A And Ar in equations (21b) to (25b) 22A At least one of them has a cyano group; Ar in formulas (21a) to (24a) 21A And Ar in equations (21b) to (25b) 22A In these groups, the sum of the number of cyano groups and the number of pyridine rings is more than 2, in R 21 The expression (21a) and / or R22 and R 23 When at least one of them is represented by equation (21b), Ar in equation (21a) 21A And Ar in equation (21b) 22A The same or different refers to an aromatic hydrocarbon group substituted with one or more cyano groups or a heteroaromatic group substituted with one or more cyano groups.

[0513] <L 21A >

[0514] In equation (2), L 21A To indicate phenylene, from the viewpoint of improving thermal stability, it is preferable to indicate ortho-phenylene or para-phenylene. 21A Corresponding to L in equation (1′) 21 .

[0515] <q 1A >

[0516] In equation (2), q 1A A single integer representing either 0 or 1. q 1A When L is 0, 21A Indicates a single bond. q 1A Corresponding to q in equation (1′) 1 .

[0517] <R 21 >

[0518] R 21 Any one of equations (21a) to (24a) can be used to represent: [Chemistry 95]

[0519] In equations (21a) to (24a), Ar 21A Same or different indicates substituted or unsubstituted aromatic hydrocarbon groups, or substituted or unsubstituted heteroaromatic groups.

[0520] Ar 21A The same or different, more preferably an aromatic hydrocarbon group substituted with a cyano group, or a heteroaromatic group that is substituted or unsubstituted.

[0521] As Ar 21ASpecific examples are not particularly limited, but preferred examples may include phenyl, tolyl, biphenyl, pyridylphenyl, naphthylphenyl, pyridyl, pyrimidinyl, pyrazinyl, triazine, naphthyl, quinolinyl, isoquinolinyl, benzothiophene, benzofuranyl, anthraceneyl, phenanthrene, fluorenyl, dibenzothiophene, dibenzofuranyl, fluoranyl, pyrene, triphenylene, triphenylene, cyanophenyl, cyanonaphthyl, or cyanopyridinyl, which may be substituted with deuterium, halogen, cyano, alkyl, alkyl with 1 to 16 carbon atoms, alkoxy with 1 to 4 carbon atoms, aromatic hydrocarbon group with 6 to 26 carbon atoms, or heteroaromatic group with 3 to 26 carbon atoms.

[0522] Furthermore, from the viewpoint of superior properties of materials used in photoelectric conversion elements for imaging devices, each of these substituents is more preferably phenyl, p-tolyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, 3-(2-pyridyl)phenyl, 4-(2-pyridyl)phenyl, 3-(3-pyridyl)phenyl, 4-(3-pyridyl)phenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-phenylpyridin-6-yl, 2-phenylpyridin-5-yl, 2-phenylpyridin-4-yl, 3-phenylpyridin-5-yl, 3-phenylpyridin-6-yl, 2,6-diphenylpyridin-4-yl, 4,6-diphenylpyridin-2-yl, 2-pyrimidinyl, 2-pyrazinyl, 1-naphthyl, 2-naphthyl. 3-Quinolinyl, 4-Quinolinyl, 3-Isoquinolinyl, 2-Benzothiopheneyl, 2-Benzofuranyl, 2-fluorenyl, 9,9-Dimethylfluoren-2-yl, 9,9-Dimethylfluoren-3-yl, 9,9-Dimethylfluoren-4-yl, 9,9-Diphenylfluoren-2-yl, 9,9-Diphenylfluoren-3-yl, 9,9-Diphenylfluoren-4-yl, 9-Anthraceneyl, 1 -Phenylenyl, 2-Phenylenyl, 3-Phenylenyl, 9-Phenylenyl, 2-Dibenzothiopheneyl, 2-Dibenzofuranyl, 4-Dibenzothiopheneyl, 4-Dibenzofuranyl, 3-Fluoranthrayl, 1-Pyrene, 2-Triphenylene, 1-Triptereneyl, 2-Triptereneyl, 2-Phenylenylsulfoneyl, 3-Phenylenylsulfoneyl, 4-Phenylenylsulfoneyl, Dibenzothiophene-5,5- Dioxide-1-yl, dibenzothiophene-5,5-dioxide-2-yl, dibenzothiophene-5,5-dioxide-3-yl, dibenzothiophene-5,5-dioxide-4-yl, 1-adamantyl, 2-adamantyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 2,3-dicyanophenyl, 2,4-dicyanophenyl, 2,5-dicyanophenyl, 2,6-dicyanophenyl, 3,4-dicyanophenyl, 3,5-dicyanophenyl, 3-cyanopyridin-2-yl, 4-cyanopyridin-2-yl, 5-cyanopyridin-2-yl, 6-cyanopyridin-2-yl, 2-cyanopyridin-3-yl, 4-cyanopyridin-3-yl, 5-cyanopyridin-3-yl, 6-cyanopyridin-3-yl 2-Cyanopyridin-4-yl, 3-Cyanopyridin-4-yl, 2,4-Dicyanopyridin-3-yl, 2,5-Dicyanopyridin-3-yl, 2,6-Dicyanopyridin-3-yl, 2,3-Dicyanopyridin-4-yl, 2,5-Dicyanopyridin-4-yl, 2,6-Dicyanopyridin-4-yl, 2-Cyanopyridin-1-naphthyl, 3-Cyanopyridin-1- Naphthyl, 4-cyano-1-naphthyl, 5-cyano-1-naphthyl, 6-cyano-1-naphthyl, 7-cyano-1-naphthyl, 8-cyano-1-naphthyl, 1-cyano-2-naphthyl, 3-cyano-2-naphthyl, 4-cyano-2-naphthyl, 5-cyano-2-naphthyl, 6-cyano-2-naphthyl, 7-cyano-2-naphthyl, 8-cyano-2-naphthyl, etc.

[0523] <R 22 R 23 >

[0524] R 22 and R 23 Each can be independently represented by any one of equations (21b) to (25b): [Chemistry 96]

[0525] In equations (21b) to (25b), Ar 22A "Same" or "different" indicates substituted or unsubstituted aromatic hydrocarbon groups, or substituted or unsubstituted heteroaromatic groups; L 22A It indicates a phenylene oxide or a single bond.

[0526] Ar 22A Whether the groups are the same or different, more preferably unsubstituted or cyano-substituted aromatic hydrocarbon groups, or substituted or unsubstituted heteroaromatic groups. As Ar 22A Specific examples are not particularly limited; for example, examples related to Ar could be cited. 21A Same group.

[0527] In equation (2), Ar in equations (21a) to (24a) is more preferred. 21A And Ar in equations (21b) to (25b) 22A At least two of them contain cyano groups. Based on this configuration, the LUMO of the material used in photoelectric conversion elements for camera sensors can be increased, thereby improving the response speed of the camera sensor.

[0528] <Compound(3)>

[0529] In one embodiment of the present invention, the material (1′) for the photoelectric conversion element of the imaging element described above can be a compound represented by the following formula (3). The compound represented by formula (3) also falls within the scope of the present invention.

[0530] [Chemistry 97]

[0531] In the above formula (3), L 31A Indicates phenylene; r 1A R represents an integer that is either 0 or 1; 31 Any one of equations (31a) to (34a) can be used to represent: [Chemistry 98]

[0532] In equations (31a) to (34a), Ar 31ASame or different, indicating phenyl, pyridyl, pyridyl substituted with one or more cyano groups, pyridyl substituted with one or more alkyl groups having 1 to 6 carbon atoms, pyridyl substituted with one or more cyano groups, or naphthyl that can be substituted; R 32 and R 33 Each can be independently represented by any one of equations (31b) to (35b): [Chemistry 99]

[0533] In equations (31b) to (35b), Ar 32A Same or different, indicating phenyl, phenyl substituted with one or more alkyl groups having 1 to 6 carbon atoms, phenyl substituted with one or more cyano groups, pyridyl, pyridyl substituted with one or more alkyl groups having 1 to 6 carbon atoms, pyridyl substituted with one or more cyano groups, or biphenyl; L 32A Indicates a phenylene oxide or a single bond; Indicates the bonding site; Ar in formulas (31a) to (34a) 31A And Ar in equations (31b) to (35b) 32A At least one of them has a cyano group; in R 31 The expression (31a) and / or R 32 and R 33 When at least one of them is represented by the formula (31b), Ar in the formula (31a) 31A And Ar in equation (31b) 32A The same or different is a phenyl group substituted with one or more cyano groups or a pyridyl group substituted with one or more cyano groups.

[0534] <L 31A >

[0535] In equation (3), L 31A To represent phenylene, from the viewpoint of improving thermal stability, it is preferable to represent ortho-phenylene or para-phenylene. Furthermore, from the viewpoint of improving thermal stability, in Ar... 31A In the case where the naphthyl group can be substituted, L 31A Preferably, it is phenylene. L 31A Corresponding to L in equation (1′) 31 .

[0536] <r 1A >

[0537] In equation (3), r 1A An integer representing either 0 or 1. r 1A When L is 0, 31A Indicates a single bond. 1A Corresponding to r in equation (1′) 1.

[0538] <R 31 >

[0539] R 31 Any one of equations (31a) to (34a) can be used to represent: [Chemistry 100]

[0540] In equations (31a) to (34a), Ar 31A Whether the terms are the same or different, they refer to phenyl, pyridyl, pyridyl with one or more cyano groups substituted, pyridyl with one or more alkyl groups having 1 to 6 carbon atoms substituted, pyridyl with one or more cyano groups substituted, or naphthyl that can be substituted. From the viewpoint of improving thermal stability, it is preferred to refer to phenyl, pyridyl, pyridyl with one or more cyano groups substituted, naphthyl, or naphthyl with one or more cyano groups substituted.

[0541] <R 32 R 33 >

[0542] R 32 and R 33 Each can be independently represented by any one of equations (31b) to (35b): [Chemistry 101]

[0543] In equations (31b) to (35b), Ar 32A Whether the terms are the same or different, they represent phenyl, phenyl substituted with one or more alkyl groups having 1 to 6 carbon atoms, phenyl substituted with one or more cyano groups, pyridyl, pyridyl substituted with one or more alkyl groups having 1 to 6 carbon atoms, pyridyl substituted with one or more cyano groups, or biphenyl. From the viewpoint of improving thermal stability, phenyl, phenyl substituted with one or more cyano groups, pyridyl, pyridyl substituted with one or more cyano groups, or biphenyl are preferred; L 32A Indicates a phenylene oxide or a single bond; Indicates the bonding site.

[0544] Preferred examples of the compounds shown in formulas (2) and (3) are illustrated in the table below, but are not limited to these. The table below shows compounds having skeletons as shown below (CC′1) to (CC′132), and groups as shown below (GC′1) to (GC′50) bonded to R groups at the # sites of the groups to the R sites of the skeletons, representing (CC′x) 31 -GC′y 31 Compounds of ). Here, x 31 y represents any integer from 1 to 132. 31Represents any integer from 1 to 50. That is, (CC′x 31 -GC′y 31 The compounds represented by ) indicate compounds in the range (CC′1-GC′1) to (CC′132-GC′50). Therefore, for example, in x 31 =105, y 31 In the case of a compound such as (CC′105-GC′1) with a ratio of 1, the following (CC′105-GC′1) compound is represented by having a (CC′105) skeleton and a (GC′1) group bonded to an R group at the # site of the group and the skeleton.

[0545] [Chemistry 102]

[0546] [Table 127]

[0547]

[0548] [Table 128]

[0549]

[0550] [Table 129]

[0551]

[0552] [Table 130]

[0553]

[0554] [Table 131]

[0555]

[0556] [Table 132]

[0557]

[0558] [Table 133]

[0559]

[0560] [Table 134]

[0561]

[0562] [Table 135]

[0563]

[0564] [Table 136]

[0565]

[0566] [Table 137]

[0567]

[0568] [Table 138]

[0569]

[0570] [Table 139]

[0571]

[0572] [Table 140]

[0573]

[0574] [Table 141]

[0575]

[0576] [Table 142]

[0577]

[0578] [Table 143]

[0579]

[0580] [Table 144]

[0581]

[0582] [Table 145]

[0583]

[0584] [Table 146]

[0585]

[0586] [Table 147]

[0587]

[0588] [Table 148]

[0589]

[0590] [Table 149]

[0591]

[0592] [Table 150]

[0593]

[0594] [Table 151]

[0595]

[0596] [Table 152]

[0597]

[0598] [Table 153]

[0599]

[0600] [Table 154]

[0601]

[0602] [Table 155]

[0603]

[0604] [Table 156]

[0605]

[0606] [Table 157]

[0607]

[0608] [Table 158]

[0609]

[0610] [Table 159]

[0611]

[0612] [Table 160]

[0613]

[0614] [Table 161]

[0615]

[0616] [Table 162]

[0617]

[0618] [Table 163]

[0619]

[0620] [Table 164]

[0621]

[0622] [Table 165]

[0623]

[0624] [Table 166]

[0625]

[0626] [Table 167]

[0627]

[0628] [Table 168]

[0629]

[0630] [Table 169]

[0631]

[0632] [Table 170]

[0633]

[0634] [Table 171]

[0635]

[0636] [Table 172]

[0637]

[0638] [Table 173]

[0639]

[0640] [Table 174]

[0641]

[0642] [Table 175]

[0643]

[0644] [Table 176]

[0645]

[0646] [Table 177]

[0647]

[0648] [Table 178]

[0649]

[0650] [Chemistry 103]

[0651] [Chemistry 104]

[0652] [Chemistry 105]

[0653] [Chemistry 106]

[0654] [Chemistry 107]

[0655] [Chemistry 108]

[0656] [Chemistry 109]

[0657] [Chemical 110]

[0658] [Chemistry 111]

[0659] [Chemistry 112]

[0660] [Chemistry 113]

[0661] [Chemistry 114]

[0662] [Chemistry 115]

[0663] Other preferred examples of materials (2) or (3) for photoelectric conversion elements for camera elements are shown below, but are not limited to these.

[0664] [Chemistry 116]

[0665] [Chemistry 117]

[0666] [Chemistry 118]

[0667] [Chemistry 119]

[0668] <Compound(4)>

[0669] In one embodiment of the present invention, the material (1′) for the photoelectric conversion element of the imaging element described above can be a compound represented by the following formula (4). The compound represented by formula (4) also falls within the scope of the present invention.

[0670] [Chemistry 120]

[0671] In equation (4), Ar 41 and Ar 42Each can independently represent an aromatic hydrocarbon group with 6 to 26 carbon atoms (substituted or unsubstituted), a nitrogen-containing heteroaromatic group with 3 to 26 carbon atoms (substituted or unsubstituted) consisting only of a 6-membered ring, an oxygen-containing or sulfur-containing heteroaromatic group with 3 to 26 carbon atoms (substituted or unsubstituted), or a cyclic aliphatic hydrocarbon group with 10 to 16 carbon atoms; L 41 ~L 43 Each can independently represent a divalent aromatic hydrocarbon group with 6 to 26 carbon atoms (substituted or unsubstituted), a divalent nitrogen-containing heteroaromatic group with 3 to 26 carbon atoms (substituted or unsubstituted) consisting only of a 6-membered ring, a divalent heteroaromatic group with 3 to 26 carbon atoms (substituted or unsubstituted), or a divalent cyclic aliphatic hydrocarbon group with 10 to 16 carbon atoms; p 4 q 4 and r 4 Each independently represents an integer from 0 to 2; Ar 41 Ar 42 L 41 L 42 and L 43 At least one of them has a cyano group.

[0672] <Ar 41 Ar 42 >

[0673] In equation (4), Ar 41 and Ar 42 Each can independently represent an aromatic hydrocarbon group with 6 to 26 carbon atoms that is substituted or unsubstituted, a nitrogen-containing heteroaromatic group with 3 to 26 carbon atoms that is substituted or unsubstituted and consists only of a 6-membered ring, an oxygen-containing or sulfur-containing heteroaromatic group with 3 to 26 carbon atoms that is substituted or unsubstituted, or a cyclic aliphatic hydrocarbon group with 10 to 16 carbon atoms.

[0674] As Ar 41 and Ar 42 Specific examples are not particularly limited; for example, examples related to Ar could be cited. 11 Ar 21 Ar 31 Ar 21A and Ar 22AThe same group. Among these groups, for example, each is preferably substituted by 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, such as phenyl, tolyl, biphenyl, pyridylphenyl, naphthylphenyl, pyridyl, pyrimidinyl, pyrazinyl, triazinyl, naphthyl, quinolinyl, isoquinolinyl, benzothiophene, benzofuranyl, anthraceneyl, phenanthrene, fluorenyl, dibenzothiophene, dibenzofuranyl, fluoranyl, pyrene, triphenylene, tripteneyl, cyanophenyl, cyanonylnaphthyl, or cyanopyridinyl, etc., from the viewpoint of excellent material properties for photoelectric conversion elements used in imaging elements. More preferably, it is phenyl, p-tolyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, 3-(2-pyridyl)phenyl, 4-(2-pyridyl)phenyl, 3-(3-pyridyl)phenyl, 4-(3-pyridyl)phenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-phenylpyridin-6-yl, 2-phenylpyridin-5-yl, 2-phenylpyridin-4-yl, 3-phenylpyridin-5-yl, 3-phenylpyridin-6-yl, 2,6-diphenylpyridin-4-yl, 4,6-diphenylpyridin-2-yl, 2-pyrimidinyl, 2-pyrazinyl, 1-naphthyl, 2-naphthyl, 3-quinolinyl, 4-quinolinyl, 3-isoquinolinyl, 2-benzothiophene, 2-benzofuranyl, 2-fluorenyl, 9, 9-Dimethylfluorene-2-yl, 9,9-dimethylfluorene-3-yl, 9,9-dimethylfluorene-4-yl, 9,9-diphenylfluorene-2-yl, 9,9-diphenylfluorene-3-yl, 9,9-diphenylfluorene-4-yl, 9-anthrayl, 1-phenanthyl, 2-phenanthyl, 3-phenanthyl, 9-phenanthyl, 2-dibenzothiophene, 2-dibenzofuranyl, 4-dibenzothiophene, 4-dibenzofuranyl, 3-fluoranthyl, 1-pyrene, 2-triphenylene, 1-tripteneyl, 2-tripteneyl, 2-phenylphenylsulfoneyl, 3-phenylphenylsulfoneyl, 4-phenylphenylsulfoneyl, dibenzothiophene-5,5-dioxide-1-yl, dibenzothiophene-5,5-dioxide-2-yl, dibenzothiophene-5,5-dioxide 3-yl, dibenzothiophene-5,5-dioxide-4-yl, 1-adamantyl, 2-adamantyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 2,3-dicyanophenyl, 2,4-dicyanophenyl, 2,5-dicyanophenyl, 2,6-dicyanophenyl, 3,4-dicyanophenyl, 3,5-dicyanophenyl, 3-cyanopyridin-2-yl, 4-cyanopyridin-2-yl, 5-cyanopyridin-2-yl, 6-cyanopyridin-2-yl, 2-cyanopyridin-3-yl, 4-cyanopyridin-3-yl, 5-cyanopyridin-3-yl, 6-cyanopyridin-3-yl, 2-cyanopyridin-4-yl, 3-cyanopyridin-4-yl, 2,4-dicyanopyridin-3-yl, 2,5-Dicyanopyridin-3-yl, 2,6-Dicyanopyridin-3-yl, 2,3-Dicyanopyridin-4-yl, 2,5-Dicyanopyridin-4-yl, or 2,6-Dicyanopyridin-4-yl, etc.

[0675] <L 41 L 42 L 43 >

[0676] In equation (4), L 41 ~L 43 Each can independently represent a divalent aromatic hydrocarbon group with 6 to 26 carbon atoms that is substituted or unsubstituted, a divalent nitrogen-containing heteroaromatic group with 3 to 26 carbon atoms that is substituted or unsubstituted and consists only of a 6-membered ring, a divalent heteroaromatic group with 3 to 26 carbon atoms that is substituted or unsubstituted and contains oxygen or sulfur, or a divalent cyclic aliphatic hydrocarbon group with 10 to 16 carbon atoms.

[0677] As L 41 L 42 and L 43 Specific examples are not particularly limited; for example, examples related to L can be given independently. 11 L 21 and L 31 The same group. Among these groups, for example, each can be independently 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, such as phenyl, biphenyl, pyridyl, pyridinyl, pyrazinyl, triazine, naphthyl, quinolinyl, benzothiophene, benzofuranyl, anthracene, phenanthrene, fluorenyl, dibenzothiophene, dibenzofuranyl, fluoranyl, pyrene, triphenylene, or tripteneyl. Furthermore, from the viewpoint of superior material properties for use in photoelectric conversion elements for imaging elements, phenyl groups that can be substituted with a cyano group or pyridyl groups that can be substituted with a cyano group are more preferred.

[0678] <p 4 q 4 r 4 >

[0679] p 4 q 4 and r 4 Each can independently represent an integer from 0 to 2.

[0680] <Ar 41 Ar 42 L 41 L 42 L 43 and the characteristics of the triazine ring >

[0681] In equation (4), Ar 41 Ar 42 L 41 L 42 and L 43 At least one of them has a cyano group. In other words, Ar 41 Ar 42 L 41 L 42 and L 43 At least one of them is substituted with a cyano group or is substituted with a group having a cyano group.

[0682] In equation (4), in Ar 41 Ar 42 L 41 L 42 and L 43 In formula (4), 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 preferably 2 or more. 41 Ar 42 L 41 L 42 and L 43 In this context, the sum of the number of cyano groups and the number of pyridino groups in these groups is more preferably 2 or more. The nitrogen-containing heteroaromatic ring composed of a 6-membered ring is selected from (1) heteroaromatic monocyclic rings selected from pyridine rings, pyridazine rings, pyrimidine rings, pyrazine rings, triazine rings, and tetraazine rings, or (2) a fused ring composed of 2 to 4 aromatic monocyclic rings, a portion of which contains at least one heteroaromatic monocyclic ring selected from the heteroaromatic monocyclic ring. The heteroaromatic monocyclic rings of pyridine rings, pyridazine rings, pyrimidine rings, pyrazine rings, triazine rings, and tetraazine rings contain a nitrogen atom as a cyclizing atom in a fully conjugated aromatic ring, and this nitrogen atom is not covalently bonded to a hydrogen atom. It should be noted that, unless otherwise specified, "aromatic monocyclic ring" in this specification refers to both "heteroaromatic monocyclic rings" and "aromatic hydrocarbon monocyclic rings." In formula (1′), the -[L 41 ] p 4 -Ar 41 、-[L 42 ] q 4 -Ar 42 and -[L 43 ] r 4 The central triazine ring of the -(tripyroxene)-bonded Ar is not contained in the Ar 41 Ar 42 L 41 L 42 and L 43The central triazine ring is a nitrogen-containing heteroaromatic ring composed of a 6-membered ring. In other words, preferably, the sum of the number of cyano groups in the three substituents of the central triazine ring and the number of nitrogen-containing heteroaromatic rings composed of a 6-membered ring is 2 or more, and more preferably, the sum of the number of cyano groups in the three substituents of the central triazine ring and the number of pyridyl groups is 2 or more.

[0683] As a preferred specific example of the compound shown in formula (4), compounds having groups GA′45 to GA′50 among the compounds of (CA′1-GA′1) to (CA′163-GA′50) can be cited, but are not limited to these. As a further preferred specific example of the compound shown in formula (4), the compounds shown in the table below can be cited. It is shown that (CE′x) has a skeleton of (CE′1) to (CE′38) as shown below, and the groups of (GE′1) to (GE′6) shown below are bonded to the R of the skeleton at the # site of the group. 41 -GE′y 41 Compounds of ). Here, x 41 y represents any integer from 1 to 38. 41 Represents any integer from 1 to 6. That is, (CE′x 41 -GE′y 41 The compounds represented by ) indicate compounds in the range (CE′1-GE′1) to (CE′38-GE′6). Therefore, for example, in x 41 =1, y 41 In the case of a compound such as (CE′1-GE′1) = 1, the following (CE′1-GE′1) compound is represented by having a (CE′1) skeleton and a (GE′1) group bonded to an R group at the # site of the group and the skeleton.

[0684] [Chemistry 121]

[0685] [Table 179]

[0686]

[0687] [Table 180]

[0688]

[0689] [Table 181]

[0690]

[0691] [Table 182]

[0692]

[0693] [Table 183]

[0694]

[0695] [Table 184]

[0696]

[0697] [Table 185]

[0698]

[0699] [Table 186]

[0700]

[0701] [Table 187]

[0702]

[0703] [Table 188]

[0704]

[0705] [Table 189]

[0706]

[0707] [Table 190]

[0708]

[0709] [Table 191]

[0710]

[0711] [Chemistry 122]

[0712] [Chemistry 123]

[0713] [Chemistry 124]

[0714] <Materials for photoelectric conversion elements in camera components, hole blocking materials for camera components>

[0715] One aspect of the present invention relates to a material for a photoelectric conversion element for an image sensor formed from, or comprising, 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)). The use of the material for a photoelectric conversion element for an image sensor according to one aspect of the present invention will be described below. As described above, the material for a photoelectric conversion element for an image sensor, by balancing response speed and external quantum efficiency, can be suitable for use in layers, such as photoelectric conversion layers and hole blocking layers, of an image sensor.

[0716] Furthermore, one aspect of the present invention relates to a material for a photoelectric conversion element for a camera element that has a high T0 g This prevents changes in film state, such as crystallization, caused by annealing during the manufacture of photoelectric conversion elements. Consequently, it prevents a decrease in external quantum efficiency in the image sensor formed from the material of the photoelectric conversion element for image sensors according to one aspect of the present invention, and reduces dark current. Therefore, the material of the photoelectric conversion element for image sensors according to one aspect of the present invention can be suitably used as a photoelectric conversion element material for image sensors and a hole-blocking material requiring resistance to annealing after the formation of the photoelectric conversion layer.

[0717] One aspect of the present invention relates to a material for a photoelectric conversion element for a camera element, such as a material that can be used as a photoelectric conversion layer in a camera element, or a hole blocking layer in the camera element, i.e., a hole blocking material.

[0718] One aspect of the present invention relates to a material for a photoelectric conversion element for an image sensor comprising the skeleton shown in formula (1) or (1′) above. The material for a photoelectric conversion element for an image sensor comprising the skeleton shown in formula (1) or (1′) and the hole-blocking material contributes to the fabrication of a material for a photoelectric conversion element for an image sensor with excellent response speed and external quantum efficiency characteristics.

[0719] <About LUMO Levels>

[0720] To reduce dark current, improve external quantum efficiency, and enhance response speed, materials used in photoelectric conversion elements for imaging devices may require rapid charge movement within the photoelectric conversion layer. For rapid charge movement, it is preferable that the LUMO energy level of the n-type semiconductor material in the photoelectric conversion layer is close to that of the material used in the hole blocking layer. For example, when fullerene (C60) is used in the photoelectric conversion layer, the LUMO energy level of the hole blocking layer, calculated using quantum chemical methods obtained through density functional theory (DFT) as described below, is sequentially 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. Furthermore, the LUMO energy level of the hole blocking layer is not limited; -5.0 eV or more is acceptable, but -4.0 eV or more is preferred.

[0721] In one aspect of the imaging element, the LUMO energy level of the material used for the photoelectric conversion element of the imaging element is a value calculated by quantum chemical calculations. The optimization of the molecular structure and the calculation of the LUMO energy level can be obtained using Gaussian programs through density functional theory (DFT) based on the calculation conditions of B3LYP functional and 6-31G(d) basis functions.

[0722] <Regarding glass transition temperature>

[0723] In one aspect of the present invention, the material used in the formation of the layer of the imaging element for the photoelectric conversion element of the imaging element is the material for the photoelectric conversion element of the imaging element shown in formula (1) or (1′). The glass transition temperature of these materials for the photoelectric conversion element of the imaging element shown in formula (1) or (1′) is not particularly limited. From the viewpoint of suitability for 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 more preferably 150°C or higher. It should be noted that this glass transition temperature is a value obtained by differential scanning calorimetry.

[0724] The differential scanning calorimeter and experimental conditions are as follows. Under the following conditions: differential scanning calorimeter model: Hitachi DSC7020 manufactured by Hitachi Advanced Technology Co., Ltd.; operating conditions: heating rate: 10℃ / min, temperature range: 40℃~400℃, the glass transition temperature was determined from the peaks of two scans.

[0725] <Regarding molecular weight>

[0726] In one aspect of the present invention, the compound represented by formula (1) or (1′) used in the formation of the layer of the imaging element is preferably a material with a molecular weight of 550 or more, which improves the glass transition temperature and the thermal stability of the film. The molecular weight of the material used in the photoelectric conversion element of the imaging element can be evaluated by mass analysis.

[0727] <On Amorphous Properties>

[0728] As one aspect of the present invention, the material for the photoelectric conversion element of the imaging element, i.e., the material for the photoelectric conversion element of the imaging element shown in formula (1) or (1′), preferably forms an amorphous layer by vapor deposition of the material. If the vapor deposition film is a crystalline layer, the interface with the adjacent layer is not uniform, thus becoming a defect factor of the element.

[0729] There is no particular limitation on the method for confirming whether a vapor-deposited film is an amorphous layer. It can be confirmed by visually judging whether crystallization is present, or by observing no sharp diffraction peaks in the XRD measurement of the vapor-deposited film.

[0730] <Camera Components>

[0731] One aspect of the present invention relates to a camera element comprising a layer containing a material for a photoelectric conversion element for a camera element according to one aspect of the present invention.

[0732] There are no particular limitations on the structure of the camera element; for example, the structures shown in (i) to (vi) below can be cited.

[0733] (i) First electrode / photoconversion layer / second electrode

[0734] (ii) First electrode / hole blocking layer / photoelectric conversion layer / second electrode

[0735] (iii) First electrode / photoelectric conversion layer / electron blocking layer / second electrode

[0736] (iv) First electrode / Hole blocking layer / Photoelectric conversion layer / Electron blocking layer / Second electrode

[0737] (v) First electrode / Hole blocking layer / Photoelectric conversion layer / Electron blocking layer / Hole transport layer / Second electrode

[0738] (vi) First electrode / Electron transport layer / Hole blocking layer / Photoelectric conversion layer / Electron blocking layer / Hole transport layer / Second electrode

[0739] Hereinafter, taking the above-described (v) configuration as an example, a camera element according to one aspect of the present invention will be described in more detail with reference to FIG1. ​​FIG1 is a schematic cross-sectional view showing an example of a laminated structure of a camera element having a layer comprising a material comprising a photoelectric conversion element for a camera element according to one aspect of the present invention.

[0740] The imaging element 100 sequentially comprises 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. Some of these layers may be omitted, or other layers may be added. It should be noted that, of the aforementioned 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.

[0741] Specifically, the imaging element 100 shown in FIG1 can be a photoelectric conversion element for imaging. Light is incident on the imaging element 100 from below the transparent first electrode 1, and the light is received by the photoelectric conversion layer 3, which serves as a light-receiving layer. The incident direction of the light is not particularly limited, and the second electrode 6 can also be made transparent so that light is incident from the second electrode 6.

[0742] The imaging element 100 utilizes an internal electric field generated by the concentration difference of charge carriers in each layer and the difference in work function between the first electrode 1 and the second electrode 6. Due to the light received by the photoelectric conversion layer 3, electrons move to the first electrode 1, and holes move to the second electrode 6. Furthermore, charge movement can also be caused by applying a voltage between the first electrode 1 and the second electrode 6. Thus, the first electrode 1 serves as an electron collecting electrode, and the second electrode 6 serves as a hole collecting electrode.

[0743] It should be noted that each layer can also be replaced with a layer with other names or functions as needed. Examples of layers with other names or functions include, for instance, hole injection layer, work function adjustment layer, and hole transport enhancement layer.

[0744] It should be noted that the substrate disposed below the first electrode 1 is omitted in Figure 1. The substrate used here is not particularly limited; examples include glass plates, quartz plates, and plastic plates. Furthermore, in the case of a structure where light is incident from the substrate side, the substrate is transparent with respect to the wavelength of the light. It should also be noted that the substrate may be disposed on the side of the second electrode 6. The layers described above will be explained below.

[0745] [A layer containing materials for photoelectric conversion elements used in camera sensors]

[0746] As one type of photoelectric conversion element, an imaging element may include, in one or more layers selected from the photoelectric conversion layer and the layer between the photoelectric conversion layer and the second electrode, the material for a photoelectric conversion element as shown in formula (1) or (1′) above. In the structural example shown in FIG1, the imaging element 100 includes the material for a photoelectric conversion element in at least one layer selected from the hole blocking layer 2 and the photoelectric conversion layer 3. In one aspect of the present invention, the imaging element preferably includes the material for a photoelectric conversion element in the hole blocking layer 2. This provides the effect of controlling the reverse movement of holes while rapidly moving the desired charge.

[0747] It should be noted that the material for the photoelectric conversion element for the camera element shown in formula (1) or (1′) above can be included in multiple layers of the camera element. In the case where an electron transport layer is provided, the electron transport layer can also include the material for the photoelectric conversion element for the camera element.

[0748] The following describes a camera photoelectric conversion element 100 in which the hole blocking layer 2 contains material for a photoelectric conversion element for a camera element.

[0749] [First Electrode 1]

[0750] A first electrode 1 is disposed on the substrate.

[0751] In the case of an imaging element having a structure in which light passes through the first electrode and is incident on the photoelectric conversion layer 3, the first electrode 1 may be formed of a transparent material that allows light to pass through or substantially pass through.

[0752] The transparent material used as the lower electrode of the first electrode 1 is not particularly limited, and examples 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.

[0753] It should be noted that when the imaging element 100 has a structure in which light is incident on the photoelectric conversion layer 3 only from the second electrode 6 side, the light transmission characteristics in the first electrode 1 are not important. Therefore, as an example of a material used in the first electrode 1 in this case, gold, iridium, molybdenum, palladium, and platinum can be cited.

[0754] [Cavity Blocking Layer 2]

[0755] A hole blocking layer 2 is provided between the first electrode 1 and the photoelectric conversion layer 3, which serves as the light-receiving layer, as described later.

[0756] The hole blocking layer 2 serves to transport electrons generated in the photoelectric conversion layer 3 to the first electrode 1, and to prevent holes from moving from the photoelectric conversion layer 3 to the first electrode 1, the destination of electron transport. Additionally, depending on the application, it may sometimes also block hole injection from the first electrode 1.

[0757] In addition to the material for photoelectric conversion element for camera element shown in formula (1) or (1′), the hole blocking layer 2 may also contain conventionally known hole blocking material (electron transport material). Examples of previously known hole-blocking materials (electron transport materials) include bis(8-hydroxyquinoline)manganese, tris(8-hydroxyquinoline)aluminum, tris(2-methyl-8-hydroxyquinoline)aluminum, BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), BAlq (bis(2-methyl-8-hydroxyquinoline)-4-(phenylphenol)aluminum), 4,6-bis(3,5-bis(pyridin-4-yl)phenyl)-2-methylpyrimidine, N,N′-diphenyl-1,4,5,8-naphthalenetetracarboxylic acid diimide, and N,N′-bis(4-pyridinyl)-1,4,5,8-naphthalenetetracarboxylic acid diimide.

[0758] The hole-blocking layer 2 can be a single-layer structure containing one or more materials, or a multi-layer stacked structure containing the same or different compositions.

[0759] [Photoelectric conversion layer 3]

[0760] A photoelectric conversion layer 3, serving as a light-receiving layer, is disposed between the hole-blocking layer 2 and the electron-blocking layer 4 (described later). The photoelectric conversion layer 3 can be made of materials with photoelectric conversion capabilities.

[0761] The photoelectric conversion layer 3 can be a single-layer structure containing one or more materials, or a multi-layer stacked structure containing the same or different compositions. Preferably, to improve photoelectric conversion efficiency, the photoelectric conversion layer 3 contains at least two types of materials (organic components).

[0762] Materials used in the photoelectric conversion layer 3, which is a single-layer structure containing a material, include, for example, (i) coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives.

[0763] Materials used in the photoelectric conversion layer 3, which is a single-layer structure comprising two materials, include, for example, combinations of (i) coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives, and (ii) fullerene and its derivatives. The photoelectric conversion layer 3 comprising these materials can be formed by vapor deposition in a pre-mixed powder state, or by co-deposition in any proportion.

[0764] Examples of materials used in the single-layer structure comprising the three materials, namely the photoelectric conversion layer 3, include (i) coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives, (ii) fullerene and its derivatives, and (iii) a combination of hole transport materials. The photoelectric conversion layer 3 comprising these materials can be formed by vapor deposition in a pre-mixed powder state, or by co-deposition in any proportion.

[0765] (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 phthalocyanine chloride and boron naphthyl phthalocyanine chloride (Sub NC).

[0766] (ii) Specific examples of fullerenes and their derivatives include

[60] fullerene,

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

[60] PCBM).

[0767] (iii) Hole transport materials can be known hole transport materials. Examples of hole transport materials include aromatic tertiary amine compounds, naphthalene compounds, anthracene compounds, tetraphenylene compounds, pentaphenylene compounds, phenanthrene compounds, pyrene compounds, perylene compounds, fluorene compounds, carbazole compounds, indole compounds, pyrrole compounds, styrene compounds, thiophene compounds, benzotrifuran compounds, benzotrithiophene compounds, naphthodithiophene compounds, naphthothiophene compounds, benzodifuran compounds, benzodithiophene compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, benzodithiophene compounds, benzothiophene compounds, indole and carbazole compounds, etc. Among them, preferred compounds include fluorene compounds, naphthodithiophene compounds, naphthothiophene compounds, benzodifuran compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, denominated dithiophene compounds, benzothiophene compounds, and indole-carbazole compounds, with more preferred compounds being fluorene compounds, denominated dithiophene compounds, benzothiophene compounds, and indole-carbazole compounds.

[0768] Specific examples of hole transport materials include 9,9′-(9,9′-spirobis[9H-fluorene]-2,7′-diyl)bis[9H-carbazole], 2,7-diphenyl[1]benzothiophene[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, and naphtho[2,3-b]naphtho[ 2′,3′:4,5]thiopheno[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, benzo[1,2-b:8,7-b′]dithiophene, [1]benzothiopheno[3,2-b][1]benzothiophene, and the following compounds (ic-1), (ic-2) and (ic-3), etc.

[0769] [Chemistry 125]

[0770] Furthermore, the material used for the photoelectric conversion element in an image sensor is not limited to being contained only in the photoelectric conversion layer. For example, the material used for the photoelectric conversion element in an image sensor may be contained in a layer adjacent to the photoelectric conversion layer 3 (hole blocking layer 2 or electron blocking layer 4).

[0771] [Electron blocking layer 4]

[0772] An electron blocking layer 4 is disposed between the photoelectric conversion layer 3 and the hole transport layer 5.

[0773] The electron blocking layer 4 serves to allow holes generated in the photoelectric conversion layer 3 to travel from the photoelectric conversion layer 3 to the second electrode 6, and to block electrons generated in the photoelectric conversion layer 3 from moving towards the second electrode 6. Additionally, depending on the application, it may sometimes also block electron injection from the second electrode 6.

[0774] The electron blocking layer 4 can be a single-layer structure containing one or more materials, or a stacked structure containing multiple layers with the same or different compositions. For example, it can be a two-layer structure containing the following layers: a layer adjacent to a photoelectric conversion layer 3 containing a material specifically for electron blocking, and a layer adjacent to a hole transport layer 5 containing a material specifically for hole transport.

[0775] The electron blocking layer 4 preferably comprises a known hole transport material. Examples of known hole transport materials include the same material used in the photoelectric conversion layer 3 described above.

[0776] [Hole transport layer 5]

[0777] A hole transport layer 5 is disposed 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 achieved by a change in the internal electric field caused by the interaction between the hole transport material and the surrounding material. In addition, when the second electrode 6 is formed by sputtering, the hole transport layer 5 has the function of reducing damage to the organic layer (e.g., the electron blocking layer 4) during sputtering.

[0778] The hole transport layer 5 can be made of known materials, such as naphthalene-1,4,5,8-tetracarboxylic acid dianhydride (NTCDA), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene (HATCN), etc.

[0779] The hole transport layer 5 can be a single-layer structure containing one or more materials, such as the materials described above and conventionally known hole transport materials. Examples of conventionally known hole transport materials include materials identical to those used in the photoelectric conversion layer 3 described above.

[0780] [Second Electrode 6]

[0781] A second electrode 6 is disposed on the electron blocking layer 5.

[0782] Materials that can be used as the second electrode 6 include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / alumina (Al2O3) mixture, indium, lithium / aluminum mixture, gold, and rare earth metals.

[0783] [Methods of forming each layer]

[0784] In addition to the first electrode 1 and the second electrode 6 described above, each layer can be formed as follows: for example, by using known methods such as vacuum evaporation, spin coating, casting, or the LB (Langmuir-Blodgett method) to thin the material of each layer (together with materials such as adhesive resin and solvent as needed).

[0785] There are no particular restrictions on the thickness of the layers formed in this way; it can be selected appropriately according to the situation, usually in the range of 5nm or more and 5μm or less.

[0786] The first electrode 1, serving as the lower electrode, and the second electrode 6, serving as the upper electrode, can be formed by thinning the electrode material using methods such as vapor deposition or sputtering. Patterns can be formed through a mask of the desired shape during vapor deposition or sputtering, or patterns of the desired shape can be formed by photolithography after thin films have been formed by vapor deposition or sputtering.

[0787] The film thickness of the first electrode 1 and the second electrode 6 is preferably less than 1 μm, and more preferably more than 10 nm and less than 200 nm.

[0788] A camera element having a photoelectric conversion element according to one aspect of the present invention is, for example, a camera element that can be applied to a digital camera, a digital camcorder, or a camera element built into a mobile phone, etc.

[0789] <Summary>

[0790] As understood from the foregoing description, this disclosure includes the following methods.

[0791] Method 1: A camera element comprising a layer containing a material for a photoelectric conversion element for a camera element, said material for the photoelectric conversion element for a camera element being represented by the following formula (1) or formula (1′): Regarding the material for the photoelectric conversion element for a camera element shown in the following formula (1): [Chemical 126]

[0792] In equation (1), CA is represented by the following equation (1a), [Chemistry 127]

[0793] 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; Ar 3 Each independently represents a substituted or unsubstituted aromatic hydrocarbon group in the 1-5 valent range, a substituted or unsubstituted heteroaromatic group in the 1-5 valent range, or a substituted or unsubstituted cyclic aliphatic hydrocarbon group in the 1-5 valent range; L 1 ~L 3 Each independently represents a substituted or unsubstituted divalent to tetravalent aromatic hydrocarbon group, a substituted or unsubstituted divalent to tetravalent heteroaromatic group, or a substituted or unsubstituted divalent to tetravalent cyclic aliphatic hydrocarbon group; R 1 and R 2 Each can be independently represented as hydrogen or Ar. 3 ;a 1 a 2 b 1 b 2c and d independently represent integers from 1 to 3; d and e independently represent integers from 1 to 2; and c + d + e represent integers from 1 to 3; p, q, and r independently represent integers from 0 to 3; n represents integers from 1 to 3; Ar 1 Ar 2 Ar 3 L 1 L 2 and L 3 At least one of the groups is selected from: heteroaromatic monocyclic groups selected from pyridyl, pyridinyl, pyrimidinyl, pyrazinyl, and tetraazinyl, or a fused-ring group composed of 2 to 4 aromatic monocyclic groups, a portion of which contains at least one selected from said heteroaromatic monocyclic groups; with respect to the material for the photoelectric conversion element for the imaging element shown in the following formula (1′); [Chemical 128]

[0794] In the aforementioned formula (1′), Ar 11 ~Ar 31 Each independently represents a substituted or unsubstituted divalent or trivalent aromatic hydrocarbon group, a substituted or unsubstituted divalent or trivalent heteroaromatic group, or a substituted or unsubstituted divalent or trivalent cyclic aliphatic hydrocarbon group; L 11 ~L 31 Each independently represents a substituted or unsubstituted divalent to tetravalent aromatic hydrocarbon group, a substituted or unsubstituted divalent to tetravalent heteroaromatic group, or a substituted or unsubstituted divalent to tetravalent cyclic aliphatic hydrocarbon group; a 11 a 21 b 11 b 21 c 11 and c 21 Each can independently represent an integer from 1 to 3; p 1 q 1 and r 1 Each represents an integer from 0 to 3 independently; Ar 11 Ar 21 Ar 31 L 11 L 21 and L 31 At least one of them has a cyano group; in Ar 11 Ar 21 Ar 31 L 11 L 21 and L 31 In these groups, the sum of the number of cyano groups and the number of nitrogen-containing heteroaromatic rings composed of 6-membered rings is more than 2.

[0795] Method 2: According to the camera element of Method 1, in the formula (1), n ​​is 1 or 2.

[0796] Method 3: Based on the imaging element of Method 1 or 2, wherein, in the formula (1), a 1 a 2 b 1 b 2 c and each independently represent an integer of 1 or 2, and p, q and r each independently represent an integer from 0 to 2.

[0797] Method 4: The imaging element according to any one of methods 1 to 3, wherein, in formula (1), the Ar 1 Ar 2 Ar 3 L 1 L 2 and L 3 At least one of them is pyridinyl or pyrimidinyl.

[0798] Method 5: The imaging element according to any one of methods 1 to 4, wherein, in formula (1), the Ar 1 Ar 2 Ar 3 L 1 L 2 and L 3 At least two of them are pyridinyl or pyrimidinyl.

[0799] Method 6: According to the imaging element of Method 1, wherein, in the formula (1′), in the Ar 11 Ar 21 Ar 31 L 11 L 21 and L 31 In these groups, the sum of the number of cyano groups and the number of pyridino groups is more than 2.

[0800] Method 7: The imaging element according to Method 1 includes a layer comprising a material for a photoelectric conversion element for the imaging element, wherein the material for the photoelectric conversion element for the imaging element is represented by the following formula (2): [Chemistry 129]

[0801] In equation (2), L 21A Indicates phenylene; q 1A R represents an integer that is either 0 or 1; 21 Any one of equations (21a) to (24a) can be used to represent: [Chemistry 130]

[0802] In equations (21a) to (24a), Ar 21A Same or different indicates substituted or unsubstituted aromatic hydrocarbon groups, or substituted or unsubstituted heteroaromatic groups; R 22 and R 23 Each can be independently represented by any one of equations (21b) to (25b): [Chemistry 131]

[0803] In equations (21b) to (25b), Ar 22A "Same" or "different" indicates substituted or unsubstituted aromatic hydrocarbon groups, or substituted or unsubstituted heteroaromatic groups; L 22A Indicates a phenylene oxide or a single bond; Indicates the bonding site; Ar in formulas (21a) to (24a) 21A And Ar in equations (21b) to (25b) 22A At least one of them has a cyano group; Ar in formulas (21a) to (24a) 21A And Ar in equations (21b) to (25b) 22A In these groups, the sum of the number of cyano groups and the number of pyridine rings is more than 2, in R 21 The expression (21a) and / or R 22 and R 23 When at least one of them is represented by equation (21b), Ar in equation (21a) 21A And Ar in equation (21b) 22A Whether the groups are the same or different, they are aromatic hydrocarbon groups substituted with one or more cyano groups or heteroaromatic groups substituted with one or more cyano groups.

[0804] Method 8: According to the camera element of Method 7, wherein, in the formula (2), the L 21A It can be an ortho-phenylene, a para-phenylene, or a single bond.

[0805] Method 9: According to the imaging element of Method 7 or 8, wherein, in the formula (2), the Ar 21A The same or different, is an aromatic hydrocarbon group substituted with a cyano group, or a heteroaromatic group that is substituted or unsubstituted.

[0806] Method 10: The imaging element according to any one of methods 7 to 9, wherein, in formula (2), the Ar 22A The same or different, is an aromatic hydrocarbon group substituted with a cyano group, or a heteroaromatic group that is substituted or unsubstituted.

[0807] Method 11: The imaging element according to any one of methods 7 to 10, wherein, in formula (2), Ar in formulas (21a) to (24a) 21A And Ar in equations (21b) to (25b) 22A At least two of them have cyano groups.

[0808] Method 12: The imaging element according to any one of methods 1 to 11, wherein the molecular weight of the material used for the photoelectric conversion element of the imaging element is 550 or more.

[0809] Method 13: A camera element according to any one of methods 1 to 12, wherein the layer comprising the material of the photoelectric conversion element for the camera element is a hole blocking layer.

[0810] Method 14: Compounds represented by formulas (11), (12), (13), (14), (3), or (4), wherein the compound represented by formula (11) is: [Chemistry 132]

[0811] In the aforementioned formula (11), Ar 111 and Ar 211 Each independently represents 3-pyridinyl or 4-pyridinyl; Ar 311 This refers to a phenanthrene group (monovalent or divalent), a dimethylfluorenyl group (monovalent or divalent), a diphenylfluorenyl group (monovalent or divalent), a spirodifluorenyl group (monovalent or divalent), a triterpenyl group (monovalent or divalent), an aromatic group having at least one sulfone group and 6 to 26 carbon atoms, or a cyclic aliphatic hydrocarbon group having 10 to 16 carbon atoms; L 311 This indicates a divalent phenyl or a divalent pyridyl group, in L... 311 In the case of multiple Ls, multiple Ls 311 They can be the same or different; r 11 n represents an integer from 0 to 2; 11 Representing an integer of 1 or 2, the compound with a triazine ring shown in the following formula (12) is: [Chemistry 133]

[0812] In the above formula (12), L 112 and L 212 The divalent pyridinyl group represents a pyridinyl group; the divalent pyridinyl group has a bond with the triazine ring at the 3- or 4-position; when the divalent pyridinyl group has a bond with the triazine ring at the 4-position, Ar 112 and Ar 212Each of these groups independently represents an aromatic hydrocarbon group with 10 to 26 carbon atoms, a nitrogen-containing heteroaromatic group with 6 to 26 carbon atoms consisting only of a 6-membered ring, an aromatic group with 6 to 26 carbon atoms having at least one sulfone group, or a cyclic aliphatic hydrocarbon group with 10 to 16 carbon atoms; when the divalent pyridinium group has a bond with the triazine ring at the 3-position, Ar 112 and Ar 212 Each can independently represent biphenyl, terphenyl, phenanthrene, dimethylfluorenyl, diphenylfluorenyl, spirodifluorenyl, triphenylenyl, an aromatic group having at least one sulfone group and 6 to 26 carbon atoms, or a cyclic aliphatic hydrocarbon group having 10 to 16 carbon atoms; Ar 312 The following groups represent aromatic hydrocarbon groups with 6 to 26 carbon atoms, nitrogen-containing heteroaromatic groups with 6 to 26 carbon atoms consisting only of a 6-membered ring, oxygen-containing or sulfur-containing heteroaromatic groups with 4 to 26 carbon atoms, aromatic groups with 6 to 26 carbon atoms having at least one sulfone group, or cyclic aliphatic hydrocarbon groups with 10 to 16 carbon atoms; L 312 Indicates a single bond, a divalent or trivalent phenyl group, or a divalent or trivalent pyridyl group; L 412 This indicates a divalent phenyl or a divalent pyridyl group, in L... 412 In the case of multiple Ls, multiple Ls 412 They can be the same or different; c 12 Representing an integer of 1 or 2, the compound shown in equation (13) below is: [Chemistry 134]

[0813] In the aforementioned formula (13), Ar 113 and Ar 213 Each independently represents 3-pyridinyl or 4-pyridinyl; Ar 313 The following groups represent aromatic hydrocarbon groups with 10 to 26 carbon atoms, nitrogen-containing heteroaromatic groups with 2 to 26 carbon atoms consisting only of a 6-membered ring, oxygen-containing or sulfur-containing heteroaromatic groups with 4 to 26 carbon atoms, aromatic groups with 6 to 26 carbon atoms having at least one sulfone group, or cyclic aliphatic hydrocarbon groups with 10 to 16 carbon atoms; L 313 Indicates a single bond, a divalent or trivalent phenyl group, or a divalent or trivalent pyridyl group; L 413 This indicates a divalent phenyl or a divalent pyridyl group, in L... 413 In the case of multiple Ls, multiple Ls 413 They can be the same or different; c 13 Representing an integer of 1 or 2, the compound shown in equation (14) is: [Chemistry 135]

[0814] In the aforementioned formula (14), Ar 114 and Ar214 Each independently represents 3-pyridinyl or 4-pyridinyl; Ar 314 The following groups represent aromatic hydrocarbon groups with 10 to 24 carbon atoms, nitrogen-containing heteroaromatic groups with 6 to 26 carbon atoms consisting only of a 6-membered ring, oxygen-containing or sulfur-containing heteroaromatic groups with 4 to 26 carbon atoms, aromatic groups with 6 to 26 carbon atoms having at least one sulfone group, or cyclic aliphatic hydrocarbon groups with 10 to 16 carbon atoms; L 314 Indicates a single bond, a divalent or trivalent phenyl group, or a divalent or trivalent pyridyl group; L 414 This indicates a divalent phenyl or a divalent pyridyl group, in L... 414 In the case of multiple Ls, multiple Ls 414 They can be the same or different; c 14 Representing an integer of 1 or 2, the compound shown in equation (3) below is: [Chemistry 136]

[0815] In the above formula (3), L 31A Indicates phenylene; r 1A R represents an integer that is either 0 or 1; 31 Any one of equations (31a) to (34a) can be used to represent: [Chemistry 137]

[0816] In equations (31a) to (34a), Ar 31A Same or different, indicating phenyl, pyridyl, pyridyl substituted with one or more cyano groups, pyridyl substituted with one or more alkyl groups having 1 to 6 carbon atoms, pyridyl substituted with one or more cyano groups, or naphthyl that can be substituted; R 32 and R 33 Each can be independently represented by any one of equations (31b) to (35b): [Chemistry 138]

[0817] In equations (31b) to (35b), Ar 32A Same or different, indicating phenyl, phenyl substituted with one or more alkyl groups having 1 to 6 carbon atoms, phenyl substituted with one or more cyano groups, pyridyl, pyridyl substituted with one or more alkyl groups having 1 to 6 carbon atoms, pyridyl substituted with one or more cyano groups, or biphenyl; L 32A Indicates a phenylene oxide or a single bond; Indicates the bonding site; Ar in formulas (31a) to (34a) 31A And Ar in equations (31b) to (35b) 32A At least one of them has a cyano group; in R 31The expression (31a) and / or R 32 and R 33 When at least one of them is represented by the formula (31b), Ar in the formula (31a) 31A And Ar in equation (31b) 32A Whether identical or different, a phenyl group substituted with one or more cyano groups or a pyridyl group substituted with one or more cyano groups, the compound represented by formula (4) below is: [Chemical 139]

[0818] In equation (4), Ar 41 and Ar 42 Each can independently represent an aromatic hydrocarbon group with 6 to 26 carbon atoms (substituted or unsubstituted), a nitrogen-containing heteroaromatic group with 3 to 26 carbon atoms (substituted or unsubstituted) consisting only of a 6-membered ring, an oxygen-containing or sulfur-containing heteroaromatic group with 3 to 26 carbon atoms (substituted or unsubstituted), or a cyclic aliphatic hydrocarbon group with 10 to 16 carbon atoms; L 41 ~L 43 Each can independently represent a divalent aromatic hydrocarbon group with 6 to 26 carbon atoms (substituted or unsubstituted), a divalent nitrogen-containing heteroaromatic group with 3 to 26 carbon atoms (substituted or unsubstituted) consisting only of a 6-membered ring, a divalent heteroaromatic group with 3 to 26 carbon atoms (substituted or unsubstituted), or a divalent cyclic aliphatic hydrocarbon group with 10 to 16 carbon atoms; p 4 q 4 and r 4 Each independently represents an integer from 0 to 2; Ar 41 Ar 42 L 41 L 42 and L 43 At least one of them has a cyano group.

[0819] Method 15: The compound according to Method 14, wherein, in formula (4), the L 41 L 42 and L 43 Each can be a phenyl group that can be substituted with a cyano group or a pyridyl group that can be substituted with a cyano group.

[0820] Method 16: The compound according to Method 14 or 15, wherein, in formula (4), in the Ar 41 Ar 42 L 41 L 42 and L 43 In these groups, the sum of the number of cyano groups and the number of nitrogen-containing heteroaromatic rings composed of 6-membered rings is more than 2.

[0821] Method 17: According to any one of methods 14 to 16, in formula (4), in the Ar 41 Ar 42 L 41 L 42 and L 43 In these groups, the sum of the number of cyano groups and the number of pyridino groups is more than 2.

[0822] Method 18: A material for a photoelectric conversion element for a camera element, comprising a compound of any one of methods 14 to 17.

[0823] Method 19: The material for the photoelectric conversion element for the camera element according to Method 18 is a hole blocking material.

[0824] Method 20: A camera element having a layer comprising a material of method 18 or 19 for a photoelectric conversion element of a camera element.

[0825] <Notes>

[0826] This invention is not limited to the embodiments described above, and various modifications can be made 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 this invention.

[0827] Example

[0828] The present invention will be further described in detail below based on embodiments, but these embodiments are not intended to limit the present invention in any way.

[0829] <Examples of materials (1) for photoelectric conversion elements used in camera components>

[0830] <Synthetic Example-101>

[0831] 2,2′-(9,9-diphenyl-9H-fluorene-2,7-diyl)bis(4,6-bis(3-pyridyl)-1,3,5-triazine)(CA31-GA2)

[0832] [Chemistry 140]

[0833] (Step 1)

[0834] N,N′-(9H-fluorene-2,7-dimethyl)bis-4-pyridylamine (X12)

[0835] In a flask equipped with a Dean-Stark tube and a reflux reflux tube, 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 the mixture was heated under reflux for 4 hours. After confirmation of the reaction's completion by NMR, the low-boiling fraction was removed under reduced pressure to yield N,N′-(9H-fluorene-2,7-dimethyl)bis-4-pyridylamine (X12). The crude product was not purified and was used in subsequent reactions (crude yield 3.0 g, 98% yield).

[0836] 1 H-NMR (400MHz, CDCl3) 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).

[0837] (Step 2)

[0838] Under an argon atmosphere, N,N′-(9H-fluorene-2,7-dimethyl)bis-4-pyridylamine (X12) (3.0 g, 5.7 mmol) was added to a suspension of 3-methylenepyridine hydrochloride (3.7 g, 23 mmol) and potassium carbonate (4.0 g, 29 mmol) in DMF (20 mL) in a two-necked flask. The mixture was stirred at 100 °C for 17 hours. After cooling to room temperature, water and methanol were added, and the solid was filtered off. The obtained 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%).

[0839] 1 H-NMR (400MHz, CDCl3) δ (ppm): 9.91 (dd, J=2.1, 0.7Hz, 4H), 8.95 (ddd, J=8.3, 3.9, 3.9Hz, 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=7.0Hz, 4H), 7.34 (t, J=7.4Hz, 4H), 7.30 (d, J=7.2Hz, 2H).

[0840] <Synthetic Example-102>

[0841] 2,2′-(9,9-diphenyl-9H-fluorene-2,7-diyl)bis[4,6-bis{4-pyridyl}-1,3,5-triazine](CA31-GA1)

[0842] [Chemistry 141]

[0843] (Step 1)

[0844] 2,2′-(9,9-diphenyl-9H-fluorene-2,7-diyl)bis[4,6-bis{4-pyridyl}-1,3,5-triazine](CA31-GA1)

[0845] In a flask, a suspension of N,N′-(9H-fluorene-2,7-dimethyl)bis-4-pyridylamine (X12) (2.1 g, 4.0 mmol), 4-methylammonium pyridine 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 cooling to room temperature, 22 mL of 10% hydrochloric acid was added, and the mixture was stirred for 30 minutes. Subsequently, water and methanol were added, and the precipitate was filtered off. The precipitate was 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%).

[0846] 1 H-NMR (400MHz, CDCl3) δ (ppm): 8.92 (brd, J=6.0Hz, 8H), 8.90 (dd, J=8.0, 1.5Hz, 2H), 8.86 (d, J=1.0Hz, 2 H), 8.52 (brd, 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).

[0847] <Synthetic Example-103>

[0848] 2-(3-(9,10-dihydro-9,10-[1,2]-benzanthracene-2-yl)phenyl)-4,6-bis(pyridin-4-yl)-1,3,5-triazine (CB31-GB49)

[0849] [Chemistry 142]

[0850] (Step 1)

[0851] 2-(3-Bromophenyl)-4,6-bis(pyridin-4-yl)-1,3,5-triazine (X32)

[0852] 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 the suspension at room temperature, and the mixture was stirred for 2 minutes at room temperature, followed by stirring at 60 °C for 20 minutes. 1,1,3,3-Tetramethyldisiloxane (13 mL, 75 mmol) was further added, and the mixture was stirred at 150 °C for 12 hours. The low-boiling fraction was then removed under reduced pressure. The resulting solid was washed with water, methanol, hexane, and a small amount of acetone to give 2-(3-bromophenyl)-4,6-bis(pyridin-4-yl)-1,3,5-triazine (X32) (yield 3.7 g, 38%).

[0853] 1 H-NMR (400MHz, CDCl3) 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 (brdd, J=8.0Hz, 1H), 7.50 (brdd, J=7.9,7.9Hz, 1H).

[0854] (Step 2)

[0855] 2-(3-(9,10-dihydro-9,10-[1,2]-benzanthracene-2-yl)phenyl)-4,6-bis(pyridin-4-yl)-1,3,5-triazine (CB31-GB49)

[0856] 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]-benzanthracene-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). A 2M potassium carbonate aqueous solution (14 mL, 28 mmol) was added to the suspension, and the mixture was stirred at 80 °C for 2 hours. 2-(9,10-dihydro-9,10[1,2]-benzanthracene-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborane (692 mg, 1.8 mmol) was further 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 and then filtered through diatomaceous earth. Further medium-pressure column chromatography using silica gel (hexane 100%, then hexane:chloroform = 50:50, then chloroform 100%), followed by washing with hot toluene, and then washing with hexane, methanol and a small amount of acetone, yielded 2-(3-(9,10-dihydro-9,10-[1,2]-benzanthracene-2-yl)phenyl)-4,6-bis(pyridin-4-yl)-1,3,5-triazine (CB31-GB49) (yield 1.6 g, 41%).

[0857] 1 H-NMR (400MHz, CDCl3) 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).

[0858] <Synthetic Example-104>

[0859] 2-(3-(6-(9,10-dihydro-9,10-[1,2]-benzanthracene-2-yl)-pyridin-3-yl)phenyl)-4,6-bis(pyridin-4-yl)-1,3,5-triazine (CB37-GB49)

[0860] [Chemistry 143]

[0861] (Step 1)

[0862] 5-Chloro-2-(9,10-dihydro-9,10-[1,2]-benzanthracene-2-yl)pyridine (X42)

[0863] Under an argon atmosphere, 2-(9,10-dihydro-9,10[1,2]-benzanthracene-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborane (12.9 g, 33.8 mmol), 2-bromo-5-chloropyridine (9.83 g, 25.8 mmol), and tetra(triphenylphosphine)palladium (2.51 g, 2.2 mmol) were suspended in THF (70 mL). A 2M potassium carbonate aqueous solution (50 mL, 100 mmol) was added to the suspension, 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, and after stirring, the mixture was filtered through diatomaceous earth under reduced pressure to remove low-boiling fractions. The obtained solid was purified by column chromatography (hexane:chloroform = 100:0 to 50:50) to obtain 5-chloro-2-(9,10-dihydro-9,10-[1,2]-benzanthracene-2-yl)pyridine (X42) (yield 6.25 g, yield 66%).

[0864] 1 H-NMR (400MHz, CDCl3) 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, 1.8Hz, 1H), 7.46 (d, J=7.7Hz, 1H), 7.42-7.37 (m, 4H), 7.02-6.98 (m, 4H), 5.51 (s, 1H), 5.47 (s, 1H).

[0865] (Step 2)

[0866] 2-(9,10-dihydro-9,10-[1,2]-benzanthracene)-2-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)pyridine (X43)

[0867] Under an argon atmosphere, 5-chloro-2-(9,10-dihydro-9,10-[1,2]benzanthracene-2-yl)pyridine (X42) (5.76 g, 15.7 mmol), bis(pinacol)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, 87% yield). After cooling to room temperature, chloroform and water were added to the reaction mixture, the organic layer was extracted, and the organic layer was further washed with saturated brine. Sodium sulfate and activated carbon were added to the organic layer and stirred. The mixture was then filtered through diatomaceous earth, and the low-boiling fraction was removed under reduced pressure to obtain 2-(9,10-dihydro-9,10-[1,2]-benzanthracene)-2-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)pyridine (X43) (crude yield 8.21 g, crude yield quant.). This crude product was used in subsequent reactions without further purification.

[0868] 1 H-NMR (400MHz, CDCl3) 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=7.6Hz, 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).

[0869] (Step 3)

[0870] 2-(3-(6-(9,10-dihydro-9,10-[1,2]-benzanthracene-2-yl)-pyridin-3-yl)phenyl)-4,6-bis(pyridin-4-yl)-1,3,5-triazine (CB37-GB49)

[0871] Under an argon atmosphere, 2-(9,10-dihydro-9,10-[1,2]-benzanthracene-2-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-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 tetra(triphenylphosphine)palladium (0.32 g, 0.28 mmol) were suspended in xylene (55 mL). A 4M potassium phosphate aqueous solution (5 mL, 20 mmol) was added to the suspension, and the mixture was stirred at 130 °C for 20 hours. After cooling to room temperature, water and methanol were added to the reaction mixture, and the precipitate was collected by filtration. The filtrate was suspended in DMF (300 mL), aerated with air at 140 °C for 1.5 hours, and then filtered through diatomaceous earth. After removing the low-boiling fraction under reduced pressure, water and methanol were added, and the precipitate was filtered off. The filtrate was suspended in toluene (150 mL), heated to 120 °C, and then filtered through diatomaceous earth under hot pressure. The low-boiling fraction was then concentrated under reduced pressure and washed with methanol to obtain 2-(3-(6-(9,10-dihydro-9,10-[1,2]-benzanthracene-2-yl)-pyridin-3-yl)phenyl)-4,6-bis(pyridin-4-yl)-1,3,5-triazine (CB37-GB49) (yield 1.27 g, 40%).

[0872] 1 H-NMR (400MHz, CDCl3) 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).

[0873] <Synthetic Example-105>

[0874] 2-([1,1′-biphenyl]-4-yl)-4,6-bis(2-[9-phenanthyl]pyridin-4-yl)-1,3,5-triazine (CB4-GB2)

[0875] [Chemistry 144]

[0876] (Step 1)

[0877] 2-(9-phenanthroline)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)pyridine (X52)

[0878] Under a nitrogen stream, bis(pinacol)diboron (2.13 g, 8.41 mmol), 4-chloro-2-(9-phenanthroline)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 and reacted at 100 °C for 14 h. A saturated aqueous sodium chloride solution was added to the reaction solution, and the mixture was extracted with tetrahydrofuran. After separation of the organic layer, the mixture was dehydrated with 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 solid was filtered off to obtain the target compound 2-(9-phenanthyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaneborane-2-yl)pyridine (X52) (yield 1.80 g, 67%).

[0879] The identification of the obtained compounds was passed 1 H-NMR was performed.

[0880] 1 H-NMR (400MHz, CDCl3) 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=8.3Hz, 1H), 8.74 (d, J=8.1Hz, 1H), 8.78 (d, J=8.1Hz, 1H), 8.86 (d, J=4.8Hz, 1H).

[0881] (Step 2)

[0882] 2-([1,1′-biphenyl]-4-yl)-4,6-bis(2-[9-phenanthyl]pyridin-4-yl)-1,3,5-triazine (CB4-GB2)

[0883] Under a nitrogen stream, 2-(9-phenanthroline)-4-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)pyridine (X52) (257 mg, 0.675 mmol), 2-([1,1′-biphenyl]-4-yl)-4,6-dichloro-1,3,5-triazine (0.102 g, 0.338 mmol), tetra(triphenylphosphine)palladium (0) (13 mg, 0.011 mmol), and 0.169 mL of 2 M sodium carbonate aqueous solution were suspended in toluene and reacted at 100 °C for 1 hour. Hexane was then added to the resulting reaction solution, and the mixture was stirred at room temperature. The solid was filtered off to obtain the target compound 2-([1,1′-biphenyl]-4-yl)-4,6-bis(2-[9-phenanthyl]pyridin-4-yl)-1,3,5-triazine (CB4-GB2) (yield 0.20 g, 80% yield).

[0884] The obtained compounds were identified by FD-MS analysis using a Hitachi M-80B microarray. FD-MS: 739.

[0885] <Synthetic Example-106>

[0886] 2,4-Bis(3,5-Di(pyridin-4-yl)phenyl)-6-(4-(naphth-1-yl)phenyl)-1,3,5-triazine (CD1-GB28)

[0887] [Chemistry 145]

[0888] (Step 1)

[0889] 2-Chloro-4,6-bis(3,5-dichlorophenyl)-1,3,5-triazine (X62)

[0890] Under an argon atmosphere, 1-bromo-3,5-dichlorobenzene (X61) (21 g, 95 mmol) was suspended in THF (260 mL) in a two-necked flask and cooled to 0 °C. 2M isopropyl magnesium chloride·THF solution (50 mL, 100 mmol) was added to the suspension, and the mixture was stirred at 0 °C for 2 hours. Then, cyanuric chloride (6.2 g, 33 mmol) was added, and the mixture was heated to room temperature and stirred overnight. The reaction solution was concentrated, and water and methanol were added. The precipitate was filtered off and washed with water, methanol, and hexane to obtain the crude product of 2-chloro-4,6-bis(3,5-dichlorophenyl)-1,3,5-triazine (X62) (crude yield 4.7 g, crude yield 69%).

[0891] 1H-NMR (400MHz, CDCl3) δ (ppm): 8.49 (d, J=2.0Hz, 4H), 7.64 (t, J=1.9Hz, 2H).

[0892] (Step 2)

[0893] 2,4-Bis(3,5-dichlorophenyl)-6-(4-(naphth-1-yl)phenyl)-1,3,5-triazine (X63)

[0894] Under an argon atmosphere, in a double-necked flask equipped with a reflux tube, 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), tetrakis(triphenylphosphine)palladium (0.3 g, 0.3 mmol), and 2M sodium carbonate aqueous solution (9.7 mL, 19 mmol) were suspended in xylene (100 mL) and stirred overnight at 140 °C. After cooling to room temperature, water and methanol were added, the precipitate was filtered off, and the precipitate was washed with water and methanol. Dissolve it in toluene at 120°C, add activated carbon, stir, and then filter and separate the liquid under warm conditions to concentrate it, thereby obtaining 2,4-bis(3,5-dichlorophenyl)-6-(4-(naphth-1-yl)phenyl)-1,3,5-triazine (X63) (yield 2.6 g, yield 84%).

[0895] 1 H-NMR (400MHz, CDCl3) δ (ppm): 8.87 (d, J=8.4Hz, 2H), 8.65 (d, J=2.0Hz, 4H), 7.95 (dd, J=9.0, 9.0Hz, 3H), 7.76 ( d, J=8.4Hz, 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).

[0896] (Step 3)

[0897] 2,4-Bis(3,5-bis(4,4,5,5-tetramethyl-1,3,2-yl)phenyl)-6-(4-(naphth-1-yl)phenyl)-1,3,5-triazine (X64)

[0898] Under an argon atmosphere, in a double-necked flask equipped with a reflux tube, 2,4-bis(3,5-dichlorophenyl)-6-(4-(naphth-1-yl)phenyl)-1,3,5-triazine (X63) (1.9 g, 3.4 mmol), bis(pinacol)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 overnight at 140 °C. After cooling to room temperature, water was added, and the organic layer was extracted. The obtained organic layer was heated to 120 °C, activated carbon and magnesium sulfate were added, and after stirring, the mixture was filtered through diatomaceous earth under warm conditions. The resulting liquid was concentrated to give 2,4-bis(3,5-bis(4,4,5,5-tetramethyl-1,3,2-yl)phenyl)-6-(4-(naphth-1-yl)phenyl)-1,3,5-triazine (X64) (yield 3.1 g, 97% yield).

[0899] 1 H-NMR (400MHz, CDCl3) δ (ppm): 9.30 (d, J=1.3Hz, 4H), 8.97 (brd, J=8.5Hz, 2H), 8.52 (dd, J=1.3, 1.3Hz, 2H), 8.00 (dd, J=8. 2,0.7Hz, 1H), 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).

[0900] (Step 4)

[0901] 2,4-Bis(3,5-Di(pyridin-4-yl)phenyl)-6-(4-(naphth-1-yl)phenyl)-1,3,5-triazine (CD1-GB28)

[0902] Under an argon atmosphere, in a two-necked flask equipped with a reflux tube, 2,4-bis(3,5-bis(4,4,5,5-tetramethyl-1,3,2-yl)phenyl)-6-(4-(naphth-1-yl)phenyl)-1,3,5-triazine (X64) (3.2 g, 3.5 mmol), 4-bromopyridine hydrochloride (3.0 g, 15 mmol), tetrakis(triphenylphosphine)palladium (0.2 g, 0.2 mmol), and 4M potassium phosphate aqueous solution (13 mL, 50 mmol) were suspended in xylene (120 mL) and stirred overnight at 140 °C. After cooling to room temperature, the precipitate was filtered off and washed with water, methanol, and hexane. The obtained solid was suspended in 500 mL of toluene and heated and stirred at 120 °C. The solid was filtered off while hot to give 2,4-bis(3,5-bis(pyridin-4-yl)phenyl)-6-(4-(naphth-1-yl)phenyl)-1,3,5-triazine (CD1-GB28) (yield 2.5 g, yield 96%).

[0903] 1 H-NMR (400MHz, CDCl3) δ (ppm): 9.13 (d, J=1.8Hz, 4H), 8.94 (brd, J=8.4Hz, 2H), 8.81 ( dd, J=6.1, 4.4Hz, 8H), 8.14 (dd, J=1.8, 1.8Hz, 2H), 7.98 (brd, J=9.0Hz, 2H), 7.95 (br d, J=8.1Hz, 2H), 7.80 (brd, J=8.4Hz, 2H), 7.74 (dd, J=6.1, 4.4Hz, 8H), 7.61 (d, J=7.0 Hz, 1H), 7.59 (d, J=7.2Hz, 1H), 7.57-7.52 (m, 2H), 7.48 (ddd, J=8.3, 6.8, 1.4Hz, 1H).

[0904] <Synthetic Example-107>

[0905] 4,6-Bis(biphenyl-4-yl)-2-[4′-(1-adamantyl)-5-(3-pyridyl)biphenyl-3-yl]-1,3,5-triazine (E-22)

[0906] [Chemistry 146]

[0907] Under an argon atmosphere, 4,6-bis(biphenyl-4-yl)-2-[3-(3-pyridyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)phenyl]-1,3,5-triazine (1.50 g, 2.26 mmol), 4-(1-adamantyl)phenyltrifluoromethanesulfonate (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 precipitate was purified by silica gel chromatography (developing solvent: a 1:2 mixture of chloroform and hexane) and toluene-based recrystallization to give 4,6-bis(biphenyl-4-yl)-2-[4′-(1-adamantyl)-5-(3-pyridyl)biphenyl-3-yl]-1,3,5-triazine (E-22) as the target compound (yield 0.97 g, 57%). The Tg of the obtained compound E-22 was... g The temperature is 155℃.

[0908] 1 H-NMR (400MHz, CDCl3) δ (ppm): 9.07 (d, J=1.7Hz, 1H), 9.05 (t, J=1.6Hz, 1H), 8.95 (t, J=1.6H z, 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, 7.9H z, 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).

[0909] <Synthetic Example-108>

[0910] 4,6-Bis(biphenyl-4-yl)-2-[3-(4-pyridyl)-5-(9-phenanthyl)phenyl]-1,3,5-triazine (E-21)

[0911] [Chemistry 147]

[0912] By performing the same procedures as in Synthesis Example-107, a white solid of 4,6-bis(biphenyl-4-yl)-2-[3-(4-pyridyl)-5-(9-phenanthyl)phenyl]-1,3,5-triazine (E-21) was obtained as the target.

[0913] <Synthetic Example-109>

[0914] 4,6-Bis(biphenyl-4-yl)-2-[4′-(3-pyridyl)-5-(9-phenanthyl)biphenyl-3-yl]-1,3,5-triazine (E-18)

[0915] [Chemistry 148]

[0916] By performing the same procedures as in Synthesis Example-107, a white solid, 4,6-bis(biphenyl-4-yl)-2-[4′-(3-pyridyl)-5-(9-phenanthyl)biphenyl-3-yl]-1,3,5-triazine (E-18), was obtained as the target.

[0917] <Synthetic Example-110>

[0918] 4,6-Bis(biphenyl-4-yl)-2-[3-(2-phenyl-4-pyridyl)-5-(9-phenanthyl)phenyl]-1,3,5-triazine (E-19)

[0919] [Chemistry 149]

[0920] By performing the same procedures as in Synthesis Example-107, a white solid of 4,6-bis(biphenyl-4-yl)-2-[3-(2-phenyl-4-pyridyl)-5-(9-phenanthyl)phenyl]-1,3,5-triazine (E-19) was obtained as the target.

[0921] <Synthetic Example-111>

[0922] 4,6-Bis(biphenyl-4-yl)-2-[4′-(4-pyridyl)-5-(9-phenanthyl)biphenyl-3-yl]-1,3,5-triazine (E-17)

[0923] [Chemistry 150]

[0924] By performing the same procedures as in Synthesis Example-107, a white solid, 4,6-bis(biphenyl-4-yl)-2-[4′-(4-pyridyl)-5-(9-phenanthyl)biphenyl-3-yl]-1,3,5-triazine (E-17), was obtained as the target.

[0925] <Synthetic Example-112>

[0926] 4,6-Bis(biphenyl-4-yl)-2-[3-(2-phenyl-3-pyridyl)-5-(9-phenanthyl)phenyl]-1,3,5-triazine (E-20)

[0927] [Chemistry 151]

[0928] By performing the same procedures as in Synthesis Example-107, a white solid, 4,6-bis(biphenyl-4-yl)-2-[3-(2-phenyl-3-pyridyl)-5-(9-phenanthyl)phenyl]-1,3,5-triazine (E-20), was obtained as the target.

[0929] <Synthetic Example-113>

[0930] 4,6-Bis(biphenyl-4-yl)-2-{4-[6-(biphenyl-4-yl)pyridin-3-yl]phenyl}-1,3,5-triazine (E-29)

[0931] [Chemistry 152]

[0932] By performing the same procedures as in Synthesis Example-107, a white solid of 4,6-bis(biphenyl-4-yl)-2-{4-[6-(biphenyl-4-yl)pyridin-3-yl]phenyl}-1,3,5-triazine (E-29) was obtained as the target.

[0933] <Synthetic Example-114>

[0934] 2,4-Bis([1,1′-biphenyl]-4-yl)-6-(4′-(adamantane-1-yl)-5-(2-phenylpyridin-3)-yl)-[1,1′-biphenyl]-3-yl)-1,3,5-triazine (E-33)

[0935] [Chemistry 153]

[0936] Under an argon atmosphere, 2,4-bis([1,1′-biphenyl]-4-yl)-6-chloro-1,3,5-triazine (1.4 g, 3.3 mmol), 3-(4′-(-adamantane-1-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)-[1,1′-biphenyl]-3-yl)-2-phenylpyridine (2.0 g, 3.5 mmol), and tetra(triphenylphosphine)palladium (0.12 g, 0.010 mmol) were suspended in THF (33 mL). A 2M potassium carbonate aqueous solution (5.4 mL, 11 mmol) was added to the suspension, and the mixture was refluxed for 17 hours. After adding water to the reaction solution, the solid was filtered off and washed with water, methanol, and hexane. The resulting solid was dissolved in hot toluene, activated carbon was added, and the mixture was stirred. The solution was then hot-filtered using diatomaceous earth. The filtrate was allowed to stand at room temperature, and the precipitated solid was filtered off to obtain 2,4-bis([1,1′-biphenyl]-4-yl)-6-(4′-(-adamantane-1-yl)-5-(2-phenylpyridin-3)-yl)-[1,1′-biphenyl]-3-yl)-1,3,5-triazine (E-33) (1.8 g, 65%).

[0937] 1 H-NMR (400MHz, CDCl3) δ (ppm): 8.92 (dd, J=1.6, 1.6Hz, 1H), 8.83 (brd, J=8.5Hz, 4H), 8.79 ( dd, J=4.8, 1.7Hz, 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, 4H), 7.73 (brd, J=7.4Hz, 4H), 7.58 (dd, J=1.6.1.6Hz, 1H), 7.55-7.49 (m, 6H), 7.4 9-7.40 (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).

[0938] <Synthetic Example-115>

[0939] 2-(4-(adamantane-1-yl)phenyl)-4,6-bis(4-(2-phenylpyridin-3-yl)phenyl)-1,3,5-triazine (E-39)

[0940] [Chemistry 154]

[0941] Under an argon atmosphere, 2-(4-(-adamantane-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-dioxaneborane-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). A 2M potassium carbonate aqueous solution (10 mL, 20 mmol) was added to the suspension, and the mixture was refluxed for 17 hours. The reaction solution was extracted with toluene by adding water, and the organic layer was washed with water. The organic layer was separated, sodium sulfate and activated carbon were added and stirred, and the mixture was filtered through diatomaceous earth and the solvent was removed by distillation. The obtained solid was washed with hot octane and hot ethanol to obtain 2-(4-(adamantane-1-yl)phenyl)-4,6-bis(4-(2-phenylpyridin-3-yl)phenyl)-1,3,5-triazine (E-39) (1.7 g, 77%).

[0942] 1 H-NMR (400MHz, CDCl3) 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, 1.7 Hz, 2H), 7.55 (brd, J=8.6Hz, 2H), 7.44-7.37 (m, 10H), 7.29-7.24 (m, 6H), 2.18-2.11 (m, 3H), 2.03-1.95 (m, 6H), 1.88-1.76 (m, 6H).

[0943] <Glass transition temperature · LUMO level>

[0944] For 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 Synthetic 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, the glass transition temperature was determined using a differential scanning calorimeter (DSC 7020 manufactured by Hitachi Advanced Technology) with an aluminum disk at a scan rate of 10°C / min. Furthermore, in the LUMO level calculation, density functional theory (DFT) based on the calculation conditions of the B3LYP functional and the 6-31G(d) basis functions was used with Gaussian 16 software 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. It should be noted that in the table below, "ND" means "not detected." That is, compounds (CA31-GA2), (CA31-GA1), and comparative compounds 1 and 2 are not amorphous but crystalline. Additionally, in the table below, "-" means not determined.

[0945] [Chemistry 155]

[0946] [Table 192]

[0947]

[0948]

[0949]

[0950] The results in the table above show that, as a material for photoelectric conversion elements, the compound shown in formula (1) has excellent thermal stability compared to comparative compounds 1 to 3, and the calculated value of the LUMO energy level (calc. LUMO) is deeper (lower in the positive direction) than that of the comparative compounds.

[0951] <Component Example-101 (Refer to Figure 1)>

[0952] As shown in Figure 1, an imaging element 100 is fabricated as a photoelectric conversion element having a stacked 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. The dark current, external quantum efficiency, and responsivity of the imaging element are evaluated.

[0953] (Preparation of the first electrode 1)

[0954] As a substrate having a first electrode on its surface, a glass substrate with a transparent ITO electrode and a 2 mm wide indium tin oxide (ITO) film (110 nm thick) patterned into stripes was prepared. Then, the substrate was cleaned with isopropanol and subjected to surface treatment by ozone ultraviolet cleaning.

[0955] (Preparation for vacuum evaporation)

[0956] On a substrate that has undergone surface treatment after cleaning, vacuum evaporation is used to deposit each layer, and the layers are stacked to form each layer.

[0957] First, the glass substrate described above is introduced into a vacuum evaporation bath, and the pressure is reduced to 7.0 × 10⁻⁶. -5 Pa. Then, the films are prepared separately according to the film-forming conditions of each layer in the following order.

[0958] (Creating Hole Blocking Layer 2)

[0959] The purified compound (CA31-GA2) was deposited into a 10 nm film at a speed of 0.03 nm / s to create a hole blocking layer 2.

[0960] (Fabrication of photoelectric conversion layer (light-receiving layer) 3)

[0961] A 120 nm film was formed by mixing N,N-dimethylquinacridone and C60 in a 4:1 (mass ratio) manner to create the photoelectric conversion layer 3. The deposition rate was 0.15 nm / s.

[0962] (Fabrication of electron blocking layer 4)

[0963] Compound (ic-3) was deposited at a speed of 0.10 nm / s to form a 10 nm film, thus creating an electron blocking layer 4. It should be noted that (ic-3) was synthesized using the method described in Japanese Patent Application Publication No. 2018-193371.

[0964] (Creation of Hole Transport Layer 5)

[0965] A hole transport layer 5 was fabricated by forming a 10 nm film of compound 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene (HATCN) at a speed of 0.10 nm / s.

[0966] (Fabrication of the second electrode 6)

[0967] Finally, a metal mask is configured orthogonally to the ITO stripes on the substrate to form a film, which serves as the second electrode 6 of the upper electrode. Specifically, silver is deposited at a rate of 0.1 nm / s to form an 80 nm film, which serves as the second electrode 6 of the upper electrode.

[0968] Thus, a 4mm² area was produced as shown in Figure 1. 2 The camera uses a photoelectric conversion element 100. It should be noted that each film thickness was measured using a stylus-type film thickness gauge (manufactured by DEKTAK or Bruker).

[0969] The component is then sealed in a nitrogen atmosphere glove box with an oxygen and moisture concentration of less than 1 ppm. The sealing is performed on a glass sealing cap and a film-forming substrate (component) using bisphenol F epoxy resin (manufactured by Nagase ChemteX).

[0970] The dark current, external quantum efficiency, and response time were evaluated when a voltage of 2.6V was applied to the imaging element fabricated as described above. The dark current was measured using a Keithley Source Measure Unit 2636B. The external quantum efficiency was measured using a solar cell spectrophotometer (Soma Optical). The wavelength of the illumination light was 560 nm, and the intensity was 50 μW / cm². 2 The measurement is performed. The response time is the time it takes for the current value to return to its initial value after the irradiation of the light pulse.

[0971] It should be noted that dark current, external quantum efficiency, and response time are relative values ​​to the baseline value (1.0) of Comparative Example-101. Lower dark current values ​​indicate better performance, higher external quantum efficiency values ​​indicate better performance, and shorter response times indicate better performance. The measured results are shown in the table below.

[0972] <Component Examples - 102 to 115, Component Comparative Examples - 101 to 103>

[0973] In Component Example-101, 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), as well as comparative compounds 1, 2, and 3, were used in place of compound (CA31-GA2). Otherwise, a photoelectric conversion element for imaging was fabricated and evaluated using the same method as in Component Example-101. The obtained measurement results are shown in the table below. It should be noted that in the table below, "-" indicates "not measured".

[0974] [Table 193]

[0975]

[0976] The results in the table above show that by using the compound shown in formula (1) as a material for photoelectric conversion elements for imaging elements to form a layer, compared with the case of using the comparative example compound to form a layer, a photoelectric conversion element for imaging with improved responsiveness, external quantum efficiency and dark current is achieved.

[0977] Furthermore, the results from Component Examples 107 to 115 show that if the compound is as shown in Formula (1), even if the calculated LUMO level (calc. LUMO) of the compound is shallower than that of the comparative compound (the value is higher in the positive direction), the compound still contributes to a photoelectric conversion element for imaging with excellent responsiveness, high external quantum efficiency, and reduced dark current. This is believed to be due to the coordination ability brought by the pyridine group and the uniform film quality brought by the amorphous nature.

[0978] <Example of material (1') for photoelectric conversion element for camera element>

[0979] <Synthetic Example-201>

[0980] 4′,4′′′′,4′′′′′′′-(1,3,5-triazine-2,4,6-triyl)tri(([1,1′:2′,1′′-terphenyl]-4,4′′-dicarboxynitrile))(D′-16)

[0981] [Chemistry 156]

[0982] 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). A 2M sodium carbonate aqueous solution (11 mL, 22 mmol) was added to the suspension, and the mixture was refluxed for 17 hours. After filtering the reaction solution, the solution was washed with water, methanol and hexane. The resulting solid was dried under vacuum and purified by sublimation to obtain 4′,4′′′′,4′′′′′′-(1,3,5-triazine-2,4,6-triyl)tris(([1,1′:2′,1′′-terphenyl]-4,4′′-dicarboxynitrile))(D′-16)(yield 0.40 g, 20% yield).

[0983] 1 H-NMR (400MHz, CDCl3) δ (ppm): 8.88 (dd, J=8.0, 1.7Hz, 3H), 8.78 (d, J=1.7Hz, 3H), 7.67 (d, J=8.0Hz, 3H ), 7.63(brd, 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).

[0984] <Synthesis Example-202>

[0985] 4′,4′′′′-(6-phenyl-1,3,5-triazine-2,4-diyl)bis(([1,1′:2′,1′′-terphenyl]-4,4′′-dicarboxynitrile))(D′-08)

[0986] [Chemistry 157]

[0987] 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). A 2M sodium carbonate aqueous solution (11 mL, 23 mmol) was added to the suspension, and the mixture was refluxed for 18 hours. The reaction solution was filtered and 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. The solution was then hot-filtered using diatomaceous earth. The filtrate was allowed to stand at room temperature, and the precipitated solid was filtered off to obtain 4′,4′′′′-(6-phenyl-1,3,5-triazine-2,4-diyl)bis(([1,1′:2′,1′′-terphenyl]-4,4′′-dicarboxynitrile))(D′-08)(yield 2.1 g, yield 77%).

[0988] 1 H-NMR (400MHz, CDCl3) δ (ppm): 8.90 (dd, J=8.1, 1.7Hz, 2H), 8.81 (d, J=1.7Hz, 2H), 8.76 ( brd, J=7.0Hz, 2H), 7.69-7.57 (m, 13H), 7.37 (brd, J=8.4Hz, 4H), 7.30 (brd, J=8.4Hz, 4H).

[0989] <Synthetic Example-203>

[0990] 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′′-dicarboxynitrile (CC′105-GC′1)

[0991] [Chemistry 158]

[0992] Under an argon atmosphere, 4′-(4-(4-chlorophenyl)-6-phenyl-1,3,5-triazin-2-yl)-[1,1′:2′,1′′-terphenyl]-4,4′′-dicarboxynitrile (1.8 g, 3.3 mmol), 4-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-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 potassium carbonate aqueous solution (5.5 mL, 11 mmol) was added to the suspension, and the mixture was refluxed for 17 hours. After adding water to the reaction solution, the solid was filtered off and washed with water, methanol, and hexane. The obtained solid was dissolved in toluene heated to 110°C, activated carbon was added and stirred, and then hot-filtered using diatomaceous earth. The filtrate was allowed to stand at room temperature, and the precipitated solid was collected 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′′-dicarboxynitrile (CC′105-GC′1) (yield 1.4 g, 69% yield).

[0993] 1 H-NMR (400MHz, CDCl3) 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).

[0994] <Synthetic Example-204>

[0995] 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′′-dicarboxynitrile (CC′94-GC′1)

[0996] [Chemistry 159]

[0997] 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′′-dicarboxynitrile (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). A 2M potassium carbonate aqueous solution (2.8 mL, 5.6 mmol) was added to the suspension, and the mixture was refluxed for 17 hours. After adding water to the reaction solution, the solid was filtered off and washed with water, methanol, and hexane. The obtained solid was dissolved in toluene heated to 110°C, activated carbon was added and stirred, and then hot-filtered using diatomaceous earth. The filtrate was allowed to stand at room temperature, and the precipitated solid was collected to obtain 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′′-dicarboxynitrile (CC′94-GC′1) (yield 1.5 g, yield 54%).

[0998] 1 H-NMR (400MHz, CDCl3) δ (ppm): 8.94 (dd, J=8.2, 1.7Hz, 1H), 8.90 (brd, J=8.5Hz, 2H), 8.86 (brd, J=8. 5Hz, 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).

[0999] <Synthetic Example-205>

[1000] 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′′-dicarboxynitrile (CC′112-GC′1)

[1001] [Chemistry 160]

[1002] 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′′-dicarboxynitrile (2.5 g, 4.0 mmol), 5-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-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). A 2M potassium carbonate aqueous solution (7.3 mL, 15 mmol) was added to the suspension, and the mixture was refluxed for 17 hours. After adding water to the reaction solution, the solid was filtered off and washed with water, methanol, and hexane. The resulting 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′′-dicarboxynitrile (CC′112-GC′1) (yield 2.0 g, 70% yield).

[1003] 1 H-NMR (400MHz, CDCl3) 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=1.6Hz, 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 ), 7.53 (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).

[1004] <Synthetic Example-206>

[1005] 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′′-dicarboxynitrile (CC′119-GC′1)

[1006] [Chemistry 161]

[1007] 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-dioxacyclopentaborane-2-yl)-[1,1′:2′,1′′-terphenyl]-4,4′′-dicarboxynitrile (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). A 2M potassium carbonate aqueous solution (7.5 mL, 15 mmol) was added to the suspension, and the mixture was refluxed for 17 hours. After adding water to the reaction solution, the solid was filtered off and 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. The solution was then hot-filtered using diatomaceous earth. The filtrate was allowed to stand at room temperature, and the precipitated solid was filtered off 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′′-dicarboxynitrile (CC′119-GC′1) (yield 1.6 g, 52% yield).

[1008] 1 H-NMR (400MHz, CDCl3) 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).

[1009] <Synthesis Example-207>

[1010] 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′′-dicarboxynitrile (CC′119-GC′21)

[1011] [Chemistry 162]

[1012] Under an argon atmosphere, 4-(4-([1,1′-biphenyl]-4-yl)-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaneborane-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′′-dicarboxynitrile (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). A 2M potassium carbonate aqueous solution (4.6 mL, 9.2 mmol) was added to the suspension, and the mixture was refluxed for 17 hours. After adding water to the reaction solution, the solid was filtered off and washed with water, methanol, and hexane. The resulting solid was washed with toluene heated to 110°C, dissolved in chloroform, and filtered using diatomaceous earth. The low-boiling solvent was removed from the filtrate by distillation, thus yielding 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′′-dicarboxynitrile (CC′119-GC′21) (yield 0.28 g, 14%).

[1013] 1 H-NMR (400MHz, CDCl3) δ (ppm): 8.90 (brd, J=8.6Hz, 2H), 8.83 (brd, J=8.6Hz, 2H), 8.71 (brd, J=8.6Hz, 2H), 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).

[1014] <Synthesis Example-208>

[1015] 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′′-dicarboxynitrile (CC′98-GC′1)

[1016] [Chemistry 163]

[1017] 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′′-dicarboxynitrile (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). A 2M potassium carbonate aqueous solution (2.8 mL, 5.6 mmol) was added to the suspension, and the mixture was refluxed for 17 hours. After adding water to the reaction solution, the solid was filtered off and washed with water, methanol, and hexane. The obtained solid was dissolved in toluene heated to 110°C, activated carbon was added and stirred, and then hot-filtered using diatomaceous earth. The filtrate was allowed to stand at room temperature, and the precipitated solid was collected to obtain 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′′-dicarboxynitrile (CC′98-GC′1) (yield 1.5 g, yield 54%).

[1018] 1H-NMR (400MHz, CDCl3) 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=1.6Hz, 1H), 7.99(dd, J=1.6,1.6Hz, 1H), 7.94(ddd, J=7.8,1.6,1.6Hz, 1 H), 7.85 (brd, J=8.3Hz, 2H), 7.80 (brd, J=8.3Hz, 2H), 7.74-7.59 (m, 8H), 7.52 (brdd, J=7.8,7.3 Hz, 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).

[1019] <Synthesis Example-209>

[1020] 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)

[1021] [Chemistry 164]

[1022] Under an argon atmosphere, 4-(4-([1,1′-biphenyl]-4-yl)-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaneborane-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). A 2M potassium carbonate aqueous solution (8.1 mL, 16 mmol) was added to the suspension, and the mixture was refluxed for 19 hours. After cooling to room temperature, water and methanol were added to the reaction solution, the solid was filtered off, 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, yield 88%).

[1023] 1H-NMR (400MHz, CDCl3) δ (ppm): 8.93 (brd, J=8.6Hz, 2H), 8.90 (brd, J=8.5Hz, 2H), 8.86 (br d, J=8.6Hz, 2H), 8.56 (brd, J=6.1Hz, 2H), 8.54 (brd, J=6.1Hz, 2H), 7.87-7.92 (m, 5H), 7.8 4(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).

[1024] <Synthetic Example-210>

[1025] 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′′-dicarboxynitrile (CC′109-GC′1)

[1026] [Chemistry 165]

[1027] 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′′-dicarboxynitrile (2.7 g, 4.3 mmol), 5-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-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). A 2M potassium carbonate aqueous solution (7.8 mL, 16 mmol) was added to the suspension, and the mixture was refluxed for 17 hours. After adding water to the reaction solution, the solid was filtered off 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. The solution was then hot-filtered using diatomaceous earth. The filtrate was allowed to stand at -20°C, and the precipitated solid was filtered off 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′′-dicarboxynitrile (CC′109-GC′1) (yield 2.0 g, yield 67%).

[1028] 1 H-NMR (400MHz, CDCl3) 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, 1H), 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).

[1029] <Synthetic Example-211>

[1030] 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′′-dicarboxynitrile (CC′129-GC′1)

[1031] [Chemistry 166]

[1032] 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′′-dicarboxynitrile (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). A 2M potassium carbonate aqueous solution (2.6 mL, 5.2 mmol) was added to the suspension, and the mixture was refluxed for 17 hours. After adding water to the reaction solution, the solid was filtered off and washed with water, methanol, and hexane. The obtained solid was dissolved in toluene heated to 110°C, activated carbon was added and stirred, and then hot-filtered using diatomaceous earth. The filtrate was allowed to stand at room temperature, and the precipitated solid was collected to obtain 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′′-dicarboxynitrile (CC′129-GC′1) (yield 1.5 g, 61% yield).

[1033] 1 H-NMR (400MHz, CDCl3) 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(br d, J=8.5Hz, 2H), 7.84 (brd, J=8.5Hz, 2H), 7.75-7.58 (m, 9H), 7.52 (brdd, J=7.3,7.0 Hz, 2H), 7.45 (brt, J=7.3Hz, 1H), 7.39 (brd, J=8.5Hz, 2H), 7.32 (brd, J=8.5Hz, 2H).

[1034] <Synthetic Example-212>

[1035] 5-(4-(4-(9,10-dihydro-9,10-[1,2]benzanthracene-2-yl)phenyl)-6-phenyl-1,3,5-triazin-2-yl)pyridinecarboxylate (CA′63-GA′45)

[1036] [Chemistry 167]

[1037] Under an argon atmosphere, 5-(4-(4-chlorophenyl)-6-phenyl-1,3,5-triazin-2-yl)pyridinium nitrile (2.0 g, 5.4 mmol), 2-(9,10-dihydro-9,10-[1,2]benzanthracene-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxane-pentaborane (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). A 2M potassium carbonate aqueous solution (9.0 mL, 18 mmol) was added to the suspension, and the mixture was refluxed for 17 hours. After adding water to the reaction solution, the solid was filtered off and washed with water, methanol, and hexane. The obtained solid was dissolved in toluene heated to 110°C and hot-filtered using diatomaceous earth. The filtrate was allowed to stand at room temperature, and the precipitated solid was collected to obtain 5-(4-(4-(9,10-dihydro-9,10-[1,2]benzanthracene-2-yl)phenyl)-6-phenyl-1,3,5-triazin-2-yl)pyridinecarboxynitrile (CA′63-GA′45) (yield 2.2 g, 69% yield).

[1038] 1 H-NMR (400MHz, CDCl3) δ (ppm): 10.02 (brd, J=2.0Hz, 1H), 9.14 (dd, J=8.0, 2.0H z, 1H), 8.77 (brd, 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).

[1039] <Synthetic Example-213>

[1040] 5,5′-((6-(9,10-dihydro-9,10-[1,2]benzanthracene-2-yl)-1,3,5-triazine-2,4-diyl)bis(4,1-phenylene))dipyridinium carbide (CA′11-GA′45)

[1041] [Chemistry 168]

[1042] Under an argon atmosphere, 2-(9,10-dihydro-9,10-[1,2]benzanthracene-2-yl)-4,6-bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaneborane-2-yl)phenyl)-1,3,5-triazine (3.5 g, 4.8 mmol), 5-bromopyridinecarboxynitrile (2.1 g, 11 mmol), and tetrakis(triphenylphosphine)palladium(0) (0.28 g, 0.24 mmol) were suspended in THF (45 mL). A 2M potassium carbonate aqueous solution (14 mL, 29 mmol) was added to the suspension, and the mixture was refluxed for 17 hours. After adding water to the reaction solution, the solid was filtered off and washed with water, methanol, and hexane. The resulting solid was dissolved in pyridine heated to 115 °C, activated carbon was added, and the mixture was stirred. The solution was then hot-filtered using diatomaceous earth. The filtrate was allowed to stand at room temperature, and the precipitated solid was filtered off to obtain 5,5′-((6-(9,10-dihydro-9,10-[1,2]benzanthracene-2-yl)-1,3,5-triazine-2,4-diyl)bis(4,1-phenylene))dipyridinium carbide (CA′11-GA′45) (yield 2.0 g, yield 61%).

[1043] 1 H-NMR (400MHz, CDCl3) δ (ppm): 9.07 (dd, J=2.3, 0.8Hz, 2H), 8.92 (brd, J=8.5Hz, 4H), 8.79 (brd, 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 =7.8Hz, 1H), 7.51-7.43(m, 4H), 7.08-7.02(m, 4H), 5.67(s, 1H), 5.57(s, 1H).

[1044] <Synthetic Example-214>

[1045] 4′,4′′′-(6-(9,10-dihydro-9,10-[1,2]benzanthracene-2-yl)-1,3,5-triazine-2,4-diyl)bis([1,1′-biphenyl]-4-carboxynitrile)(CA′4-GA′45)

[1046] [Chemistry 169]

[1047] Under an argon atmosphere, 2,4-bis(4-chlorophenyl)-6-(9,10-dihydro-9,10-[1,2]benzanthracene-2-yl)-1,3,5-triazine (2.5 g, 4.5 mmol), 4-(5,5-dimethyl-1,3,2-dioxaborhexane-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). A 2M potassium carbonate aqueous solution (16 mL, 33 mmol) was added to the suspension, and the mixture was refluxed for 17 hours. After adding water to the reaction solution, the solid was filtered off and washed with water, methanol, and hexane. The resulting solid was dissolved in toluene heated to 110 °C and hot-filtered using diatomaceous earth. The filtrate was allowed to stand at room temperature, and the precipitated solid was filtered off to obtain 4′,4′′′-(6-(9,10-dihydro-9,10-[1,2]benzanthracene-2-yl)-1,3,5-triazine-2,4-diyl)bis([1,1′-biphenyl]-4-carboxynitrile)(CA′4-GA′45) (yield 2.8 g, 90% yield).

[1048] 1 H-NMR (400MHz, CDCl3) 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).

[1049] <Synthetic Example-215>

[1050] 5-(4-(4-(9,10-dihydro-9,10-[1,2]benzanthracene-2-yl)phenyl)-6-phenyl-1,3,5-triazin-2-yl)isophthalonitrile (CA′75-GA′45)

[1051] [Chemistry 170]

[1052] 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]benzanthracene-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxane (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). A 2M potassium carbonate aqueous solution (7.2 mL, 14 mmol) was added to the suspension, and the mixture was refluxed for 17 hours. After adding water to the reaction solution, the solid was filtered off and washed with water, methanol, and hexane. The obtained solid was dissolved in toluene heated to 110°C and hot-filtered using diatomaceous earth. The filtrate was allowed to stand at room temperature, and the precipitated solid was collected to obtain 5-(4-(4-(9,10-dihydro-9,10-[1,2]benzanthracene-2-yl)phenyl)-6-phenyl-1,3,5-triazin-2-yl)isophthalonitrile (CA′75-GA′45) (yield 1.5 g, 56% yield).

[1053] 1 H-NMR (400MHz, CDCl3) 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).

[1054] <Synthetic Example-216>

[1055] 4′,4′′′-{6-[4-(1-adamantyl)phenyl]-1,3,5-triazine-2,4-diyl}-bis[(1,1′-biphenyl)-4-carboxynitrile](CA′4-GA′43)

[1056] [Chemistry 171]

[1057] 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-dioxaborhexane-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). A 2M tripotassium phosphate aqueous solution (3.7 mL, 7.4 mmol) was added to the suspension, and the mixture was refluxed for 3.5 hours. After filtering the reaction solution, the solution was washed with water, methanol and hexane. The resulting solid was dried under vacuum and then recrystallized from toluene to obtain 4′,4′′′-{6-[4-(1-adamantyl)phenyl]-1,3,5-triazine-2,4-diyl}-bis[(1,1′-biphenyl)-4-carboxynitrile](CA′4-GA′43) (yield 0.51 g, 64% yield).

[1058] 1 H-NMR (400MHz, CDCl3) δ (ppm): 8.89 (d, J=8.7Hz, 4H), 8.73 (d, J=8.6Hz, 2H), 7.78-7.83 (m, 1 2H), 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).

[1059] <Synthetic Example-217>

[1060] 4′,4′′′-[6-(fluoranthene-3-yl)]-1,3,5-triazine-2,4-diyl}-bis[(1,1′-biphenyl)-4-carboxylonitrile](CA′4-GA′29)

[1061] [Chemistry 172]

[1062] 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-dioxaborhexane-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). A 2M tripotassium phosphate aqueous solution (6.0 mL, 11.9 mmol) was added to the suspension, and the mixture was refluxed for 1 hour. After filtering the reaction solution, the solution was washed with water, methanol and hexane. The resulting solid was dried under vacuum and then recrystallized from toluene to obtain 4′,4′′′-[6-(fluoranthene-3-yl)]-1,3,5-triazine-2,4-diyl}-bis[(1,1′-biphenyl)-4-carboxynitrile](CA′4-GA′29) (yield 1.06 g, 84% yield).

[1063] 1 H-NMR (400MHz, CDCl3) 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).

[1064] <Synthetic Example-218>

[1065] 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)

[1066] [Chemistry 173]

[1067] 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-dioxaneborane-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). A 2M tripotassium phosphate aqueous 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 washed with THF, water, ethanol and hexane. The resulting solid was dried under vacuum 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%).

[1068] 1 H-NMR (400MHz, CDCl3) δ (ppm): 8.93 (dt, J=8.7, 1.9Hz, 2H), 8.89 (dt, J=8.6, 2. 0Hz, 2H), 8.86 (dt, 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).

[1069] <Synthetic Example-219>

[1070] 4-(3-(4-(9,10-dihydro-9,10-[1,2]benzanthracene-2-yl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)pyridine-2,6-dicarboxynitrile (CA′127-GA′45)

[1071] [Chemistry 174]

[1072] Under a nitrogen atmosphere, 2-((9,10-dihydro-9,10-[1,2]benzanthracene-2-yl)-4-phenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaneborane-2-yl)phenyl)-1,3,5-triazine (1.50 g, 2.45 mmol), 4-chloropyridine-2,6-dicarboxynitrile (0.531 g, 3.25 mmol), palladium acetate (12.0 mg, 0.0534 mmol), and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (50.1 mg, 0.105 mmol) were suspended in THF (25 mL). A 2M tripotassium phosphate aqueous solution (3... 7 mL, 7.4 mmol), refluxed for 5 hours. The reaction solution was cooled to room temperature, ethanol was added, and the solid was filtered off and washed with water, methanol, and hexane. The obtained solid was dissolved in a mixed solvent of 25 mL toluene and 25 mL pyridine and heated to 110 °C. 0.17 g of activated carbon was added to the solution, and the mixture was hot-filtered with diatomaceous earth. The filtrate was allowed to stand at room temperature, and the precipitated solid was filtered off to obtain 4-(3-(4-(9,10-dihydro-9,10-[1,2]benzanthracene-2-yl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)pyridine-2,6-dicarboxynitrile (CA′127-GA′45) (yield 1.3 g, 87%).

[1073] 1 H-NMR (400MHz, CDCl3) 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).

[1074] <Synthetic Example-220>

[1075] 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)

[1076] [Chemistry 175]

[1077] 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-dioxacyclopentaborane-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). A 2M potassium carbonate aqueous solution (0.36 mL, 0.72 mmol) was added to the suspension, and the mixture was refluxed for 17 hours. After adding water to the reaction solution, the solid was filtered off and washed with water, methanol, and hexane. The obtained solid was dissolved in hot toluene, activated carbon was added, and the mixture was stirred. The solution was then hot-filtered using diatomaceous earth. The filtrate was allowed to stand at room temperature, and the precipitated solid was filtered off 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% yield).

[1078] 1 H-NMR (400MHz, CDCl3) 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, 9.8 H), 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).

[1079] <Synthetic Example-221>

[1080] 4,4′-(4-(4,6-bis([1,1′-biphenyl]-4-yl)-1,3,5-triazin-2-yl)-1,2-phenylene)bis(1-naphthonitrile)(CC′135-GC′51)

[1081] [Chemistry 176]

[1082] Under an argon atmosphere, 2,4-bis([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-dioxacyclopentaborane-2-yl)-1,2-phenylene)bis(1-naphthonitrile) (1.4 g, 2.8 mmol), and tetra(triphenylphosphine)palladium (0.091 g, 0.079 mmol) were suspended in THF (26 mL). A 2M potassium carbonate aqueous solution (4.3 mL, 8.7 mmol) was added to the suspension, and the mixture was refluxed for 17 hours. After adding water to the reaction solution, activated carbon and sodium sulfate were added to the solution extracted with toluene, and the mixture was stirred and then filtered through diatomaceous earth. The solvent in the obtained solution was removed by distillation, methanol and hexane were added and ultrasonically treated, and the resulting solid was recrystallized with hot toluene to obtain 4,4′-(4-(4,6-bis([1,1′-biphenyl]-4-yl)-1,3,5-triazine-2-yl)-1,2-phenylene)bis(1-naphthonitrile) (CC′135-GC′51) (yield 1.5 g, yield 75%).

[1083] 1 H-NMR (400MHz, CDCl3) δ (ppm): 9.10-9.05 (m, 1H), 8.96 (d, J=1.5Hz, 0.4H), 8.9 0(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).

[1084] <Synthetic Example-222>

[1085] 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)

[1086] [Chemistry 177]

[1087] 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-dioxacyclopentaborane-2-yl)-1,2-phenylene)bis(1-naphthonitrile) (1.7 g, 3.4 mmol), and tetra(triphenylphosphine)palladium (0.11 g, 0.097 mmol) were suspended in THF (32 mL). A 2M potassium carbonate aqueous solution (5.4 mL, 11 mmol) was added to the suspension, and the mixture was refluxed for 17 hours. After adding water to the reaction solution, activated carbon and sodium sulfate were added to the solution extracted with toluene, and the mixture was stirred and filtered through a silica pad. The solvent in the obtained solution was removed by distillation, methanol and hexane were added and ultrasonically treated, and the resulting solid was washed with hot octane to obtain 4,4′-(4′-(4-([1,1′-biphenyl]-4-yl)-6-phenyl-1,3,5-triazine-2-yl)-[1,1′-biphenyl]-3,4-diyl)bis(1-naphthonitrile) (CC′137-GC′51) (yield 1.3 g, yield 53%).

[1088] 1 H-NMR (400MHz, CDCl3) 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).

[1089] <Synthetic Example-223>

[1090] 4′-(4,6-bis(4-(6-cyanopyridin-3-yl)phenyl)-1,3,5-triazin-2-yl)-[1,1′:2′,1′′-terphenyl]-4,4′′-dicarboxynitrile (CC′7-GC′1)

[1091] [Chemistry 178]

[1092] Under an argon atmosphere, 4′-(4,6-bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaneborane-2-yl)phenyl)-1,3,5-triazin-2-yl)-[1,1′:2′,1′′-terphenyl]-4,4′′-dicarboxynitrile (3.3 g, 4.3 mmol), 5-bromopyridinium carboxynitrile (1.9 g, 10.4 mmol), and tetrakis(triphenylphosphine)palladium (0.25 g, 0.22 mmol) were suspended in THF (43 mL). A 2M potassium carbonate aqueous solution (14 mL, 29 mmol) was added to the suspension, and the mixture was refluxed for 17 hours. The reaction solution was filtered after adding water and washing with water, methanol, hexane, and hot toluene. The resulting solid was dissolved in hot pyridine, activated carbon was added, and the mixture was stirred. The solution was then hot-filtered using diatomaceous earth. The filtrate was allowed to stand at room temperature, and the precipitated solid was filtered off 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′′-dicarboxynitrile (CC′7-GC′1) (yield 2.5 g, yield 81%).

[1093] 1 H-NMR (400MHz, CDCl3) 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).

[1094] <Glass transition temperature · LUMO level>

[1095] For the compounds (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- The glass transition temperatures (GLTs) of the following compounds were determined using a differential scanning calorimeter (DSC7020, manufactured by Hitachi Advanced Technology Co., Ltd.) at a scan rate of 10 °C / min, with an aluminum disk. The GLTs were calculated using density functional theory (DFT) based on the B3LYP functional and 6-31G(d) basis functions. The results for the glass transition temperatures and GLTs (calc. LUMO) were summarized in the table below. (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. It should be noted that in the table below, "ND" means "not detected." That is, compound (D′-16) and comparison compound 1 are not amorphous but crystalline. Additionally, in the table below, "-" means not determined.

[1096] [Chemistry 179]

[1097] [Table 194-1]

[1098]

[1099] [Table 194-2]

[1100]

[1101] [Table 194-3]

[1102]

[1103] [Table 194-4]

[1104]

[1105] The results in the table above show that, as a material for photoelectric conversion elements, the compound shown in formula (1) has excellent thermal stability compared to comparative compounds 1 and 3, and the calculated value of the LUMO energy level (calc. LUMO) is deeper (lower in the positive direction) than that of the comparative compounds.

[1106] <Component Example-201 (Refer to Figure 1)>

[1107] As shown in Figure 1, an imaging element 100 is fabricated as a photoelectric conversion element having a stacked 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. The dark current, external quantum efficiency, and responsivity of the imaging element are evaluated.

[1108] (Preparation of the first electrode 1)

[1109] As a substrate having a first electrode on its surface, a glass substrate with a transparent ITO electrode and a 2 mm wide indium tin oxide (ITO) film (110 nm thick) patterned into stripes was prepared. Then, the substrate was cleaned with isopropanol and subjected to surface treatment by ozone ultraviolet cleaning.

[1110] (Preparation for vacuum evaporation)

[1111] On a substrate that has undergone surface treatment after cleaning, vacuum evaporation is used to deposit each layer, and the layers are stacked to form each layer.

[1112] First, the glass substrate described above is introduced into a vacuum evaporation bath, and the pressure is reduced to 7.0 × 10⁻⁶. -5 Pa. Then, the films are prepared separately according to the film-forming conditions of each layer in the following order.

[1113] (Creating Hole Blocking Layer 2)

[1114] The sublimated and purified compound (D′-16) was deposited into a 10 nm film at a speed of 0.03 nm / s to create a hole blocking layer 2.

[1115] (Fabrication of photoelectric conversion layer (light-receiving layer) 3)

[1116] A 120 nm film was formed by mixing N,N-dimethylquinacridone and C60 in a 4:1 (mass ratio) manner to create the photoelectric conversion layer 3. The deposition rate was 0.15 nm / s.

[1117] (Fabrication of electron blocking layer 4)

[1118] Compound (ic-3) was deposited at a speed of 0.10 nm / s to form a 10 nm film, thus creating an electron blocking layer 4. It should be noted that (ic-3) was synthesized using the method described in Japanese Patent Application Publication No. 2018-193371.

[1119] (Creation of Hole Transport Layer 5)

[1120] A hole transport layer 5 was fabricated by forming a 10 nm film of compound 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene (HATCN) at a speed of 0.10 nm / s.

[1121] (Fabrication of the second electrode 6)

[1122] Finally, a metal mask is configured orthogonally to the ITO stripes on the substrate to form a film, which serves as the second electrode 6 of the upper electrode. Specifically, silver is deposited at a rate of 0.1 nm / s to form an 80 nm film, which serves as the second electrode 6 of the upper electrode.

[1123] Thus, a 4mm² area was produced as shown in Figure 1. 2 The camera uses a photoelectric conversion element 100. It should be noted that each film thickness was measured using a stylus-type film thickness gauge (manufactured by DEKTAK or Bruker).

[1124] The component is then sealed in a nitrogen atmosphere glove box with an oxygen and moisture concentration of less than 1 ppm. The sealing is performed on a glass sealing cap and a film-forming substrate (component) using bisphenol F epoxy resin (manufactured by Nagase ChemteX).

[1125] The dark current, external quantum efficiency, and response time were evaluated when a voltage of 2.6V was applied to the imaging element fabricated as described above. The dark current was measured using a Keithley Source Measure Unit 2636B. The external quantum efficiency was measured using a solar cell spectrophotometer (Soma Optical). The wavelength of the illumination light was 560 nm, and the intensity was 50 μW / cm². 2 The measurement is performed. The response time is the time it takes for the current value to return to its initial value after the irradiation of the light pulse.

[1126] It should be noted that the dark current, external quantum efficiency, and response time are relative values ​​to the reference value (1.0) of Comparative Example-201. Lower dark current values ​​indicate better performance, higher external quantum efficiency values ​​indicate better performance, and shorter response times indicate better performance. The measured results are shown in the table below.

[1127] <Component Examples - 202-206, 211, 214, 215, 219, 222, 223; Component Comparative Examples - 21, 22>

[1128] In Element Example-201, 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 in place of compound (D′-16). Otherwise, a photoelectric conversion element for imaging was fabricated and evaluated using the same method as in Element Example-201. The obtained measurement results are shown in the table below.

[1129] [Table 195]

[1130]

[1131] The results in the table above show that by using the compound shown in formula (1′) as the material for the photoelectric conversion element for the camera element to form the layer, compared with the case of using the comparative example compound to form the layer, a photoelectric conversion element for the camera element with improved responsiveness, external quantum efficiency and dark current is achieved.

[1132] Industrial availability

[1133] A camera element incorporating a photoelectric conversion element according to one aspect of the present invention may be, for example, a camera element applicable to a digital camera, a digital camcorder, a camera element built into a mobile phone, or an image input device for a driver assistance system.

[1134] Explanation of reference numerals in the attached figures

[1135] 1 First electrode

[1136] 2. Cavity blocking layer

[1137] 3. Photoelectric conversion layer (light-receiving layer)

[1138] 4 Electron blocking layer

[1139] 5. Hole transport layer

[1140] 6 Second electrode

[1141] 10 Organic Layers

[1142] 100 camera elements.

Claims

1. A camera element, characterized in that, The device comprises a layer containing a material for a photoelectric conversion element for an image sensor, the material for the photoelectric conversion element for an image sensor being represented by the following formula (1) or formula (1′), regarding the material for the photoelectric conversion element for an image sensor shown in the following formula (1): In equation (1), CA is represented by the following equation (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; Ar 3 Each independently represents a substituted or unsubstituted aromatic hydrocarbon group in the 1-5 valent range, a substituted or unsubstituted heteroaromatic group in the 1-5 valent range, or a substituted or unsubstituted cyclic aliphatic hydrocarbon group in the 1-5 valent range; L 1 ~L 3 Each independently represents a substituted or unsubstituted divalent to tetravalent aromatic hydrocarbon group, a substituted or unsubstituted divalent to tetravalent heteroaromatic group, or a substituted or unsubstituted divalent to tetravalent cyclic aliphatic hydrocarbon group; R 1 and R 2 Each can be independently represented as hydrogen or Ar. 3 ;a 1 a 2 b 1 b 2 c and d independently represent integers from 1 to 3; d and e independently represent integers from 1 to 2; and c + d + e represent integers from 1 to 3; p, q, and r independently represent integers from 0 to 3; n represents integers from 1 to 3; Ar 1 Ar 2 Ar 3 L 1 L 2 and L 3 At least one of the groups is selected from: heteroaromatic monocyclic groups selected from pyridyl, pyridinyl, pyrimidinyl, pyrazinyl, and tetraazinyl; or a fused-ring group consisting of 2 to 4 aromatic monocyclic groups, a portion of which contains at least one of the heteroaromatic monocyclic groups described above, regarding the material for the photoelectric conversion element for the imaging element shown in the following formula (1′): In the aforementioned formula (1′), Ar 11 ~Ar 31 Each independently represents a substituted or unsubstituted divalent or trivalent aromatic hydrocarbon group, a substituted or unsubstituted divalent or trivalent heteroaromatic group, or a substituted or unsubstituted divalent or trivalent cyclic aliphatic hydrocarbon group; L 11 ~L 31 Each independently represents a substituted or unsubstituted divalent to tetravalent aromatic hydrocarbon group, a substituted or unsubstituted divalent to tetravalent heteroaromatic group, or a substituted or unsubstituted divalent to tetravalent cyclic aliphatic hydrocarbon group; a 11 a 21 b 11 b 21 c 11 and c 21 Each can independently represent an integer from 1 to 3; p 1 q 1 and r 1 Each represents an integer from 0 to 3 independently; Ar 11 Ar 21 Ar 31 L 11 L 21 and L 31 At least one of them has a cyano group; in Ar 11 Ar 21 Ar 31 L 11 L 21 and L 31 In these groups, the sum of the number of cyano groups and the number of nitrogen-containing heteroaromatic rings composed of 6-membered rings is more than 2.

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

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

4. The imaging element according to any one of claims 1 to 3, wherein, In the formula (1), the Ar 1 Ar 2 Ar 3 L 1 L 2 and L 3 At least one of them is pyridinyl or pyrimidinyl.

5. The imaging element according to any one of claims 1 to 4, wherein, In the formula (1), the Ar 1 Ar 2 Ar 3 L 1 L 2 and L 3 At least two of them are pyridinyl or pyrimidinyl.

6. The imaging element according to claim 1, wherein, In the aforementioned formula (1′), in the Ar 11 Ar 21 Ar 31 L 11 L 21 and L 31 In these groups, the sum of the number of cyano groups and the number of pyridino groups is more than 2.

7. The imaging element according to claim 1, wherein, The imaging element includes a layer comprising a material for a photoelectric conversion element for the imaging element, the material for the photoelectric conversion element for the imaging element being represented by the following formula (2): In equation (2), L 21A Indicates phenylene; q 1A R represents an integer that is either 0 or 1; 21 Any one of equations (21a) to (24a) can be used to express: In equations (21a) to (24a), Ar 21A Same or different indicates substituted or unsubstituted aromatic hydrocarbon groups, or substituted or unsubstituted heteroaromatic groups; R 22 and R 23 Each can be independently represented by any one of equations (21b) to (25b): In equations (21b) to (25b), Ar 22A "Same" or "different" indicates substituted or unsubstituted aromatic hydrocarbon groups, or substituted or unsubstituted heteroaromatic groups; L 22A Indicates a phenylene oxide or a single bond; Indicates the bonding site; Ar in formulas (21a) to (24a) 21A And Ar in equations (21b) to (25b) 22A At least one of them has a cyano group; Ar in formulas (21a) to (24a) 21A And Ar in equations (21b) to (25b) 22A In these groups, the sum of the number of cyano groups and the number of pyridine rings is more than 2, in R 21 The expression (21a) and / or R 22 and R 23 When at least one of them is represented by equation (21b), Ar in equation (21a) 21A And Ar in equation (21b) 22A Whether the groups are the same or different, they are aromatic hydrocarbon groups substituted with one or more cyano groups, or heteroaromatic groups substituted with one or more cyano groups.

8. The imaging element according to claim 7, wherein, In equation (2), the L 21A It can be an ortho-phenylene, a para-phenylene, or a single bond.

9. The imaging element according to claim 7 or 8, wherein, In equation (2), the Ar 21A The same or different, is an aromatic hydrocarbon group substituted with a cyano group, or a heteroaromatic group that is substituted or unsubstituted.

10. The imaging element according to any one of claims 7 to 9, wherein, In equation (2), the Ar 22A The same or different, is an aromatic hydrocarbon group substituted with a cyano group, or a heteroaromatic group that is substituted or unsubstituted.

11. The imaging element according to any one of claims 7 to 10, wherein, In equation (2), Ar in equations (21a) to (24a) 21A And Ar in equations (21b) to (25b) 22A At least two of them have cyano groups.

12. The imaging element according to any one of claims 1 to 11, wherein, The material used for the photoelectric conversion element of the camera element has a molecular weight of 550 or higher.

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

14. A compound represented by formula (11), formula (12), formula (13), formula (14), formula (3) or formula (4), characterized in that, The compound represented by the following formula (11) is: In the aforementioned formula (11), Ar 111 and Ar 211 Each independently represents 3-pyridinyl or 4-pyridinyl; Ar 311 This refers to a phenanthrene group (monovalent or divalent), a dimethylfluorenyl group (monovalent or divalent), a diphenylfluorenyl group (monovalent or divalent), a spirodifluorenyl group (monovalent or divalent), a triterpenyl group (monovalent or divalent), an aromatic group having at least one sulfone group and 6 to 26 carbon atoms, or a cyclic aliphatic hydrocarbon group having 10 to 16 carbon atoms; L 311 This indicates a divalent phenyl or a divalent pyridyl group, in L... 311 In the case of multiple Ls, multiple Ls 311 Same or different; r 11 n represents an integer from 0 to 2; 11 Representing an integer of 1 or 2, the compound with a triazine ring shown in the following formula (12) is: In the above formula (12), L 112 and L 212 The divalent pyridinyl group represents a pyridinyl group; the divalent pyridinyl group has a bond with the triazine ring at position 3 or 4; when the divalent pyridinyl group has a bond with the triazine ring at position 4, Ar 112 and Ar 212 Each can independently represent an aromatic hydrocarbon group with 10 to 26 carbon atoms, a nitrogen-containing heteroaromatic group with 6 to 26 carbon atoms consisting only of a 6-membered ring, an aromatic group with 6 to 26 carbon atoms having at least one sulfone group, or a cyclic aliphatic hydrocarbon group with 10 to 16 carbon atoms; when the divalent pyridinium group has a bond with the triazine ring at the 3 position, Ar 112 and Ar 212 Each can independently represent biphenyl, terphenyl, phenanthrene, dimethylfluorenyl, diphenylfluorenyl, spirodifluorenyl, triphenylenyl, an aromatic group having at least one sulfone group and 6 to 26 carbon atoms, or a cyclic aliphatic hydrocarbon group having 10 to 16 carbon atoms; Ar 312 The following groups represent aromatic hydrocarbon groups with 6 to 26 carbon atoms, nitrogen-containing heteroaromatic groups with 6 to 26 carbon atoms consisting only of a 6-membered ring, oxygen-containing or sulfur-containing heteroaromatic groups with 4 to 26 carbon atoms, aromatic groups with 6 to 26 carbon atoms having at least one sulfone group, or cyclic aliphatic hydrocarbon groups with 10 to 16 carbon atoms; L 312 Indicates a single bond, a divalent or trivalent phenyl group, or a divalent or trivalent pyridyl group; L 412 This indicates a divalent phenyl or a divalent pyridyl group, in L... 412 In the case of multiple Ls, multiple Ls 412 Same or different; c 12 The compound represented by the following formula (13) is an integer representing 1 or 2: In the aforementioned formula (13), Ar 113 and Ar 213 Each independently represents 3-pyridinyl or 4-pyridinyl; Ar 313 The following groups represent aromatic hydrocarbon groups with 10 to 26 carbon atoms, nitrogen-containing heteroaromatic groups with 2 to 26 carbon atoms consisting only of a 6-membered ring, oxygen-containing or sulfur-containing heteroaromatic groups with 4 to 26 carbon atoms, aromatic groups with 6 to 26 carbon atoms having at least one sulfone group, or cyclic aliphatic hydrocarbon groups with 10 to 16 carbon atoms; L 313 Indicates a single bond, a divalent or trivalent phenyl group, or a divalent or trivalent pyridyl group; L 413 This indicates a divalent phenyl or a divalent pyridyl group, in L... 413 In the case of multiple Ls, multiple Ls 413 Same or different; c 13 The compound represented by the following formula (14) is an integer representing 1 or 2: In the aforementioned formula (14), Ar 114 and Ar 214 Each independently represents 3-pyridinyl or 4-pyridinyl; Ar 314 The following groups represent aromatic hydrocarbon groups with 10 to 24 carbon atoms, nitrogen-containing heteroaromatic groups with 6 to 26 carbon atoms consisting only of a 6-membered ring, oxygen-containing or sulfur-containing heteroaromatic groups with 4 to 26 carbon atoms, aromatic groups with 6 to 26 carbon atoms having at least one sulfone group, or cyclic aliphatic hydrocarbon groups with 10 to 16 carbon atoms; L 314 Indicates a single bond, a divalent or trivalent phenyl group, or a divalent or trivalent pyridyl group; L 414 This indicates a divalent phenyl or a divalent pyridyl group, in L... 414 In the case of multiple Ls, multiple Ls 414 Same or different; c 14 The compound represented by the following formula (3) is an integer representing 1 or 2: In the above formula (3), L 31A Indicates phenylene; r 1A R represents an integer that is either 0 or 1; 31 Any one of equations (31a) to (34a) can be used to express: In equations (31a) to (34a), Ar 31A Same or different, indicating phenyl, pyridyl, pyridyl substituted with one or more cyano groups, pyridyl substituted with one or more alkyl groups having 1 to 6 carbon atoms, pyridyl substituted with one or more cyano groups, or naphthyl group substituted or unsubstituted; R 32 and R 33 Each can be independently represented by any one of equations (31b) to (35b): In equations (31b) to (35b), Ar 32A Same or different, indicating phenyl, phenyl substituted with one or more alkyl groups having 1 to 6 carbon atoms, phenyl substituted with one or more cyano groups, pyridyl, pyridyl substituted with one or more alkyl groups having 1 to 6 carbon atoms, pyridyl substituted with one or more cyano groups, or biphenyl; L 32A Indicates a phenylene oxide or a single bond; Indicates the bonding site; Ar in formulas (31a) to (34a) 31A And Ar in equations (31b) to (35b) 32A At least one of them has a cyano group; in R 31 The expression (31a) and / or R 32 and R 33 When at least one of them is represented by the formula (31b), Ar in the formula (31a) 31A And Ar in equation (31b) 32A Whether identical or different, a phenyl group substituted with one or more cyano groups, or a pyridyl group substituted with one or more cyano groups, the compound represented by the following formula (4) is: In equation (4), Ar 41 and Ar 42 Each can independently represent an aromatic hydrocarbon group with 6 to 26 carbon atoms (substituted or unsubstituted), a nitrogen-containing heteroaromatic group with 3 to 26 carbon atoms (substituted or unsubstituted) consisting only of a 6-membered ring, an oxygen-containing or sulfur-containing heteroaromatic group with 3 to 26 carbon atoms (substituted or unsubstituted), or a cyclic aliphatic hydrocarbon group with 10 to 16 carbon atoms; L 41 ~L 43 Each can independently represent a divalent aromatic hydrocarbon group with 6 to 26 carbon atoms (substituted or unsubstituted), a divalent nitrogen-containing heteroaromatic group with 3 to 26 carbon atoms (substituted or unsubstituted) consisting only of a 6-membered ring, a divalent heteroaromatic group with 3 to 26 carbon atoms (substituted or unsubstituted), or a divalent cyclic aliphatic hydrocarbon group with 10 to 16 carbon atoms; p 4 q 4 and r 4 Each independently represents an integer from 0 to 2; Ar 41 Ar 42 L 41 L 42 and L 43 At least one of them has a cyano group.

15. The compound according to claim 14, wherein, In equation (4), the L 41 L 42 and L 43 Each is independently a phenyl group, either substituted with or unsubstituted with a cyano group, or a pyridyl group, either substituted with or unsubstituted with a cyano group.

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

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

18. A material for a photoelectric conversion element used in a camera element, characterized in that, The compound comprising any one of claims 14 to 17.

19. The material for a photoelectric conversion element for a camera element according to claim 18, wherein the material is a hole-blocking material.

20. A camera element, characterized in that, It comprises a layer containing the material of the photoelectric conversion element for a camera element as described in claim 18 or 19.

Images