Compound, composition, ink, photoelectric conversion element, and optical sensor

Abstract

Provided are a compound, a composition, an ink, a photoelectric conversion element, and a photosensor capable of performing photoelectric conversion in a short-wave infrared (SWIR) region and having excellent solubility.SOLUTION: A compound represented by the following formula (1): In formula (1), A1, A2, L1, L2, D, m and n are as defined in the description.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a compound, a composition, an ink, a photoelectric conversion element, and an optical sensor. [Background technology]

[0002] Photoelectric conversion elements are attracting attention as extremely useful devices from the viewpoints of, for example, energy conservation and reduction of carbon dioxide emissions.

[0003] A photoelectric conversion element is an element that includes at least a pair of electrodes consisting of an anode and a cathode, and an active layer disposed between the pair of electrodes. In a photoelectric conversion element, at least one of the pair of electrodes is made of a transparent or semitransparent material, and light is incident on the active layer from the transparent or semitransparent electrode side. The energy (hν) of light incident on the active layer generates charges (holes and electrons) in the active layer, and the generated holes move toward the anode and the electrons move toward the cathode. The charges that reach the anode and cathode are then extracted to the outside of the element.

[0004] In recent years, there has been a demand for further improvements in the properties of photoelectric conversion elements, and various semiconductor materials have been developed and reported to meet this demand.

[0005] Patent Document 1 discloses a compound having a specific chemical structure that can absorb near-infrared light. Patent Document 2 discloses a compound having a specific chemical structure that has excellent external quantum efficiency. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Chinese Patent Application Publication No. 114195801 [Patent Document 2] Japanese Patent Application Publication No. 2023-107154 Summary of the Invention [Problem to be solved by the invention]

[0007] However, there is a demand for further semiconductor materials that can satisfy the properties required for photoelectric conversion elements. The present disclosure has been made in view of the above, and relates to providing a compound, composition, ink, photoelectric conversion element, and optical sensor that are capable of photoelectric conversion in the short-wave infrared (SWIR) region and have excellent solubility. [Means for solving the problem]

[0008] The present disclosure includes the following aspects. <1> A compound represented by the following formula (1):

[0009] [ka]

[0010] (In formula (1), D is a divalent aromatic group having two bonds, and the conjugated structure connecting the two bonds in D by the shortest distance contains three or more double bonds; L1 and L2 each independently represent a divalent aromatic group different from D, and among all units represented by L1 and L2, at least one unit has a side chain that is incapable of non-covalently interacting with an element in another adjacent unit, but does not have a side chain that is capable of non-covalently interacting with an element in another adjacent unit, and at least one other unit different from the at least one unit has a side chain that is capable of non-covalently interacting with an element in another adjacent unit, L1 and L2 may be the same or different, m is 2 or 3, and n is an integer from 1 to 3; A1 and A2 each independently represent an electron-withdrawing monovalent group having at least one aromatic ring. <2> m is 2 and n is 1 or 2; <1> The compound described in <3> L1 and L2 each independently represent any of groups represented by the following formulae (L1-1) to (L1-8): <1> or <2> The compound described in

[0011] [ka]

[0012] (In formulas (L1-1) to (L1-8), R L1 are each independently hydrogen atoms, halogen atoms, an alkyl group which may have a substituent, an optionally substituted cycloalkyl group, an optionally substituted aryl group; an alkyloxy group which may have a substituent; an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an alkylthio group which may have a substituent; an optionally substituted cycloalkylthio group, an optionally substituted arylthio group; an optionally substituted monovalent heterocyclic group, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted carbonyl group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; a substituted sulfonyl group which may have a substituent; a substituted oxysulfonyl group which may have a substituent; an alkenyl group which may have a substituent; an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group; an optionally substituted cycloalkynyl group, a cyano group, or represents a nitro group, Further R L1 is a side chain capable of non-covalent interactions, R L1 each independently has at least one atom selected from the group consisting of a halogen atom, a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, and a phosphorus atom. <4> D is any of the structures represented by the following formulas (D-1) to (D-7): <1> ~ <3> 1. The compound according to any one of claims 1 to 9.

[0013] [ka]

[0014] In formulas (D-1), (D-2), (D-6) and (D-7), X is any of the groups represented by the following formulas (X-1) to (X-6).

[0015] [ka]

[0016] In formulas (D-3) to (D-7) and formulas (X-1) to (X-6), R d are each independently hydrogen atoms, halogen atoms, an alkyl group which may have a substituent, an optionally substituted cycloalkyl group, an optionally substituted aryl group; an alkyloxy group which may have a substituent; an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an alkylthio group which may have a substituent; an optionally substituted cycloalkylthio group, an optionally substituted arylthio group; an optionally substituted monovalent heterocyclic group, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted carbonyl group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; a substituted sulfonyl group which may have a substituent; a substituted oxysulfonyl group which may have a substituent; an alkenyl group which may have a substituent; an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group; an optionally substituted cycloalkynyl group, a cyano group, or represents a nitro group, In formula (D-2), formula (D-5) and formula (D-7), Ar 1 and Ar 2 are each independently an aromatic carbocyclic ring which may have a substituent and may be further condensed with a plurality of ring structures, or an aromatic heterocyclic ring which may have a substituent and may be further condensed with a plurality of ring structures. 1 and Ar 2 Either one of them may not be present.) <5> A1 and A2 each independently represent any one of groups represented by the following formulae (a-1) to (a-5): <1> ~ <4> 1. The compound according to any one of claims 1 to 9.

[0017] [ka]

[0018] (In the above formulas (a-1) to (a-5), T represents a carbocyclic ring which may have a substituent, or a heterocyclic ring which may have a substituent. The carbocyclic ring and the heterocyclic ring may be a monocyclic ring or a condensed ring. When these rings have a plurality of substituents, the plurality of substituents may be the same or different. X 4 , X 5 , and X 6 are each independently an oxygen atom, a sulfur atom, an alkylidene group, ═C(—CN)2, or ═C(—CN)—CR a represents a group represented by R a represents an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an aromatic alkyl group having 5 to 30 carbon atoms, an aromatic alkenyl group having 5 to 30 carbon atoms, or an aromatic alkynyl group having 5 to 30 carbon atoms, and the alkyl group, alkenyl group, alkynyl group, aromatic alkyl group, aromatic alkenyl group, and aromatic alkynyl group may have a substituent and may be linear, branched, or cyclic. <6> The semiconductor material includes a p-type semiconductor material and an n-type semiconductor material, <1> ~ <5> A composition comprising a compound according to any one of claims 1 to 4. <7> The p-type semiconductor material is a polymer compound containing at least one selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4): <6> The composition described in

[0019] [ka]

[0020] (In formula (3), Ar 3 and Ar 4 each independently represents a trivalent aromatic heterocyclic group which may have a substituent, and Z represents any of the groups represented by the following formulae (Z-1) to (Z-7).

[0021] [ka]

[0022] In formulas (Z-1) to (Z-7), R is independently hydrogen atoms, halogen atoms, an alkyl group which may have a substituent, an optionally substituted cycloalkyl group, an optionally substituted aryl group; an alkyloxy group which may have a substituent; an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an alkylthio group which may have a substituent; an optionally substituted cycloalkylthio group, an optionally substituted arylthio group; an optionally substituted monovalent heterocyclic group, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; an alkenyl group which may have a substituent; an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group; an optionally substituted cycloalkynyl group, an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, a cyano group, or represents a nitro group, In each of formulas (Z-1) to (Z-7), when there are two R, the two R may be the same or different, In formula (4), Ar 5 represents a divalent aromatic heterocyclic group. <8> <1> ~ <5> 10. An ink comprising the compound according to any one of the above items and a solvent. <9> an anode, a cathode, and an active layer provided between the anode and the cathode and including a p-type semiconductor material and an n-type semiconductor material; The n-type semiconductor material is <1> ~ <5> A photoelectric conversion element comprising the compound according to any one of the above items. <10> A photodetector element, <9> The photoelectric conversion element according to claim 1. <11> <9> or <10> An optical sensor comprising the photoelectric conversion element according to claim 1. [Effects of the Invention]

[0023] According to the present disclosure, there are provided a compound, composition, ink, photoelectric conversion element, and optical sensor that are capable of photoelectric conversion in the short-wave infrared (SWIR) region and have excellent solubility. [Brief explanation of the drawings]

[0024] [Figure 1] FIG. 1 is a diagram schematically illustrating an example of the configuration of a photoelectric conversion element. DETAILED DESCRIPTION OF THE INVENTION

[0025] An embodiment of the present disclosure will be described in detail below. However, the present disclosure is not limited to the following embodiment. In the following disclosure, components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the present disclosure.

[0026] The compounds of the present disclosure will be described below, and further, a photoelectric conversion element using the compounds of the present disclosure will be described with reference to the drawings. Note that the drawings merely show the shapes, sizes, and arrangements of the components to the extent that the invention can be understood. The present disclosure is not limited by the following description, and each component can be appropriately modified within the scope of the present disclosure. Furthermore, the configuration of the present disclosure is not necessarily manufactured or used in the arrangement shown in the drawings.

[0027] In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the lower and upper limits, respectively. In the numerical ranges described in stages in this disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples. In the present disclosure, when a composition contains multiple substances corresponding to each component, the content of each component in the composition means the total content of the multiple substances present in the composition, unless otherwise specified. In the present disclosure, when multiple elements are listed using "or" or "or," unless otherwise expressly stated, it does not exclude the selection of a combination of the multiple elements unless a technical contradiction arises. In the present disclosure, even if an element is referred to in the singular, unless expressly stated otherwise, it does not exclude the presence of a plurality insofar as it does not create a technical contradiction. In the present disclosure, multiple exemplary aspects described separately may be combined with each other to form a new aspect, unless they contradict each other.

[0028] The following describes commonly used terms in this disclosure. In the description of this disclosure, the following descriptions apply unless otherwise specified.

[0029] The term "non-fullerene compound" refers to a compound that is neither a fullerene nor a fullerene derivative.

[0030] The term "π-conjugated system" refers to a system in which π electrons are delocalized among multiple bonds.

[0031] "Polymer compounds" are compounds that have a molecular weight distribution and have a number average molecular weight equivalent to polystyrene of 1 x 10 3 More than 1×10 8 The term "polymer" refers to a polymer having the following structure: The total amount of structural units contained in the polymer compound is 100 mol %.

[0032] The term "structural unit" refers to a residue derived from a raw material compound (monomer), of which one or more are present in a compound or polymer compound.

[0033] The "hydrogen atom" may be a protist atom or a deuterium atom.

[0034] Examples of "halogen atoms" include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0035] In the present disclosure, "side chain A" refers to hydrogen atoms, halogen atoms, an alkyl group which may have a substituent, an optionally substituted cycloalkyl group, an optionally substituted aryl group; an alkyloxy group which may have a substituent; an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an alkylthio group which may have a substituent; an optionally substituted cycloalkylthio group, an optionally substituted arylthio group; an optionally substituted monovalent heterocyclic group, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted carbonyl group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; a substituted sulfonyl group which may have a substituent; a substituted oxysulfonyl group which may have a substituent; an alkenyl group which may have a substituent; an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group; an optionally substituted cycloalkynyl group, a cyano group, or nitro group, This means that

[0036] In the present disclosure, "side chain B" refers to the group options in the above "side chain A" excluding hydrogen atoms.

[0037] The embodiment in which "may have a substituent" includes both a case in which all hydrogen atoms constituting the compound or group are unsubstituted, and a case in which one or more hydrogen atoms are partially or entirely substituted with a substituent.

[0038] Examples of the "substituent" include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an alkyloxy group, a cycloalkyloxy group, an alkylthio group, a cycloalkylthio group, an aryl group, an aryloxy group, an arylthio group, a monovalent heterocyclic group, a substituted amino group, an acyl group, an imine residue, an amide group, an acid imide group, a substituted oxycarbonyl group, a cyano group, an alkylsulfonyl group, and a nitro group. In this specification, the number of carbon atoms generally does not include the number of carbon atoms of substituents.

[0039] In this specification, unless otherwise specified, the "alkyl group" may be any of linear, branched, and cyclic. The number of carbon atoms in a linear alkyl group, not including the number of carbon atoms in the substituent, is usually preferably 1 to 50, more preferably 1 to 30, and even more preferably 1 to 20. The number of carbon atoms in a branched or cyclic alkyl group, not including the number of carbon atoms in the substituent, is usually preferably 3 to 50, more preferably 3 to 30, and even more preferably 4 to 20.

[0040] Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isoamyl group, a 2-ethylbutyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, a cyclohexylmethyl group, a cyclohexylethyl group, an n-octyl group, a 2-ethylhexyl group, a 3-n-propylheptyl group, an adamantyl group, an n-decyl group, a 3,7-dimethyloctyl group, a 2-ethyloctyl group, a 2-n-hexyl-decyl group, an n-dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, and an eicosyl group.

[0041] The alkyl group may have a substituent. The substituted alkyl group is, for example, a group in which a hydrogen atom in the above-exemplified alkyl group is substituted with a substituent such as an alkyloxy group, an aryl group, or a fluorine atom.

[0042] Specific examples of the alkyl having a substituent include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a 3-phenylpropyl group, a 3-(4-methylphenyl)propyl group, a 3-(3,5-dihexylphenyl)propyl group, and a 6-ethyloxyhexyl group.

[0043] The "cycloalkyl group" may be a monocyclic group or a polycyclic group. The cycloalkyl group may have a substituent. The number of carbon atoms in the cycloalkyl group, not including the number of carbon atoms in the substituent, is usually preferably 3 to 30, and more preferably 12 to 19.

[0044] Examples of cycloalkyl groups include unsubstituted alkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and an adamantyl group, as well as groups in which the hydrogen atoms in these groups are substituted with substituents such as an alkyl group, an alkyloxy group, an aryl group, or a fluorine atom.

[0045] Specific examples of the substituted cycloalkyl group include a methylcyclohexyl group and an ethylcyclohexyl group.

[0046] The term "aromatic carbocyclic group" refers to an atomic group remaining after removing any number of hydrogen atoms directly bonded to carbon atoms constituting the ring from an aromatic hydrocarbon that may have a substituent. The aromatic carbocyclic group may further have a substituent. The term "aromatic carbocyclic ring" also includes a structure in which two or more carbocyclic rings (aromatic rings) are connected together via, for example, a group (substituent) containing a heteroatom.

[0047] Specific examples of the aromatic carbocyclic ring include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring.

[0048] The term "aryl group" refers to a monovalent aromatic carbocyclic group, which is the atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom constituting the ring from an aromatic hydrocarbon which may have a substituent.

[0049] The aryl group may have a substituent. Specific examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a 1-pyrenyl group, a 2-pyrenyl group, a 4-pyrenyl group, a 2-fluorenyl group, a 3-fluorenyl group, a 4-fluorenyl group, a 2-phenylphenyl group, a 3-phenylphenyl group, a 4-phenylphenyl group, and groups in which a hydrogen atom in these groups is substituted with a substituent such as an alkyl group, an alkyloxy group, an aryl group, or a fluorine atom.

[0050] The term "arylene group" refers to a divalent aromatic carbocyclic group, which is an atomic group remaining after removing two hydrogen atoms directly bonded to carbon atoms constituting the ring from an aromatic hydrocarbon which may have a substituent.

[0051] The "alkyloxy group" (alkoxy group) may be linear, branched, or cyclic. The number of carbon atoms in a linear alkyloxy group, not including the number of carbon atoms in the substituent, is usually preferably 1 to 40, more preferably 1 to 10. The number of carbon atoms in a branched or cyclic alkyloxy group, not including the number of carbon atoms in the substituent, is usually preferably 3 to 40, more preferably 4 to 10.

[0052] The alkyloxy group may have a substituent. Specific examples of the alkyloxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a tert-butyloxy group, an n-pentyloxy group, an n-hexyloxy group, a cyclohexyloxy group, an n-heptyloxy group, an n-octyloxy group, a 2-ethylhexyloxy group, an n-nonyloxy group, an n-decyloxy group, a 3,7-dimethyloctyloxy group, a 3-heptyldodecyloxy group, a lauryloxy group, and groups in which a hydrogen atom in these groups is substituted with an alkyloxy group, an aryl group, or a fluorine atom.

[0053] The cycloalkyl group in the "cycloalkyloxy group" may be a monocyclic group or a polycyclic group. The cycloalkyloxy group may have a substituent. The number of carbon atoms in the cycloalkyloxy group, not including the number of carbon atoms of the substituent, is usually preferably 3 to 30, and more preferably 12 to 19.

[0054] Examples of the cycloalkyloxy group include unsubstituted cycloalkyloxy groups such as a cyclopentyloxy group, a cyclohexyloxy group, and a cycloheptyloxy group, as well as groups in which a hydrogen atom in these groups has been substituted with a fluorine atom or an alkyl group.

[0055] The number of carbon atoms in the "aryloxy group" is usually preferably 6 to 60, and more preferably 6 to 48, not including the number of carbon atoms of the substituent.

[0056] The aryloxy group may have a substituent. Specific examples of the aryloxy group include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 1-anthracenyloxy group, a 9-anthracenyloxy group, a 1-pyrenyloxy group, and groups in which a hydrogen atom in these groups is substituted with a substituent such as an alkyl group, an alkyloxy group, or a fluorine atom.

[0057] The "alkylthio group" may be linear, branched, or cyclic. The number of carbon atoms in a linear alkylthio group, not including the number of carbon atoms in the substituent, is usually preferably 1 to 40, more preferably 1 to 10. The number of carbon atoms in a branched or cyclic alkylthio group, not including the number of carbon atoms in the substituent, is usually preferably 3 to 40, more preferably 4 to 10.

[0058] The alkylthio group may have a substituent. Specific examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, an isobutylthio group, a tert-butylthio group, a pentylthio group, a hexylthio group, a cyclohexylthio group, a heptylthio group, an octylthio group, a 2-ethylhexylthio group, a nonylthio group, a decylthio group, a 3,7-dimethyloctylthio group, a laurylthio group, and a trifluoromethylthio group.

[0059] The cycloalkyl group in the "cycloalkylthio group" may be a monocyclic group or a polycyclic group. The cycloalkylthio group may have a substituent. The number of carbon atoms in the cycloalkylthio group, not including the number of carbon atoms in the substituent, is usually preferably 3 to 30, more preferably 12 to 19.

[0060] Examples of the optionally substituted cycloalkylthio group include a cyclohexylthio group.

[0061] The number of carbon atoms in the "arylthio group" is usually preferably 6 to 60, and more preferably 6 to 48, not including the number of carbon atoms in the substituent.

[0062] The arylthio group may have a substituent. Examples of the arylthio group include a phenylthio group, a C1-C12 alkyloxyphenylthio group (C1-C12 indicates that the group immediately following it has 1 to 12 carbon atoms, and the same applies below), a C1-C12 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a pentafluorophenylthio group.

[0063] The term "heterocyclic group" refers to an atomic group remaining after removing any number of hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting the ring from an optionally substituted heterocyclic compound.

[0064] The heterocyclic group may further have a substituent. The number of carbon atoms in the heterocyclic group is usually preferably 2 to 30, more preferably 2 to 6, not including the number of carbon atoms in the substituent.

[0065] Examples of substituents that the heterocyclic compound may have include a halogen atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, a monovalent heterocyclic group, a substituted amino group, an acyl group, an imine residue, an amide group, an acid imide group, a substituted oxycarbonyl group, an alkenyl group, an alkynyl group, a cyano group, and a nitro group. The heterocyclic group includes an "aromatic heterocyclic group."

[0066] The term "aromatic heterocyclic group" refers to an atomic group remaining after removing any number of hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting the ring from an aromatic heterocyclic compound which may have a substituent. The aromatic heterocyclic group may further have a substituent.

[0067] Specific examples of the aromatic heterocycle include an oxadiazole ring, a thiadiazole ring, a thiazole ring, an oxazole ring, a thiophene ring, a pyrrole ring, a phosphole ring, a furan ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a pyridazine ring, a quinoline ring, an isoquinoline ring, a carbazole ring, a dibenzophosphole ring, a phenoxazine ring, a phenothiazine ring, a dibenzoborole ring, a dibenzosilole ring, and a benzopyran ring.

[0068] Aromatic heterocyclic compounds include compounds in which the heterocycle itself exhibits aromaticity, as well as compounds in which an aromatic ring is condensed with a heterocycle even if the heterocycle itself does not exhibit aromaticity.

[0069] Among aromatic heterocyclic compounds, specific examples of compounds in which the heterocycle itself exhibits aromaticity include oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, and dibenzophosphole.

[0070] Among aromatic heterocyclic compounds, specific examples of compounds in which the aromatic heterocycle itself does not exhibit aromaticity and an aromatic ring is condensed with the heterocycle include phenoxazine, phenothiazine, dibenzoborole, dibenzosilole, and benzopyran.

[0071] The number of carbon atoms in the monovalent heterocyclic group is usually preferably 2 to 60, and more preferably 4 to 20, not including the number of carbon atoms in the substituent.

[0072] The monovalent heterocyclic group may have a substituent. Specific examples of the monovalent heterocyclic group include a thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a piperidyl group, a quinolyl group, an isoquinolyl group, a pyrimidinyl group, a triazinyl group, and groups in which a hydrogen atom in these groups is substituted with an alkyl group, an alkyloxy group, or the like.

[0073] The term "substituted amino group" refers to an amino group having a substituent. Examples of the substituent on the amino group include an alkyl group, an aryl group, and a monovalent heterocyclic group, and an alkyl group, an aryl group, or a monovalent heterocyclic group is preferred. The number of carbon atoms in the substituted amino group is usually preferably 2 to 30.

[0074] Examples of the substituted amino group include dialkylamino groups such as a dimethylamino group and a diethylamino group; and diarylamino groups such as a diphenylamino group, a bis(4-methylphenyl)amino group, a bis(4-tert-butylphenyl)amino group, and a bis(3,5-di-tert-butylphenyl)amino group.

[0075] The "acyl group" may have a substituent. The number of carbon atoms in the acyl group, not including the number of carbon atoms in the substituent, is usually preferably 2 to 20, and more preferably 2 to 18. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.

[0076] The term "imine residue" refers to the atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom or nitrogen atom constituting a carbon-nitrogen double bond from an imine compound. The term "imine compound" refers to an organic compound having a carbon-nitrogen double bond within the molecule. Examples of imine compounds include aldimines, ketimines, and compounds in which the hydrogen atom bonded to the nitrogen atom constituting the carbon-nitrogen double bond in an aldimine is substituted with an alkyl group or the like.

[0077] The imine residue usually preferably has 2 to 20 carbon atoms, more preferably 2 to 18 carbon atoms. Examples of the imine residue include groups represented by the structural formula described in paragraph

[0058] of WO 2023 / 100844. In the structural formula, Me represents a methyl group.

[0078] The term "amide group" refers to the atomic group remaining after removing one hydrogen atom bonded to a nitrogen atom from an amide. The number of carbon atoms in the amide group is usually preferably 1 to 20, and more preferably 1 to 18. Specific examples of the amide group include a formamide group, an acetamide group, a propioamide group, a butyromido group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyromido group, a dibenzamide group, a ditrifluoroacetamide group, and a dipentafluorobenzamide group.

[0079] The term "acid imide group" refers to the atomic group remaining after removing one hydrogen atom bonded to a nitrogen atom from an acid imide. The number of carbon atoms in the acid imide group is usually preferably 4 to 20. Specific examples of the acid imide group include groups represented by the structural formula described in paragraph

[0061] of WO 2023 / 100844. In the structural formula, Me represents a methyl group.

[0080] A "substituted carbonyl group" is a -(C=O)-R X where R X represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

[0081] "Substituted oxycarbonyl group" means -(C=O)-OR X or -O-(C=O)-R X where R X represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

[0082] "Substituted sulfonyl group" means -SO2-R X where R X represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

[0083] "Substituted oxysulfonyl group" means -(SO2)-OR X or -O-(SO2)-R X where R X represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

[0084] The number of carbon atoms in the substituted oxycarbonyl group is usually preferably 2 to 60, more preferably 2 to 48, not including the number of carbon atoms in the substituent.

[0085] Specific examples of the substituted oxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a tert-butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, a cyclohexyloxycarbonyl group, a heptyloxycarbonyl group, an octyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, a nonyloxycarbonyl group, a decyloxycarbonyl group, a 3,7-dimethyloctyloxycarbonyl group, a dodecyloxycarbonyl group, a trifluoromethoxycarbonyl group, a pentafluoroethoxycarbonyl group, a perfluorobutoxycarbonyl group, a perfluorohexyloxycarbonyl group, a perfluorooctyloxycarbonyl group, a phenoxycarbonyl group, a naphthoxycarbonyl group, and a pyridyloxycarbonyl group.

[0086] The "alkenyl group" may be linear, branched, or cyclic. The number of carbon atoms in a linear alkenyl group, not including the number of carbon atoms in the substituent, is usually preferably 2 to 30, more preferably 3 to 20. The number of carbon atoms in a branched or cyclic alkenyl group, not including the number of carbon atoms in the substituent, is usually preferably 3 to 30, more preferably 4 to 20.

[0087] The alkenyl group may have a substituent. Specific examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 2-butenyl group, a 3-butenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-hexenyl group, a 5-hexenyl group, a 7-octenyl group, and groups in which a hydrogen atom in these groups is substituted with an alkyl group, an alkyloxy group, an aryl group, or a fluorine atom.

[0088] The "cycloalkenyl group" may be a monocyclic group or a polycyclic group. The cycloalkenyl group may have a substituent. The number of carbon atoms in the cycloalkenyl group, not including the number of carbon atoms in the substituent, is usually preferably 3 to 30, and more preferably 12 to 19.

[0089] Examples of the cycloalkenyl group include unsubstituted cycloalkenyl groups such as a cyclohexenyl group, and groups in which a hydrogen atom in these groups has been substituted with an alkyl group, an alkyloxy group, an aryl group, or a fluorine atom.

[0090] Examples of the substituted cycloalkenyl group include a methylcyclohexenyl group and an ethylcyclohexenyl group.

[0091] The "alkynyl group" may be linear, branched, or cyclic. The number of carbon atoms in a linear alkynyl group, not including the number of carbon atoms in the substituent, is usually preferably 2 to 20, more preferably 3 to 20. The number of carbon atoms in a branched or cyclic alkynyl group, not including the number of carbon atoms in the substituent, is usually preferably 4 to 30, more preferably 4 to 20.

[0092] The alkynyl group may have a substituent. Specific examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, a 3-pentynyl group, a 4-pentynyl group, a 1-hexynyl group, a 5-hexynyl group, and groups in which a hydrogen atom in these groups is substituted with an alkyloxy group, an aryl group, or a fluorine atom.

[0093] The "cycloalkynyl group" may be a monocyclic group or a polycyclic group. The cycloalkynyl group may have a substituent. The number of carbon atoms in the cycloalkynyl group, not including the number of carbon atoms of the substituent, is usually preferably 4 to 30, and more preferably 12 to 19.

[0094] Examples of the cycloalkynyl group include unsubstituted cycloalkynyl groups such as a cyclohexynyl group, and groups in which the hydrogen atoms in these groups are substituted with alkyl groups, alkyloxy groups, aryl groups, or fluorine atoms.

[0095] Examples of the substituted cycloalkynyl group include a methylcyclohexynyl group and an ethylcyclohexynyl group.

[0096] The "alkylsulfonyl group" may be linear or branched. The alkylsulfonyl group may have a substituent. The number of carbon atoms in the alkylsulfonyl group, not including the number of carbon atoms in the substituent, is usually preferably 1 to 30. Specific examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, and a dodecylsulfonyl group.

[0097] The symbol "*" in a chemical formula represents a bond. A dotted line in a chemical formula also represents a bond. When a chemical formula contains two symbols "*" or two dotted lines, there is no particular limitation as to which of the two bonds the "*" and dotted line represent.

[0098] "Ink" refers to a liquid used in a coating method, and is not limited to a colored liquid. Furthermore, "coating method" encompasses methods for forming a film (layer) using a liquid substance, such as slot die coating, slit coating, knife coating, spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, screen printing, gravure printing, flexographic printing, offset printing, inkjet coating, dispenser printing, nozzle coating, and capillary coating.

[0099] The ink may be a solution or a dispersion such as an emulsion or suspension.

[0100] The "peak absorption wavelength" is a parameter determined based on the absorption peak of an absorption spectrum measured in a predetermined wavelength range, and refers to the wavelength of the absorption peak with the greatest absorbance among the absorption peaks of the absorption spectrum.

[0101] "External quantum efficiency" is also called EQE (External Quantum Efficiency), and refers to the ratio (%) of the number of electrons that can be extracted outside the photoelectric conversion element out of the number of electrons generated relative to the number of photons irradiated onto the photoelectric conversion element.

[0102] ≪Compound≫ The compound of the present disclosure is represented by the following formula (1):

[0103] [ka]

[0104] (In formula (1), D is a divalent aromatic group having two bonds, and the conjugated structure connecting the two bonds in D by the shortest distance contains three or more double bonds; L1 and L2 each independently represent a divalent aromatic group different from D, and among all units represented by L1 and L2, at least one unit has a side chain that is incapable of non-covalently interacting with an element in another adjacent unit, but does not have a side chain that is capable of non-covalently interacting with an element in another adjacent unit, and at least one other unit different from the at least one unit has a side chain that is capable of non-covalently interacting with an element in another adjacent unit, L1 and L2 may be the same or different, m is 2 or 3, and n is an integer from 1 to 3; A1 and A2 each independently represent an electron-withdrawing monovalent group having at least one aromatic ring.

[0105] The compounds of the present disclosure are capable of photoelectric conversion in the short wave infrared (SWIR) region and also have excellent solubility. The action of the compounds of the present disclosure is presumed to be as follows.

[0106] In the compound of the present disclosure, represented by formula (1), the group represented by D is a core, the groups represented by L1 and L2 are each linkers, and the groups represented by A1 and A2 are each acceptors.

[0107] In the present disclosure, the main skeleton (also referred to as the mother skeleton) refers to a chemical structure represented only by a ring structure (such as a single ring or a fused ring). In the compounds of the present disclosure, each ring structure (which may be a single ring structure or a fused ring structure) having two bonds and contained in the main skeleton chemical structure connecting A1 and A2 by the shortest distance is considered to be one unit. That is, A1, L1, D, L2, and A2 each constitute one structural unit, and the structural unit is referred to as a unit. For example, the compound of the present disclosure represented by formula (1) is a compound consisting of one A1, m L1s, one D, n L2s, and one A2, for a total of (3 + m + n) units.

[0108] In the compound of the present disclosure, among the multiple units represented by L1 and L2, at least one unit has a side chain that cannot non-covalently interact with elements in other adjacent units, and does not have a side chain that can interact. When a compound has a side chain that cannot interact, but does not have a side chain that can interact, rotation between units in the main skeleton is likely to occur, reducing the planarity (i.e., π-plane) of the main skeleton of the unit, making the compound of the present disclosure less likely to aggregate and resulting in excellent solubility. Furthermore, excellent solubility of the compound makes it easier to produce high-quality thin films. On the other hand, among the multiple units represented by L1 and L2, at least one other unit different from the at least one unit has a side chain capable of non-covalently interacting with an element in an adjacent unit. That is, the side chain capable of interacting forms a non-covalent bridge between the adjacent unit. In other words, the planarity of the main skeleton of the unit is more likely to be maintained, and the compound is more likely to J-associate, so that the compound of the present disclosure is more likely to absorb light of long wavelengths in the SWIR region. As described above, the compound of the present disclosure has both a unit having a side chain that cannot interact non-covalently with an element in another adjacent unit, and a unit having a side chain that can interact non-covalently with an element in another adjacent unit, and therefore is capable of photoelectric conversion in the SWIR region and has excellent solubility. It should be noted that the present disclosure is in no way limited to the above-mentioned presumed mechanism.

[0109] <D;コア> [Aromatic group] In formula (1), D is a divalent aromatic group having two bonds. The aromatic group in D is preferably a polycyclic aromatic group. The polycyclic aromatic group may be either a polycyclic aromatic heterocyclic group or a polycyclic aromatic carbocyclic group, and a polycyclic aromatic heterocyclic group is preferred from the viewpoint of absorbing long wavelength light. The heteroatom in the polycyclic aromatic heterocyclic group is preferably at least one selected from the group consisting of a sulfur atom, a silicon atom, a selenium atom, a nitrogen atom, and an oxygen atom, more preferably at least one selected from the group consisting of a sulfur atom, a silicon atom, a nitrogen atom, and an oxygen atom, and even more preferably a sulfur atom. That is, the aromatic group in D preferably has a sulfur-containing heterocycle, and more preferably is a sulfur-containing heterocyclic group.

[0110] From the viewpoint that the compound easily absorbs light with a long wavelength, D is preferably a polycyclic aromatic group having a fused 5- or 6-membered ring, may be a polycyclic aromatic group having a fused 5- or 6-membered ring, and is more preferably a polycyclic aromatic group having a fused 5-membered ring.

[0111] From the viewpoint of the compound being likely to absorb light of a long wavelength, D preferably has a thiophene structure, and more preferably has a thiophene structure in the main skeleton, that is, D is preferably a polycyclic aromatic group in which rings including a thiophene ring are condensed.

[0112] The number of double bonds contained in the conjugated structure connecting the two bonds in D at the shortest distance is three or more. From the viewpoint of reducing dark current in a photoelectric conversion element, the number of double bonds contained in the conjugated structure connecting the two bonds in D at the shortest distance is preferably 4 to 12, more preferably 4 to 8, even more preferably 4 to 6, still more preferably 4 or 5, and even more preferably 4.

[0113] From the viewpoint that the compound easily absorbs light of a long wavelength, D is preferably a donor group (also referred to as a group with donating properties).

[0114] [Side chain] In the formula (1), the aromatic group in D preferably has a side chain. In the present disclosure, the side chain refers to a group bonded to an atom constituting the main skeleton (such as a single ring or a fused ring). The side chain of the aromatic group in D is preferably the "side chain B" of the present disclosure.

[0115] In D, the side chain preferably has an aromatic ring or a branched chain, and more preferably has a branched chain.

[0116] In D, the aromatic group may have a plurality of side chains, and when the aromatic group has a plurality of side chains, the plurality of side chains may be the same or different.

[0117] In D, when a plurality of side chains are present, each side chain is preferably an alkyl group, a cycloalkyl group, an aryl group, an alkyloxy group, a cycloalkyloxy group, or an aryloxy group, which may have a substituent, more preferably an alkyl group or an aryl group, which may have a substituent, and even more preferably an alkyl group.

[0118] In D, the side chain preferably has 2 or more carbon atoms, more preferably 2 to 40 carbon atoms, even more preferably 3 to 30 carbon atoms, and even more preferably 3 to 20 carbon atoms.

[0119] The aromatic group in D preferably has at least one of sp3 carbon and silicon, more preferably has sp3 carbon or silicon, and even more preferably has sp3 carbon. The main skeleton of the aromatic group in D preferably has at least one of sp3 carbon and silicon, more preferably has sp3 carbon or silicon, and even more preferably has sp3 carbon.

[0120] [Chemical structure of D] In view of the compound's tendency to absorb light of a long wavelength, D in the formula (1) is preferably any one of the groups represented by the following formulas (D-1) to (D-7), and more preferably a group represented by the following formula (D-1), (D-2) or (D-6). In the following formulas (D-1) to (D-7), the symbol "*" represents a bond to L1 or L2. There are no particular limitations on which bonds the two symbols "*" in the chemical formulas represent.

[0121] [ka]

[0122] In formulas (D-1), (D-2), (D-6), and (D-7), X represents any of the groups represented by the following formulas (X-1) to (X-6): In formulas (X-1) to (X-6), the dotted lines indicate bonds to formula (D-1), (D-2), (D-6), or (D-7).

[0123] [ka]

[0124] In formulas (X-1) to (X-6), R d each independently represents a "side chain A" of the present disclosure. In formula (D-2), formula (D-5) and formula (D-7), Ar 1 and Ar 2are each independently an aromatic carbocyclic ring which may have a substituent and may be further condensed with a plurality of ring structures, or an aromatic heterocyclic ring which may have a substituent and may be further condensed with a plurality of ring structures. 1 and Ar 2 Either one of them may not be present.

[0125] The aromatic group in D preferably has a side chain, and in formulas (X-1) to (X-6), a plurality of R d At least one of these is preferably not a hydrogen atom.

[0126] In each of the formulas (X-1) to (X-6), R d If there are two, then two R d may be the same or different from each other. From the viewpoint that the compound easily absorbs light of a long wavelength, X is more preferably a group represented by formula (X-1). In formulas (X-1) to (X-6), R d are each independently preferably an alkyl group, a cycloalkyl group, an aryl group, an alkyloxy group, a cycloalkyloxy group, or an aryloxy group, which may have a substituent, more preferably an alkyl group or an aryl group, which may have a substituent, and even more preferably an alkyl group.

[0127] In formula (D-2), formula (D-5) and formula (D-7), Ar 1 and Ar 2 are each independently an aromatic carbocyclic ring which may have a substituent and may be further condensed with a plurality of ring structures, or an aromatic heterocyclic ring which may have a substituent and may be further condensed with a plurality of ring structures. 1 and Ar 2 Either one of them may not be present.

[0128] Ar 1 and Ar 2The aromatic heterocycle that can constitute the above ring includes not only a single ring and a fused ring in which the heterocycle itself exhibits aromaticity, but also a ring in which an aromatic ring is fused to a heterocycle even if the heterocycle itself does not exhibit aromaticity.

[0129] Ar 1 and Ar 2 The aromatic heterocycles that can constitute the above may each be a single ring or a fused ring. When the aromatic heterocycle is a fused ring, all of the rings constituting the fused ring may be fused rings having aromaticity, or only some of the rings may be fused rings having aromaticity. When these rings have multiple substituents, these substituents may be the same or different.

[0130] Ar 1 and Ar 2 Specific examples of aromatic carbocyclic rings that can constitute the above ring include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring, and are preferably a benzene ring and a naphthalene ring, more preferably a benzene ring and a naphthalene ring, and even more preferably a benzene ring. These rings may have a substituent.

[0131] Ar 1 and Ar 2 Specific examples of aromatic heterocycles that can constitute the above include an oxadiazole ring, a thiadiazole ring, a thiazole ring, an oxazole ring, a thiophene ring, a pyrrole ring, a phosphole ring, a furan ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a pyridazine ring, a quinoline ring, an isoquinoline ring, a carbazole ring, a dibenzophosphole ring, a phenoxazine ring, a phenothiazine ring, a dibenzoborole ring, a dibenzosilole ring, and a benzopyran ring. These rings may have a substituent.

[0132] In formulas (D-3) to (D-7), R d The definition and preferred embodiments of R in the above formulas (X-1) to (X-6) are as follows: d In formula (D-3), two R dmay be the same or different from each other.

[0133] (Example of D) Examples of formula (D-1) include groups represented by the following formulae (d-1-1) to (d-1-2). Examples of formula (D-2) include groups represented by the following formulae (d-2-1) to (d-2-12). Examples of formula (D-3) include groups represented by the following formulae (d-3-1) to (d-3-4). Examples of formula (D-4) include groups represented by the following formulae (d-4-1) to (d-4-2). Examples of formula (D-5) include groups represented by the following formulae (d-5-1) to (d-5-10). Examples of formula (D-6) include groups represented by the following formulae (d-6-1) to (d-6-2). Examples of formula (D-7) include groups represented by the following formulae (d-7-1) to (d-7-9).

[0134] In addition, in formulas (d-1-1) to (d-1-2), formulas (d-2-1) to (d-2-12), formulas (d-3-1) to (d-3-4), formulas (d-4-1) to (d-4-2), formulas (d-5-1) to (d-5-10), formulas (d-6-1) to (d-6-2), and formulas (d-7-1) to (d-7-9), R d1 The definition of R d is the same as the definition of In the following formulas (d-2-1) to (d-2-12), (d-5-1) to (d-5-10), and (d-7-1) to (d-7-9), U each independently represents CR d1 2, S, SiR d1 2, Se, NR d1 or O. Preferably, U is S. In the following formulas (d-1-1) to (d-1-2), (d-2-1) to (d-2-12), (d-3-1) to (d-3-4), (d-4-1) to (d-4-2), (d-5-1) to (d-5-10), (d-6-1) to (d-6-2), and (d-7-1) to (d-7-9), the symbol "*" represents a bond to L1 or L2.

[0135] From the viewpoint that the compound easily absorbs light of long wavelengths, D is Preferably, it is a group represented by formula (d-1-1), formula (d-2-1) to formula (d-2-3), formula (d-3-1) to formula (d-3-4), formula (d-4-1) to formula (d-4-2), formula (d-5-1), formula (d-5-3), formula (d-6-1), formula (d-6-2), or formula (d-7-2) to formula (d-7-5), More preferably, it is a group represented by formula (d-1-1), formula (d-2-2) to formula (d-2-3), formula (d-3-4), formula (d-6-1) or formula (d-6-2), More preferably, it is a group represented by formula (d-1-1), formula (d-2-3), formula (d-3-4) or formula (d-6-1).

[0136] [ka]

[0137] [ka]

[0138] [ka]

[0139] [ka]

[0140] [ka]

[0141] [ka]

[0142] [ka]

[0143] (Specific examples of D) Specific examples of D include groups represented by the following formulas. In each formula, the symbol "*" represents a bond to L1 or L2. "**" is a bond to the chemical structure shown on each left side. In the formulas, when there are multiple R d1 s, they may have the same structure or different structures from each other. When there are multiple R d1 s in the chemical structure shown on each left side and multiple examples of R d1 are also described, any of the R d1 s in the chemical structure shown on each left side is not particularly limited as to which example of R d1 it is, meaning that all combinations are included as preferred embodiments.

[0144] [Chemical formula]

[0145] [Chemical formula]

[0146] [Chemical formula]

[0147] [Chemical formula]

[0148] [Chemical formula]

[0149] <L1 and L2; linker> [Aromatic group] In formula (1), L1 and L2 are each independently a divalent aromatic group. Note that L1 and L2 do not have the same chemical structure as D and have different chemical structures.

[0150] The aromatic groups in L1 and L2 each preferably independently have a monocyclic or fused ring main skeleton. The aromatic groups in L1 and L2 may be either aromatic heterocyclic groups or aromatic carbocyclic groups, and aromatic heterocyclic groups are preferred from the viewpoint of absorbing long wavelength light. The heteroatom in the aromatic heterocyclic group is preferably at least one selected from the group consisting of sulfur atom, silicon atom, selenium atom, nitrogen atom, and oxygen atom, more preferably at least one selected from the group consisting of sulfur atom, nitrogen atom, and oxygen atom, and even more preferably sulfur atom. That is, the aromatic groups in L1 and L2 preferably have a sulfur-containing heterocycle, more preferably a sulfur-containing heterocyclic group, and even more preferably a sulfur-containing heterocyclic group.

[0151] From the viewpoint of absorbing light of long wavelengths, L1 and L2 preferably have at least a structure selected from the group consisting of a thiophene structure, a thiazole structure, and a thiadiazole structure, and may have at least one of any of the structures, may contain two or more of the same structure, or may contain two of these structures. L1 and L2 may have at least one of any of the structures selected from the group consisting of a thiophene structure, a thiazole structure, and a thiadiazole structure, or may contain a structure other than these structures. In L1 and L2, it is more preferable that the main skeleton contains a thiophene structure, and even more preferable that it consists of a thiophene structure.

[0152] In the aromatic groups having two bonds in L1 and L2, the number of double bonds contained in the conjugated structure connecting the two bonds at the shortest distance is preferably each independently 3 or less. From the viewpoint of reducing dark current in a photoelectric conversion element, the number of double bonds contained in the conjugated structure connecting the two bonds at the shortest distance is preferably each independently 1 to 3, more preferably 2 to 3, even more preferably 2 or 3, and even more preferably 2.

[0153] L1 and L2 may have the same chemical structure or different chemical structures.

[0154] Specifically, L1 and L2 are atomic groups remaining after removing two hydrogen atoms from an aromatic compound which may have a substituent. Here, the aromatic compound also includes compounds having fused rings in which multiple ring structures are fused.

[0155] The number of carbon atoms in the main skeleton of the divalent aromatic carbocyclic group represented by L1 and L2 (i.e., the number of carbon atoms in the divalent aromatic carbocyclic group not including the number of carbon atoms in the substituents) is usually preferably 2 to 30, more preferably 2 to 20, and even more preferably 2 to 10. The number of carbon atoms in the aromatic carbocyclic group including the substituents is usually preferably 2 to 100.

[0156] [Non-covalent interactions] In formula (1), of all units represented by L1 and L2, at least one unit has a side chain that is incapable of non-covalently interacting with an element in another adjacent unit, but does not have a side chain that is capable of non-covalently interacting with an element in another adjacent unit, and at least one other unit different from the at least one unit has a side chain that is capable of non-covalently interacting with an element in another adjacent unit. Note that, in the present disclosure, the adjacent units may be units on both sides, or one of the two adjacent units.

[0157] (Side chains capable of non-covalent interactions) In the present disclosure, "capable of non-covalent interaction" means Among six consecutive atoms bonded by a covalent bond, there is at least one combination of two atoms selected from the group consisting of halogen atoms, sulfur atoms, oxygen atoms, nitrogen atoms, selenium atoms, and phosphorus atoms, and The two atoms are present in one each of the main skeleton and the side chain, or in two different side chains, and This means that of the atoms present between the two atoms and the atom, the number of atoms constituting the main skeleton is four or less.

[0158] That is, in the present disclosure, a non-covalent interaction is an interaction between an atom constituting the main skeleton and an atom constituting a side chain, or an interaction between atoms present in two different side chains. Furthermore, for the two atoms to interact with each other, the distance between the two atoms must be within a certain range. Therefore, if the number of atoms constituting the main skeleton between the two atoms and the atom is four or less, the distance between the atoms is sufficient for the atoms to interact with each other.

[0159] The distance between the two atoms is preferably 5.0 Å or less, more preferably 4.0 Å or less, and even more preferably 3.5 Å or less. There is no particular lower limit to the distance between the two atoms, as long as it is greater than 0 Å. In the following examples, the distance between the two atoms was calculated using the quantum chemistry calculation program Gaussian 03, by performing ground state structural optimization by density functional theory at the B3LYP level, and using GaussVeiw 6 for the optimized ground state structure obtained using 6-31g* as the basis function.

[0160] The presence or absence of a non-covalent interaction can also be determined by X-ray crystal structure analysis. If the distance between two atoms is smaller than the van der Waals radius from a known crystal structure without the presence of a covalent bond, it can be considered that a covalent interaction exists.

[0161] The combination of two atoms is preferably a sulfur atom-oxygen atom, a sulfur atom-fluorine atom, a sulfur atom-chlorine atom, a sulfur atom-nitrogen atom, a sulfur atom-sulfur atom, a selenium atom-oxygen atom, a selenium atom-nitrogen atom, a selenium atom-fluorine atom, a selenium atom-sulfur atom, or a selenium atom-chlorine atom, more preferably a sulfur atom-oxygen atom, a sulfur atom-fluorine atom, a sulfur atom-nitrogen atom, a sulfur atom-sulfur atom, or a selenium atom-oxygen atom, and even more preferably a sulfur atom-oxygen atom, a sulfur atom-nitrogen atom, or a sulfur atom-sulfur atom.

[0162] That is, in the present disclosure, the side chain capable of non-covalent interaction preferably contains at least one atom selected from the group consisting of a halogen atom, a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, and a phosphorus atom, more preferably contains at least one atom selected from the group consisting of a sulfur atom, an oxygen atom, a fluorine atom, and a nitrogen atom, and even more preferably contains at least one atom of a sulfur atom and an oxygen atom. The side chain capable of non-covalent interaction is preferably an alkyloxy group which may have a substituent, an alkylthio group which may have a substituent, or a substituted amino group which may have a substituent, more preferably an alkyloxy group which may have a substituent or an alkylthio group which may have a substituent, and even more preferably an alkylthio group or an alkyloxy group.

[0163] The other unit adjacent to L1 or L2 having a side chain capable of non-covalent interaction preferably has an element capable of non-covalent interaction selected from the group consisting of sulfur-oxygen, sulfur-fluorine, sulfur-chlorine, sulfur-nitrogen, sulfur-sulfur, selenium-oxygen, selenium-nitrogen, selenium-fluorine, selenium-sulfur, and selenium-chlorine. The other unit adjacent to L1 or L2 having a side chain capable of non-covalent interaction preferably has at least one atom selected from the group consisting of halogen, sulfur, oxygen, nitrogen, selenium, and phosphorus.

[0164] In addition, when m is 2 and n is 1 in formula (1), the compound of the present disclosure is represented by "A1-L1-L1-D-L2-A2". That is, in this case, the unit adjacent to L1 is A1 and / or another L1, or D and / or another L1. As described above, in the present disclosure, the adjacent units may be the units on both sides, or one of the units on both sides.

[0165] From the viewpoint of enabling non-covalent interactions, when the side chain or main skeleton in L1 or L2 has a sulfur atom, it is preferable that the unit adjacent to L1 or L2 has at least one atom selected from the group consisting of an oxygen atom, a halogen atom, a sulfur atom, and a nitrogen atom. When the side chain or main skeleton in L1 or L2 has an oxygen atom, the unit adjacent to L1 or L2 preferably has at least one atom selected from the group consisting of a sulfur atom, a selenium atom, and a phosphorus atom. When the side chain or main skeleton in L1 or L2 has a fluorine atom, the unit adjacent to L1 or L2 preferably has at least one atom selected from the group consisting of a sulfur atom, a selenium atom, and a phosphorus atom. When the side chain or main skeleton in L1 or L2 has a nitrogen atom, the unit adjacent to L1 or L2 preferably has at least one atom selected from the group consisting of a sulfur atom, a selenium atom, and a phosphorus atom. When the side chain or main skeleton in L1 or L2 has a selenium atom, the unit adjacent to L1 or L2 preferably has at least one atom selected from the group consisting of a sulfur atom, a selenium atom, an oxygen atom, and a nitrogen atom. When the side chain or main skeleton in L1 or L2 contains a phosphorus atom, the unit adjacent to L1 or L2 preferably contains an oxygen atom.

[0166] At least one atom selected from the group consisting of a sulfur atom, an oxygen atom, a halogen atom, a nitrogen atom, a selenium atom, and a phosphorus atom may be contained in the main skeleton of the monocyclic or fused ring constituting the aromatic group in L1 or L2, or may be contained in a side chain bonded to the main skeleton of the monocyclic or fused ring constituting the aromatic group in L1 or L2, and may be contained in a side chain R L1 may be included in The non-covalent interaction may be formed between the main skeleton of a single ring or fused ring constituting the aromatic group in L1 or L2 and a side chain bonded to the main skeleton of a linker unit adjacent to the main skeleton; between the side chain bonded to the main skeleton of a single ring or fused ring constituting the aromatic group in L1 or L2 and a main skeleton of a unit adjacent to the side chain; or between the side chain bonded to the main skeleton of a single ring or fused ring constituting the aromatic group in L1 or L2 and a side chain bonded to the main skeleton of a unit adjacent to the side chain.

[0167] As described above, when the side chain in L1 or L2 has an element capable of non-covalently interacting with an element in an adjacent unit, a non-covalent bridge is formed between the element in L1 or L2 and the unit adjacent to L1 or L2. In other words, the planarity of the main skeleton (i.e., π plane) of the monocyclic or fused ring constituting the aromatic group in L1 or L2 is easily maintained.

[0168] (side chains that cannot form non-covalent interactions) In the present disclosure, "not capable of non-covalent interaction" means anything other than the above-mentioned "capable of non-covalent interaction." In other words, "not being able to form non-covalent interactions" means Among six consecutive atoms bonded by a covalent bond, there is no combination of at least one two atoms selected from the group consisting of halogen atoms, sulfur atoms, oxygen atoms, nitrogen atoms, selenium atoms, and phosphorus atoms; Even if the combination exists, both of the two atoms are present in the main skeleton, or Even when the above combination exists, it means that the number of atoms constituting the main skeleton is five or more among the atoms present between the above two atoms and the atom.

[0169] That is, in the present disclosure, the side chain incapable of non-covalent interaction may be any side chain that does not interact with adjacent units. The side chain incapable of non-covalent interaction may contain any of a halogen atom, a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, and a phosphorus atom, as long as it is located at a position that does not interact with adjacent units. The side chain incapable of non-covalent interaction may, for example, contain any one of a halogen atom, a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, and a phosphorus atom among six consecutive atoms bonded by a covalent bond. Preferably, the side chain does not contain any of a halogen atom, a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, and a phosphorus atom, and more preferably, the side chain is composed of carbon atoms and hydrogen atoms. The side chain that is not capable of non-covalent interaction is preferably an alkyl group or an aryl group that may have a substituent, more preferably an alkyl group or an aryl group, and even more preferably an alkyl group.

[0170] [Chemical structures of L1 and L2] From the viewpoint that the compound easily absorbs light of long wavelengths, in the formula (1), L1 and L2 are each independently preferably any of the groups represented by the following formulae (L1-1) to (L1-8), more preferably any of the groups represented by the following formulae (L1-1) to (L1-7), still more preferably any of the groups represented by the following formulae (L1-1) to (L1-4), and particularly preferably a group represented by the following formula (L1-1). In each formula, the dotted line represents a bond to an adjacent unit. That is, from the viewpoint that the compound easily absorbs light of a long wavelength, it is preferable that L1 and L2 each independently have a thiophene structure, a thienothiophene structure, a thiazole structure, or a benzothiadiazole structure.

[0171] [ka]

[0172] In formulas (L1-1) to (L1-8), R L1 are each independently a "side chain A" of the present disclosure, and R L1 is a side chain capable of non-covalent interaction, it preferably has at least one atom selected from the group consisting of a sulfur atom, an oxygen atom, a halogen atom, a nitrogen atom, a selenium atom, and a phosphorus atom. As mentioned above, R L1 has at least one atom selected from the group consisting of a sulfur atom, an oxygen atom, a halogen atom, a nitrogen atom, a selenium atom, and a phosphorus atom, and R L1 The unit adjacent to L1 or L2 having the R L1 If the element has a non-covalent interaction with R L1 and the R L1 A non-covalent bridge is formed between adjacent units of L1 or L2 having

[0173] R L1 is a side chain capable of non-covalent interactions, R L1is preferably an alkyloxy group which may have a substituent, an alkylthio group which may have a substituent, or a substituted amino group which may have a substituent, more preferably an alkyloxy group which may have a substituent or an alkylthio group which may have a substituent, and even more preferably an alkylthio group or an alkyloxy group. L1 or L2 is plural R L1 If there is at least one R L1 is preferably an alkyloxy group which may have a substituent, an alkylthio group which may have a substituent, or a substituted amino group which may have a substituent, more preferably an alkyloxy group which may have a substituent or an alkylthio group which may have a substituent, and even more preferably an alkylthio group or an alkyloxy group.

[0174] (Specific examples of L1 and L2) Specific examples of L1 and L2 include groups represented by the following formulae. In each formula, the dotted line represents a bond to the adjacent unit. "**" represents a bond to the chemical structure shown on the left side. In the formulae, R L1 When there are multiple R groups, they may be the same or different. L1 exists and R L1 When multiple examples of R are listed, any of the R in the chemical structure shown on the left side of each example may be used. L1 But R L1 There is no particular limitation on which of the above examples is used, and all combinations are included as preferred embodiments.

[0175] [ka]

[0176] [m and n] In formula (1), m is 2 or 3, and is preferably 2. In formula (1), n ​​is an integer of 1 to 3, and is preferably 1 or 2.

[0177] (L1) m The plurality of L1s in m may be the same or different. When n is 2 or 3, (L2) n The plurality of L2s in n may be the same or different.

[0178] <A1 and A2; acceptor> In formula (1), A1 and A2 are each independently an electron-withdrawing monovalent group having at least one aromatic ring. The chemical structures of A1 and A2 may be the same as or different from each other. From the viewpoint of ease of compound synthesis, it is preferable that the chemical structures of A1 and A2 are the same.

[0179] A1 and A2 are each independently preferably any of the groups represented by the following formulas (a-1) to (a-5), and more preferably the group represented by formula (a-1). In the formulas, the symbol “*” represents a bond with L1 or L2 in formula (1).

[0180] [Chemical formula]

[0181] (T) In the above formulas (a-1) to (a-5), T represents a carbocyclic ring which may have a substituent, or a heterocyclic ring which may have a substituent. The carbocyclic ring and the heterocyclic ring may be a monocyclic ring or a condensed ring. When these rings have a plurality of substituents, the plurality of substituents may be the same or different.

[0182] Examples of the carbocyclic ring represented by T which may have a substituent include aromatic carbocyclic rings, preferably aromatic carbocyclic rings. Specific examples of the carbocyclic ring represented by T which may have a substituent include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring, preferably a benzene ring, a naphthalene ring, and a phenanthrene ring, more preferably a benzene ring and a naphthalene ring, and even more preferably a benzene ring. These rings may have a substituent.

[0183] Examples of the heterocycle represented by T which may have a substituent include aromatic heterocycles, preferably aromatic heterocycles. Specific examples of the heterocycle represented by T which may have a substituent include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a thienothiophene ring, a quinoline ring, a quinoxaline ring, a pyridopyrazine ring, and a pyrazinopyrazine ring, preferably a thiophene ring, a pyridine ring, a pyrazine ring, a thiazole ring, a thienothiophene ring, a quinoxaline ring, a pyridopyrazine ring, and a pyrazinopyrazine ring, more preferably a pyridine ring, a pyrazine ring, a quinoxaline ring, a pyridopyrazine ring, and a pyrazinopyrazine ring. These rings may have a substituent.

[0184] Examples of the substituent that the carbocyclic ring or heterocyclic ring represented by T may have include a halogen atom, an alkyl group, an alkyloxy group, an aryl group, a nitro group, a cyano group, and a monovalent heterocyclic group, and are preferably a fluorine atom, a chlorine atom, an alkyloxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a nitro group, or a cyano group, and more preferably a fluorine atom, a chlorine atom, a nitro group, or a cyano group.

[0185] (X 4 , X 5 , X 6 ) X 4 , X 5 , and X 6are each independently an oxygen atom, a sulfur atom, an alkylidene group, ═C(—CN)2, or ═C(—CN)—CR a X represents a group represented by the formula: 4 , X 5 , and X 6 are preferably each independently an oxygen atom or =C(-CN)2.

[0186] R a represents an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an aromatic alkyl group having 5 to 30 carbon atoms, an aromatic alkenyl group having 5 to 30 carbon atoms, or an aromatic alkynyl group having 5 to 30 carbon atoms, and the alkyl group, alkenyl group, alkynyl group, aromatic alkyl group, aromatic alkenyl group, and aromatic alkynyl group may have a substituent and may be linear, branched, or cyclic.

[0187] (Examples of A1 and A2) In the above, preferred embodiments of T, X 4 , X 5 , and X 6 Preferred embodiments of the formula: a The preferred embodiments of A1 and A2 have been described above, but the combination of each of the preferred embodiments results in more preferred embodiments A1 and A2. Examples of A1 and A2 include groups represented by the following formulae (a-1-1) to (a-1-22), (a-2-1), (a-2-2), and (a-3-1). In each formula, the symbol "*" represents a bond to L1 or L2 in formula (1).

[0188] From the viewpoint that the compound easily absorbs light of a long wavelength, in formula (1), A1 and A2 are each independently preferably a group represented by the following formula (a-1-1), (a-1-6), (a-1-7), (a-1-14), (a-1-15) or (a-1-16), more preferably a group represented by the following formula (a-1-1), (a-1-15) or (a-1-16), and even more preferably a group represented by the following formula (a-1-1).

[0189] [ka]

[0190] [ka]

[0191] In formulas (a-1-1) to (a-1-22), (a-2-1), (a-2-2), and (a-3-1), R a1 ~R a9 each independently represents a hydrogen atom or a substituent. R a1 ~R a9 are preferably each independently a hydrogen atom, a halogen atom, a cyano group, a straight-chain alkyl group, a branched alkyl group, a silyl group, an ester group, an alkyloxy group, a thioalkyl group, a haloalkyl group, an alkene group, an alkyne group, a cyano-substituted alkyl group, a nitro-substituted alkyl group, a hydroxy-substituted alkyl group, or a keto-substituted alkyl group, more preferably each independently a hydrogen atom, a halogen atom, an alkyloxy group, a cyano group, or an alkyl group, and even more preferably each independently a hydrogen atom, a fluorine atom, a chlorine atom, or a cyano group.

[0192] The linear alkyl group preferably has 1 to 30 carbon atoms, the branched alkyl group preferably has 3 to 30 carbon atoms, the silyl group preferably has 1 to 30 carbon atoms, the ester group preferably has 2 to 30 carbon atoms, the alkyloxy group preferably has 1 to 30 carbon atoms, the thioalkyl group preferably has 1 to 30 carbon atoms, the haloalkyl group preferably has 1 to 30 carbon atoms, the alkene group preferably has 2 to 30 carbon atoms, the alkyne group preferably has 2 to 30 carbon atoms, the cyano-substituted alkyl group preferably has 2 to 30 carbon atoms, the nitro-substituted alkyl group preferably has 1 to 30 carbon atoms, the hydroxy-substituted alkyl group preferably has 1 to 30 carbon atoms, and the keto-substituted alkyl group preferably has 3 to 30 carbon atoms.

[0193] Examples of A1 and A2 include groups represented by the following formulae: In each formula, the symbol "*" represents a bond to L1 or L2 in formula (1).

[0194] [ka]

[0195] <Specific Examples of Compounds of the Present Disclosure> In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. The compounds of the present disclosure are represented by formula (1): D is any of the groups represented by formulae (D-1) to (D-7), L1 and L2 each independently represent any of groups represented by formula (L1-1) to formula (L1-8), Among all the units represented by L1 and L2, at least one unit has a side chain that is incapable of non-covalently interacting with an element in another adjacent unit, but does not have a side chain that is capable of non-covalently interacting with an element in another adjacent unit, and at least one other unit different from the at least one unit has a side chain that is capable of non-covalently interacting with an element in another adjacent unit, m is 2 or 3, and n is an integer from 1 to 3; It is preferable that A1 and A2 each independently represent any of the groups represented by formulae (a-1) to (a-5).

[0196] The compounds of the present disclosure are represented by formula (1): D is a group represented by formula (d-1-1), formula (d-2-3), formula (d-3-4), or formula (d-6-1), L1 and L2 each independently represent any of the groups represented by formula (L1-1) to formula (L1-4), Among all units represented by L1 and L2, at least one unit has only an alkyl group or an aryl group as a side chain, and at least one other unit different from the at least one unit has an alkylthio group or an alkyloxy group; m is 2, n is 1 or 2, It is more preferable that A1 and A2 are each independently any group represented by Formula (a-1) to Formula (a-5).

[0197] More preferable specific examples of the compound of the present disclosure include compounds represented by the following formula.

[0198] [Chemical formula]

[0199] [Chemical formula]

[0200] ≪Composition≫ The composition of the present disclosure includes a p-type semiconductor material and an n-type semiconductor material, and it is preferable that the n-type semiconductor material contains the compound of the present disclosure.

[0201] The composition of the present disclosure may contain components other than the p-type semiconductor material and the n-type semiconductor material. Further, the composition of the present disclosure may contain only the compound of the present disclosure as the n-type semiconductor material, or may contain other compounds other than the compound of the present disclosure. Other compounds that may be included as the n-type semiconductor material may be low molecular weight compounds or high molecular weight compounds.

[0202] <n-type semiconductor material> Examples of the low molecular weight compound that may be included as the n-type semiconductor material include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, and phenanthrene derivatives such as bathocuproine.

[0203] Examples of polymer compounds that can be included as n-type semiconductor materials include polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having an aromatic amine structure in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylenevinylene and derivatives thereof, polythienylenevinylene and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, and polyfluorene and derivatives thereof.

[0204] The other compound may also be a fullerene derivative.

[0205] Here, the fullerene derivative is fullerene (C 60 Fullerene, C 70 Fullerene, C 76 Fullerene, C 78 Fullerene and C 84 It refers to a compound in which at least a part of a fullerene (C) is modified. In other words, it refers to a compound having one or more groups added to the fullerene skeleton. Hereinafter, C 60 Fullerene derivatives are called "C 60 "Fullerene derivatives" and C 70 Fullerene derivatives are called "C 70 They are sometimes called "fullerene derivatives."

[0206] The fullerene derivative that can be included as the n-type semiconductor material is not particularly limited as long as it does not impair the objective of the present disclosure.

[0207] C that can be contained as an n-type semiconductor material 60 Specific examples of fullerene derivatives include the following compounds.

[0208] [ka]

[0209] Above C 60In the formula of the fullerene derivative, the definition of R is as described in paragraph number

[0203] of International Publication No. 2023 / 100844. When there are multiple Rs, the multiple Rs may be the same as or different from each other.

[0210] C 70 Examples of the fullerene derivative include the following compounds.

[0211]

Chemical formula

[0212] <p-type semiconductor material> The p-type semiconductor material is preferably a polymer compound having a predetermined weight average molecular weight in terms of polystyrene.

[0213] Here, the weight average molecular weight in terms of polystyrene means the weight average molecular weight calculated using gel permeation chromatography (GPC) with a standard sample of polystyrene.

[0214] From the viewpoint of particularly improving the solubility in a solvent, the weight average molecular weight of the p-type semiconductor material in terms of polystyrene is preferably 3000 or more and 500000 or less.

[0215] The p-type semiconductor material is preferably a π-conjugated polymer compound (also referred to as a D-A type conjugated polymer compound) containing a donor structural unit (also referred to as a D structural unit) and an acceptor structural unit (also referred to as an A structural unit). Whether it is a donor structural unit or an acceptor structural unit can be relatively determined from the energy levels of HOMO or LUMO.

[0216] Here, the donor structural unit is a structural unit with excessive π electrons, and the acceptor structural unit is a structural unit lacking π electrons.

[0217] In the present disclosure, structural units that can constitute a p-type semiconductor material include structural units in which a donor structural unit and an acceptor structural unit are directly bonded, as well as structural units in which a donor structural unit and an acceptor structural unit are bonded via any suitable spacer (group or structural unit).

[0218] Examples of p-type semiconductor materials that are polymer compounds include polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives containing an aromatic amine structure in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylenevinylene and derivatives thereof, polythienylenevinylene and derivatives thereof, and polyfluorene and derivatives thereof.

[0219] The p-type semiconductor material is preferably a polymer compound containing at least one selected from the group consisting of a constitutional unit represented by the following formula (3) and a constitutional unit represented by the following formula (4). The constitutional unit represented by the following formula (3) is usually preferably a donor constitutional unit. The constitutional unit represented by the following formula (4) is usually preferably an acceptor constitutional unit.

[0220] [ka]

[0221] -Formula (3)- In formula (3), Ar 3 and Ar 4 each independently represents a trivalent aromatic heterocyclic group which may have a substituent, and Z represents any of the groups represented by the following formulae (Z-1) to (Z-7).

[0222] [ka]

[0223] In formulas (Z-1) to (Z-7), R is each independently hydrogen atoms, halogen atoms, an alkyl group which may have a substituent, an optionally substituted cycloalkyl group, an optionally substituted aryl group; an alkyloxy group which may have a substituent; an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an alkylthio group which may have a substituent; an optionally substituted cycloalkylthio group, an optionally substituted arylthio group; an optionally substituted monovalent heterocyclic group, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; an alkenyl group which may have a substituent; an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group; an optionally substituted cycloalkynyl group, an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, a cyano group, or represents a nitro group, In each of formulas (Z-1) to (Z-7), when there are two Rs, the two Rs may be the same or different.

[0224] Ar 3 and Ar 4The aromatic heterocycle that can constitute the above ring includes not only a single ring and a fused ring in which the heterocycle itself exhibits aromaticity, but also a ring in which an aromatic ring is fused to a heterocycle even if the heterocycle itself does not exhibit aromaticity.

[0225] Ar 3 and Ar 4 The aromatic heterocycles that can constitute the above may each be a single ring or a fused ring. When the aromatic heterocycle is a fused ring, all of the rings constituting the fused ring may be fused rings having aromaticity, or only some of the rings may be fused rings having aromaticity. When these rings have multiple substituents, these substituents may be the same or different.

[0226] Ar 3 and Ar 4 Specific examples of aromatic carbocyclic rings that can constitute the above ring include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring, and are preferably a benzene ring and a naphthalene ring, more preferably a benzene ring and a naphthalene ring, and even more preferably a benzene ring. These rings may have a substituent.

[0227] Specific examples of the aromatic heterocycle include the ring structures of the compounds already described as aromatic heterocyclic compounds, such as an oxadiazole ring, a thiadiazole ring, a thiazole ring, an oxazole ring, a thiophene ring, a pyrrole ring, a phosphole ring, a furan ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a pyridazine ring, a quinoline ring, an isoquinoline ring, a carbazole ring, a dibenzophosphole ring, a phenoxazine ring, a phenothiazine ring, a dibenzoborole ring, a dibenzosilole ring, and a benzopyran ring. These rings may have a substituent.

[0228] The constitutional unit represented by formula (3) is preferably a constitutional unit represented by the following formula (3-1), (3-2) or (3-3).

[0229] [ka]

[0230] In formulas (3-1), (3-2) and (3-3), Ar 3 , Ar 4 The definitions of and R are respectively defined as Ar in formula (3). 3 , Ar 4 and the definition of R above.

[0231] Specific examples of suitable structural units represented by formula (3) include structural units represented by the following formulas.

[0232] [ka]

[0233] In the above formula, the definition of R is the same as the definition of R above. When there are two R's, the two R's may be the same or different.

[0234] More specific examples of preferred structural units represented by formula (3) include structural units represented by the following formulas.

[0235] [ka]

[0236] -Formula (4)- In formula (4), Ar 5 represents a divalent aromatic heterocyclic group.

[0237] Ar 5 The divalent aromatic heterocyclic group represented by the following formula (I) preferably has 2 to 60 carbon atoms, more preferably 4 to 60 carbon atoms, and even more preferably 4 to 20 carbon atoms.

[0238] Ar 5 The divalent aromatic heterocyclic group represented by the formula (Ar) may have a substituent. 5Examples of the substituent that the divalent aromatic heterocyclic group represented by the formula (I) may have include a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted monovalent heterocyclic group, an optionally substituted substituted amino group, an optionally substituted acyl group, an optionally substituted imine residue, an optionally substituted amide group, an optionally substituted acid imide group, an optionally substituted substituted oxycarbonyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a cyano group, and a nitro group.

[0239] As the constitutional unit represented by formula (4), constitutional units represented by the following formulae (4-1) to (4-10) are preferred.

[0240] [ka]

[0241] In the formulas (4-1) to (4-10), R is defined as above. X 2 and X 3 each independently represents an oxygen atom or a sulfur atom. Z 1 and Z 2 each independently represents a group represented by ═C(R)— or a nitrogen atom. When there are two R's, the two R's may be the same or different.

[0242] X in formulas (4-1) to (4-10) 2 and X 3 are preferably sulfur atoms from the viewpoint of availability of raw material compounds.

[0243] As described above, the structural units represented by formulae (4-1) to (4-10) can generally function as acceptor structural units. However, without being limited thereto, the structural units represented by formulae (4-4), (4-5), and (4-7) in particular can also function as donor structural units.

[0244] The p-type semiconductor material is preferably a π-conjugated polymer compound that includes a structural unit containing a thiophene skeleton and that includes a π-conjugated system.

[0245] Ar 5 Specific examples of the divalent aromatic heterocyclic group represented by the formula (101) to the formula (191) described in paragraphs

[0255] to

[0258] of WO 2023 / 100844. These groups may further have a substituent.

[0246] The polymer compound that is a p-type semiconductor material is preferably a π-conjugated polymer compound that includes a constitutional unit represented by formula (3) as a donor constitutional unit and a constitutional unit represented by formula (4) as an acceptor constitutional unit.

[0247] In a polymer compound that is a p-type semiconductor material, the polymer compound that is a p-type semiconductor material may contain, as a structural unit, a structure in which the structural unit represented by formula (3) and the structural unit represented by formula (4) already explained are linked together.

[0248] The polymer compound that is a p-type semiconductor material may contain two or more types of constitutional units represented by formula (3), or may contain two or more types of constitutional units represented by formula (4).

[0249] For example, from the viewpoint of improving solubility in a solvent, the polymer compound that is a p-type semiconductor material may contain a constitutional unit represented by formula (IV) described in paragraphs

[0263] to

[0277] of WO 2023 / 100844.

[0250] The constitutional unit represented by formula (IV) is preferably a constitutional unit represented by the following formula (IV-1) or formula (IV-2).

[0251] [ka]

[0252] In formula (IV-1) and formula (IV-2), R is defined as the same as the above definition of R. The two R may be the same or different.

[0253] The structural unit constituting the polymer compound that is a p-type semiconductor material may be a structural unit in which two or more structural units selected from the above structural units are combined and linked together.

[0254] When a polymer compound serving as a p-type semiconductor material contains a constitutional unit represented by formula (3) and / or a constitutional unit represented by formula (4), the total amount of the constitutional unit represented by formula (3) and the constitutional unit represented by formula (4) is usually preferably 20 mol % to 100 mol %, assuming the amount of all constitutional units contained in the polymer compound as 100 mol %. From the viewpoint of improving the charge transport properties as a p-type semiconductor material, it is more preferably 40 mol % to 100 mol %, and even more preferably 50 mol % to 100 mol %.

[0255] Specific examples of polymer compounds that are p-type semiconductor materials include polymer compounds represented by the following formulas (P-1) to (P-19).

[0256] [ka]

[0257] [ka]

[0258] [ka]

[0259] [ka]

[0260] [ka]

[0261] [ka]

[0262] [ka]

[0263] In the above formula, R is defined as the above definition of R. Multiple R may be the same or different.

[0264] When the polymer compound exemplified above is used as a p-type semiconductor material, it is possible to suppress a decrease in EQE due to heat treatment during a manufacturing process of a photoelectric conversion element or a process of incorporating the photoelectric conversion element into a device, or the like, or to further improve the EQE, thereby improving the heat resistance of the photoelectric conversion element.

[0265] Ink The ink of the present disclosure preferably contains the compound of the present disclosure and a solvent. The ink of the present disclosure also preferably contains the p-type semiconductor material, n-type semiconductor material, and solvent of the present disclosure. Since the ink of the present disclosure contains the compound of the present disclosure as the n-type semiconductor material, it is preferably an ink for forming an active layer of a photoelectric conversion element, and more preferably an ink for forming a bulk heterojunction active layer.

[0266] According to the ink of the present disclosure, by containing a p-type semiconductor material and a compound of the present disclosure, it is possible to suppress a decrease in EQE or to further improve the EQE due to heat treatment during, for example, a manufacturing process of a photoelectric conversion element or a process of incorporating the photoelectric conversion element into a device, thereby improving heat resistance.

[0267] The solvent may be, for example, a mixed solvent that combines the first and second solvents described below. Specifically, when the ink contains two or more solvents, it preferably contains a main solvent (first solvent) that is the main component, and an additional solvent (second solvent) that is added to improve solubility, etc. The solvent may be the first solvent alone.

[0268] The first and second solvents and their combinations that can be suitably used in the ink for forming the active layer will be described below.

[0269] <First solvent> The first solvent is preferably a solvent in which the p-type semiconductor material can be dissolved, and is preferably an aromatic hydrocarbon.

[0270] Examples of aromatic hydrocarbons include toluene, xylenes (e.g., o-xylene, m-xylene, p-xylene), chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, trimethylbenzenes (e.g., mesitylene, 1,2,4-trimethylbenzene (pseudocumene)), butylbenzenes (e.g., n-butylbenzene, sec-butylbenzene, tert-butylbenzene), methylnaphthalenes (e.g., 1-methylnaphthalene), 1-chloronaphthalene, bromobenzene, tetralin, and indane.

[0271] The first solvent may be composed of one type of aromatic hydrocarbon or two or more types of aromatic hydrocarbons, but is preferably composed of one type of aromatic hydrocarbon.

[0272] The first solvent is preferably one or more selected from the group consisting of toluene, o-xylene, m-xylene, p-xylene, mesitylene, chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, methylnaphthalene, 1-chloronaphthalene, bromobenzene, tetralin, and indan, and more preferably toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, o-dichlorobenzene, mesitylene, 1,2,4-trichlorobenzene, 1,2,4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, methylnaphthalene, 1-chloronaphthalene, bromobenzene, tetralin, or indan.

[0273] <Second solvent> The second solvent is preferably selected from the viewpoint of facilitating the production process and further improving the properties of the photoelectric conversion element. Examples of the second solvent include ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, acetophenone, and propiophenone; ester solvents such as ethyl acetate, butyl acetate, phenyl acetate, ethyl cellosolve acetate, methyl benzoate, butyl benzoate, and benzyl benzoate; ether solvents such as 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, and 1-methoxynaphthalene; 1,2,4-trimethylbenzene, 1,2,4-trichlorobenzene, tetralin, 2-isopropylphenol, 2-isopropyl-5-methylanisole, and bromobenzene.

[0274] The second solvent is preferably, for example, acetophenone, propiophenone, butyl benzoate, or methyl benzoate from the viewpoint of increasing wavelength.

[0275] <Combination of first and second solvents> Examples of suitable combinations of the first solvent and the second solvent include combinations of tetralin and ethyl benzoate, tetralin and propyl benzoate, tetralin and butyl benzoate, o-dichlorobenzene and 1,2-dimethoxybenzene, and o-dichlorobenzene and methyl benzoate, and more preferably combinations of tetralin and butyl benzoate, and o-dichlorobenzene and 1,2-dimethoxybenzene.

[0276] <Mass ratio of first solvent to second solvent> The mass ratio of the first solvent, which is the main solvent, to the second solvent, which is the additive solvent (first solvent:second solvent), is preferably in the range of 50:50 to 99:1, from the viewpoint of further improving the solubility of the p-type semiconductor material and the n-type semiconductor material.

[0277] <any other solvent> The solvent may contain any other solvent in addition to the first and second solvents. When the total mass of all solvents contained in the ink is taken as 100 mass%, the content of the other solvent is preferably 5 mass% or less, more preferably 3 mass% or less, and even more preferably 1 mass% or less. The other solvent is preferably a solvent with a boiling point higher than that of the second solvent.

[0278] In addition to the first solvent, the second solvent, the p-type semiconductor material, and the n-type semiconductor material, the ink may contain optional components such as a surfactant, an ultraviolet absorber, an antioxidant, a sensitizer for increasing the function of generating charges by absorbed light, and a light stabilizer for increasing stability against ultraviolet light, to the extent that the objects and effects of the present disclosure are not impaired.

[0279] The concentrations of the p-type semiconductor material and the n-type semiconductor material in the ink can be set to any suitable concentration within a range that does not impair the object of the present disclosure, taking into consideration factors such as solubility in the solvent.

[0280] The mass ratio of the "p-type semiconductor material" to the "n-type semiconductor material" in the ink is usually preferably in the range of 1 / 0.1 to 1 / 10, more preferably in the range of 1 / 0.5 to 1 / 2, and even more preferably 1 / 1.5.

[0281] The total content of the "p-type semiconductor material" and "n-type semiconductor material" in the ink is usually preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.25% by mass or more. The total content of the "p-type semiconductor material" and "n-type semiconductor material" in the ink is usually preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 7.50% by mass or less.

[0282] The content of the "p-type semiconductor material" in the ink is usually preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.10% by mass or more. The content of the "p-type semiconductor material" in the ink is usually preferably 10% by mass or less, more preferably 5.00% by mass or less, and even more preferably 3.00% by mass or less.

[0283] The content of the "n-type semiconductor material" in the ink is usually preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.15% by mass or more. The content of the "n-type semiconductor material" in the ink is usually preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 4.50% by mass or less.

[0284] The ink can be prepared by a known method, for example, by mixing a first solvent or a first solvent and a second solvent to prepare a mixed solvent, and then adding a p-type semiconductor material and an n-type semiconductor material to the resulting mixed solvent, or by adding a p-type semiconductor material to the first solvent, adding an n-type semiconductor material to the second solvent, and then mixing the first solvent and the second solvent to which each material has been added.

[0285] The first and second solvents and the p-type and n-type semiconductor materials may be mixed by heating to a temperature equal to or lower than the boiling point of the solvent.

[0286] After mixing the first and second solvents with the p-type and n-type semiconductor materials, the resulting mixture may be filtered using a filter, and the resulting filtrate may be used as a filtrate. The filter may be, for example, a filter made of a fluororesin such as polytetrafluoroethylene (PTFE).

[0287] <Photoelectric conversion element> The photoelectric conversion element of the present disclosure includes an anode, a cathode, and an active layer provided between the anode and the cathode and including a p-type semiconductor material and an n-type semiconductor material, and the n-type semiconductor material preferably includes the compound of the present disclosure. Preferred aspects of the p-type semiconductor material and the n-type semiconductor material are as described above.

[0288] According to the photoelectric conversion element of the present disclosure, by having the above-mentioned configuration, it is possible to suppress a decrease in external quantum efficiency due to heat treatment during the manufacturing process of the photoelectric conversion element or the process of incorporating the photoelectric conversion element into a device to which the photoelectric conversion element is applied, and to effectively improve heat resistance.

[0289] Here, an example of a configuration that the photoelectric conversion element of the present disclosure can take will be described. Figure 1 is a diagram schematically showing the configuration of the photoelectric conversion element of the present disclosure.

[0290] 1, a photoelectric conversion element 10 is provided on a support substrate 11. The photoelectric conversion element 10 includes an anode 12 provided in contact with the support substrate 11, a hole transport layer 13 provided in contact with the anode 12, an active layer 14 provided in contact with the hole transport layer 13, an electron transport layer 15 provided in contact with the active layer 14, and a cathode 16 provided in contact with the electron transport layer 15. In this configuration example, a sealing member 17 is further provided in contact with the cathode 16.

[0291] Another example of a photoelectric conversion element includes a cathode provided in contact with a support substrate, an electron transport layer provided in contact with the cathode, an active layer provided in contact with the electron transport layer, a hole transport layer provided in contact with the active layer, and an anode provided in contact with the hole transport layer. In this example, a sealing member is further provided in contact with the anode.

[0292] Components that can be included in the photoelectric conversion element of the present disclosure will be specifically described below.

[0293] <Substrate> A photoelectric conversion element is usually formed on a substrate (support substrate). It may also be sealed with a further substrate (sealing substrate). One of a pair of electrodes, consisting of an anode and a cathode, is usually formed on the substrate. The material of the substrate is not particularly limited, as long as it is a material that is not chemically changed, especially when a layer containing an organic compound is formed.

[0294] Examples of materials for the substrate include glass, plastic, polymer film, and silicon. When an opaque substrate is used, it is preferable that the electrode on the opposite side to the electrode provided on the opaque substrate side (in other words, the electrode on the side farther from the opaque substrate) be a transparent or semi-transparent electrode.

[0295] <Electrode> The photoelectric conversion element includes a pair of electrodes, an anode and a cathode, at least one of which is preferably a transparent or semi-transparent electrode to allow light to enter.

[0296] Examples of transparent or semitransparent electrode materials include conductive metal oxide films and semitransparent metal thin films. Specific examples include conductive materials such as indium oxide, zinc oxide, tin oxide, and their composites, such as indium tin oxide (ITO), indium zinc oxide (IZO), and NESA, as well as gold, platinum, silver, and copper. Preferred transparent or semitransparent electrode materials include ITO, IZO, and tin oxide. Alternatively, transparent conductive films made of organic compounds such as polyaniline and its derivatives, polythiophene and its derivatives, etc. may be used as electrodes. The transparent or semitransparent electrode may be an anode or a cathode.

[0297] As long as one electrode of a pair of electrodes is transparent or translucent, the other electrode may have low optical transparency. Examples of materials for electrodes with low optical transparency include metals and conductive polymers. Specific examples of materials for electrodes with low optical transparency include metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, and ytterbium, alloys of two or more of these metals, alloys of one or more of these metals with one or more metals selected from the group consisting of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin, graphite, graphite intercalation compounds, polyaniline and its derivatives, and polythiophene and its derivatives. The alloys include magnesium-silver alloys, magnesium-indium alloys, magnesium-aluminum alloys, indium-silver alloys, lithium-aluminum alloys, lithium-magnesium alloys, lithium-indium alloys, and calcium-aluminum alloys.

[0298] <Active layer> The active layer included in the photoelectric conversion element of the present disclosure is assumed to have a bulk heterojunction structure and includes a p-type semiconductor material and an n-type semiconductor material, and the active layer includes the compound of the present disclosure as the n-type semiconductor material.

[0299] The thickness of the active layer is not particularly limited. The thickness of the active layer can be any suitable thickness taking into consideration the balance between suppressing dark current and extracting the generated photocurrent. In particular, from the viewpoint of further reducing dark current, the thickness of the active layer is preferably 100 nm or more, more preferably 150 nm or more, and even more preferably 200 nm or more. In addition, the thickness of the active layer is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 1 μm or less.

[0300] <Middle class> As shown in FIG. 1, the photoelectric conversion element of the present disclosure preferably includes an intermediate layer (buffer layer) such as a charge transport layer (electron transport layer, hole transport layer, electron injection layer, hole injection layer) as a component for improving properties such as photoelectric conversion efficiency.

[0301] Examples of materials used for the intermediate layer include metals such as calcium, inorganic oxide semiconductors such as molybdenum oxide and zinc oxide, and a mixture (PEDOT:PSS) of PEDOT (poly(3,4-ethylenedioxythiophene)) and PSS (poly(4-styrenesulfonate)).

[0302] As shown in Figure 1, the photoelectric conversion element preferably includes a hole transport layer between the anode and the active layer. The hole transport layer has the function of transporting holes from the active layer to the electrode.

[0303] The hole transport layer provided in contact with the anode may be particularly referred to as a hole injection layer. The hole transport layer (hole injection layer) provided in contact with the anode has the function of promoting the injection of holes into the anode. The hole transport layer (hole injection layer) may be in contact with the active layer.

[0304] The hole transport layer includes a hole transport material. Examples of the hole transport material include polythiophene and its derivatives, aromatic amine compounds, polymer compounds containing structural units having aromatic amine residues, CuSCN, CuI, NiO, tungsten oxide (WO), and molybdenum oxide (MoO). Examples of hole transport material products include Avantama P-10 and P-21.

[0305] The intermediate layer can be formed by any suitable conventionally known forming method, such as a vacuum deposition method or a coating method similar to the method for forming the active layer.

[0306] The photoelectric conversion element of the present disclosure preferably has a configuration in which the intermediate layer is an electron transport layer, and the substrate (support substrate), anode, hole transport layer, active layer, electron transport layer, and cathode are laminated in this order so as to be in contact with each other.

[0307] As shown in Figure 1, the photoelectric conversion element of the present disclosure preferably includes an electron transport layer as an intermediate layer between the cathode and the active layer. The electron transport layer has a function of transporting electrons from the active layer to the cathode. The electron transport layer may be in contact with the cathode. The electron transport layer may be in contact with the active layer.

[0308] The electron transport layer provided in contact with the cathode is sometimes called an electron injection layer. The electron transport layer (electron injection layer) provided in contact with the cathode has the function of promoting the injection of electrons generated in the active layer into the cathode.

[0309] The electron transport layer contains an electron transporting material, such as polyalkyleneimine and its derivatives, polymer compounds containing a fluorene structure, metals such as calcium, and metal oxides.

[0310] Examples of polyalkyleneimines and derivatives thereof include polymers obtained by polymerizing one or more alkyleneimines having 2 to 8 carbon atoms, such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, and octyleneimine, in particular alkyleneimines having 2 to 4 carbon atoms, by a conventional method, as well as polymers obtained by reacting these with various compounds to chemically modify them. Preferred polyalkyleneimines and derivatives thereof are polyethyleneimine (PEI) and ethoxylated polyethyleneimine (PEIE).

[0311] Examples of polymer compounds containing a fluorene structure include poly[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-ortho-2,7-(9,9'-dioctylfluorene)] (PFN) and PFN-P2.

[0312] Examples of metal oxides include zinc oxide, gallium-doped zinc oxide, aluminum-doped zinc oxide, titanium oxide, and niobium oxide. Metal oxides containing zinc are preferred, with zinc oxide being particularly preferred. Examples of metal oxide products include Avantama's N-10, N-11, N-12, N-13, N-20X, and N-21X, and Infinity PV's ZnO, ZnO (2.8%), ZnO (5.6%), and Doped ZnO.

[0313] Other examples of electron transporting materials include poly(4-vinylphenol) and perylene diimide.

[0314] <Sealing member> The photoelectric conversion element of the present disclosure preferably further includes a sealing member and is sealed with such a sealing member to form a sealed body. Any suitable conventionally known member can be used as the sealing member, and an example of the sealing member is a combination of a glass substrate (sealing substrate) and a sealing material (adhesive) such as a UV-curable resin.

[0315] The sealing member may be a sealing layer having a structure of one or more layers. Examples of layers constituting the sealing layer include a gas barrier layer and a gas barrier film.

[0316] The sealing layer is preferably formed from a material that has a moisture-blocking property (water vapor barrier property) or an oxygen-blocking property (oxygen barrier property). Suitable examples of materials for the sealing layer include organic materials such as trifluoropolyethylene, polytrifluorochloroethylene (PCTFE), polyimide, polycarbonate, polyethylene terephthalate, alicyclic polyolefin, and ethylene-vinyl alcohol copolymer, and inorganic materials such as silicon oxide, silicon nitride, aluminum oxide, and diamond-like carbon.

[0317] The sealing member is generally made of a material that can withstand the heat treatment that is carried out when the photoelectric conversion element is incorporated into a device, for example, the application example described below.

[0318] <Applications of photoelectric conversion elements> The photoelectric conversion element of the present disclosure may be used as a photodetector element or a solar cell. The photoelectric conversion element of the present disclosure may be used immediately after production, or may be left to stand or stored after production and then used. More specifically, the photoelectric conversion element of the present disclosure can generate a photocurrent by irradiating light from the transparent or semitransparent electrode side while a voltage (reverse bias voltage) is applied between the electrodes, and can function as a photodetector (photosensor). Furthermore, by integrating a plurality of photodetectors, the element can also be used as an image sensor. Thus, the photoelectric conversion element of the present disclosure can be particularly suitably used as a photodetector.

[0319] Furthermore, the photoelectric conversion element of the present disclosure can generate photovoltaic power between the electrodes when irradiated with light, and can operate as a solar cell. A solar cell module can also be formed by integrating a plurality of photoelectric conversion elements.

[0320] The photoelectric conversion element of the present disclosure can be suitably applied as a photodetector element to detectors provided in various electronic devices such as workstations, personal computers, mobile information terminals, access control systems, digital cameras, and medical equipment.

[0321] The photoelectric conversion element of the present disclosure can be suitably applied to the image detection units (e.g., image sensors such as X-ray sensors) for solid-state imaging devices such as X-ray imaging devices and CMOS image sensors, detection units (e.g., near-infrared sensors) of biometric information authentication devices that detect predetermined features of a part of a living body, such as fingerprint detection units, face detection units, vein detection units, and iris detection units, and detection units of optical biosensors such as pulse oximeters, which are included in the above-mentioned exemplary electronic devices.

[0322] The photoelectric conversion element of the present disclosure includes the compound of the present disclosure, and therefore operates at a longer wavelength than conventional elements.

[0323] <Method of manufacturing photoelectric conversion element> The method for manufacturing the photoelectric conversion element of the present disclosure is not particularly limited. The photoelectric conversion element of the present disclosure can be manufactured by combining a suitable forming method with materials selected for forming the components. Hereinafter, a method for manufacturing a photoelectric conversion element having a configuration in which a substrate (support substrate), an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode are in contact with each other in this order will be described.

[0324] (Process of preparing the substrate) In this step, for example, a support substrate provided with an anode is prepared. Alternatively, a substrate provided with a conductive thin film formed from the electrode material already described can be purchased from the market, and the conductive thin film can be patterned to form an anode as needed, thereby preparing a support substrate provided with an anode. When an anode is formed on a support substrate, the method for forming the anode is not particularly limited. The anode can be formed on the structure where the anode is to be formed (e.g., support substrate, active layer, hole transport layer) by any suitable conventional method such as vacuum deposition, sputtering, ion plating, plating, or coating using the materials already described.

[0325] (Hole transport layer forming step) The method for manufacturing a photoelectric conversion element may include a step of forming a hole transport layer (hole injection layer) provided between the active layer and the anode. The method for forming the hole transport layer is not particularly limited. From the viewpoint of simplifying the step of forming the hole transport layer, it is preferable to form the hole transport layer by any suitable conventional coating method. The hole transport layer can be formed, for example, by a coating method using a coating liquid containing the material for the hole transport layer and a solvent already described above, or by a vacuum deposition method.

[0326] (Active layer formation process) In the method for producing a photoelectric conversion element of the present disclosure, an active layer is formed on a hole transport layer. The active layer, which is a main component, can be formed by any suitable conventionally known formation process. The active layer is preferably produced by a coating method using an ink (coating liquid). Preferred embodiments of the ink are as described above. Steps (i) and (ii) included in the process for forming the active layer, which is a main component of the present disclosure, are described below.

[0327] Process (i) Any suitable coating method can be used as a method for applying the ink to a coating target, and examples of the coating method include slit coating, knife coating, spin coating, microgravure coating, gravure coating, bar coating, inkjet printing, nozzle coating, and capillary coating, more preferably slit coating, spin coating, capillary coating, and bar coating, and even more preferably slit coating or spin coating.

[0328] The ink for forming an active layer is applied to a target selected depending on the photoelectric conversion element and its manufacturing method. The ink for forming an active layer can be applied to a functional layer of the photoelectric conversion element, in which an active layer may be present, during the manufacturing process of the photoelectric conversion element. Therefore, the target to which the ink for forming an active layer is applied varies depending on the layer structure of the photoelectric conversion element to be manufactured and the order of layer formation. For example, if the photoelectric conversion element has a layer structure in which a substrate, an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode are stacked, and the layer listed on the left is formed first, the target to which the ink for forming an active layer is applied will be the hole transport layer. Furthermore, for example, if the photoelectric conversion element has a layer structure in which a substrate, a cathode, an electron transport layer, an active layer, a hole transport layer, and an anode are stacked, and the layer listed on the left is formed first, the target to which the ink for forming an active layer is applied will be the electron transport layer.

[0329] Process (ii) Any suitable method can be used to remove the solvent from the ink coating, i.e., to remove the solvent from the coating and solidify it. Examples of the method for removing the solvent include a method of directly heating using a hot plate in an inert gas atmosphere such as nitrogen gas, hot air drying, infrared heating drying, flash lamp annealing drying, and reduced pressure drying.

[0330] The thickness of the active layer can be adjusted to any desired thickness by appropriately adjusting the solid content concentration in the coating solution and the conditions of step (i) and / or step (ii).

[0331] The step of forming the active layer may include other steps in addition to steps (i) and (ii) as long as the other steps do not impair the object and effect of the present disclosure. The method for manufacturing a photoelectric conversion element may be a method for manufacturing a photoelectric conversion element including a plurality of active layers, or may be a method in which steps (i) and (ii) are repeated multiple times.

[0332] The manufacturing method of the photoelectric conversion device of the present disclosure includes a step of forming an electron transport layer (electron injection layer) provided on an active layer. The method of forming the electron transport layer is not particularly limited. From the viewpoint of making the formation step of the electron transport layer simpler, it is preferable to form the electron transport layer by any conventionally known suitable vacuum evaporation method.

[0333] (Step of forming the cathode) The method of forming the cathode is not particularly limited. The cathode can be formed on the electron transport layer by any conventionally known suitable method such as a coating method, a vacuum evaporation method, a sputtering method, an ion plating method, a plating method, etc. using the electrode materials exemplified above. Through the above steps, the photoelectric conversion device of the present disclosure is manufactured.

[0334] (Step of forming the encapsulant) In forming the encapsulant, any conventionally known suitable encapsulant (adhesive) and substrate (encapsulation substrate) are used. Specifically, after applying an encapsulant such as a UV curable resin on a support substrate so as to surround the periphery of the manufactured photoelectric conversion device, and then bonding it without gaps with the encapsulant, the photoelectric conversion device is encapsulated in the gap between the support substrate and the encapsulation substrate using a method suitable for the selected encapsulant such as irradiation with UV light, whereby an encapsulant of the photoelectric conversion device can be obtained.

[0335] <Photo-detection element> The photoelectric conversion device of the present disclosure, particularly a photo-detection element (photo sensor), can be incorporated into an image sensor, a biometric authentication device (fingerprint authentication device, vein authentication device) and function as described above.

Examples

[0336] Hereinafter, examples are shown to explain the present disclosure in more detail. The present disclosure is not limited to the examples described below.

[0337] A photoelectric conversion device was fabricated using a p-type semiconductor material and an n-type semiconductor material.

[0338] <p-type semiconductor material> As p-type semiconductor materials, polymer compounds P-1, P-2, and P-20 were used. The synthesis method will be described later.

[0339]

Chem.

[0340]

Chem.

[0341] <n-type semiconductor material> As n-type semiconductor materials, the following compounds were used. The synthesis method will be described later.

[0342] (Compound N-1)

[0343]

Chem.

[0344] (Compound N-2)

[0345]

Chem.

[0346] (Compound N-3)

[0347]

Chem.

[0348] (Compound N-4)

[0349]

Chem.

[0350] (Compound N-5)

[0351]

Chem.

[0352] (Compound RN-1)

[0353] [ka]

[0354] (Compound RN-2)

[0355] [ka]

[0356] (Compound RN-3)

[0357] [ka]

[0358] (Synthesis of Compound N-1) Compound 2 was synthesized using compound 1.

[0359] [ka]

[0360] A 50 mL four-neck flask was charged with 4-Bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b']dithiophene (Tokyo Chemical Industry Co., Ltd., 1.00 g, 2.48 mmol), bis(pinacolato)diboron (1.58 g, 6.21 mmol), [Ir(OMe)(cod)]2 (19.8 mg, 0.0298 mmol), and tBu-bpy (16.0 mg, 0.0596 mmol). After purging with nitrogen, 15.0 g of cyclohexane was added and the flask was placed in an oil bath heated to 60 °C. After stirring for 2 hours, the flask was removed from the oil bath and allowed to cool to room temperature. The cooled mass was quenched by pouring it into water. The aqueous layer was removed from the resulting mass by separation, then dried over magnesium sulfate, and filtered while passing through silica gel. The entire amount was then concentrated using a rotary evaporator to obtain 2.30 g of crude compound 2.

[0361] Compound 4 was synthesized using compound 2.

[0362] [ka]

[0363] Crude compound 2 (1.60 g), 2-Bromo-3-(2-ethylhexyl)thiophene (1.30 g, 4.73 mmol) (TCI), and THF (36.1 mL) were charged into a 100 mL four-neck flask and subjected to nitrogen bubbling for 30 minutes. Pd2(dba)3 (0.157 g, 0.172 mmol), P(tBu3)HBF4 (0.099 g, 0.344 mmol), and 3 mol / L K3PO4 aqueous solution (9.96 g) were added in that order, and the mixture was heated to 65 °C. After stirring for 2 hours, the mixture was cooled to room temperature. The mixture was diluted with heptane, washed twice with water, dried over magnesium sulfate, filtered, and then concentrated to the full volume using a rotary evaporator. The resulting crude product was purified using a silica gel column (eluent: heptane) to obtain 1.34 g of compound 4. The NMR spectrum of the obtained compound 4 was analyzed, and the results are as follows. 1H-NMR (300 MHz, CHLOROFORM-D) δ 7.15 (2H), 6.93 (4H), 2.72 (4H), 1.90 (4H), 1.66 (2H), 1.26 (18H), 0.50-1.10 (m, 40H)

[0364] Compound 5 was synthesized using compound 4.

[0365] [ka]

[0366] Compound 4 (1.34 g) and chloroform (amylene-added) (14.1 mL) were placed in a 100 mL four-neck flask and bubbled with nitrogen for 30 minutes. The internal temperature was cooled to 3°C in an ice bath, and N-bromosuccinimide (0.646 g, 3.64 mmol) (manufactured by TCI) was added in three portions and stirred for 30 minutes. The reaction was quenched with 3% aqueous sodium sulfate (6.7 mL). The temperature was raised to room temperature, and the aqueous layer was removed by separation. The organic layer was washed once with water, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane) to obtain 1.68 g of compound 5. The NMR spectrum of the resulting compound 5 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 6.90 (2H), 6.87 (2H), 2.65 (4H), 1.87 (4H), 1.63 (2H), 1.26 (18H), 0.50-1.10 (m, 40H)

[0367] Compound 6 was synthesized using compound 5.

[0368] [ka]

[0369] Compound 5 (1.68 g, 1.76 mmol) was placed in a 100 mL four-neck flask, and after purging with nitrogen, THF (28.5 mL) was added and cooled to -73°C. A 1.6 M nBuLi hexane solution (Kanto Chemical, 2.51 mL) was added and the internal temperature was maintained at -70°C for 1 hour. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.21 mL, 5.33 mmol) and THF (9.5 mL) were placed in a dropping funnel and added dropwise to the reaction mass at an internal temperature of -70°C. After the addition was complete, the internal temperature was maintained at -70°C for 1 hour, then the temperature was raised to room temperature and the mixture was stirred overnight. After quenching by adding 20% ​​aqueous ammonium chloride solution (7.6 mL), the aqueous layer was separated from the resulting mass, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator to obtain 1.52 g of crude compound 6. The NMR spectrum of the resulting compound 6 was analyzed. The results are as follows: 1 H-NMR (300 MHz, CHLOROFORM-D) δ 7.42 (2H), 7.02 (2H), 2.72 (4H), 1.87 (4H), 1.70 (2H), 0.50-1.40 (82H)

[0370] Compound 8 was synthesized using compound 7.

[0371] [ka]

[0372] A 300 mL four-neck flask was charged with 3-Methoxythiophene (Tokyo Chemical Industry Co., Ltd., 5.00 g, 43.8 mmol), 2-Hexyl-1-decanol (31.9 g, 131 mmol), p-TsOH·HO (0.833 g, 4.38 mmol), and toluene (100 g). The atmosphere was replaced with nitrogen and the mixture was heated to 110 °C. After stirring for 23 hours, the mixture was cooled to room temperature. The mixture was diluted with toluene, washed twice with water, dried over magnesium sulfate, filtered, and then concentrated to the full volume using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: hexane = 100 wt%) to obtain 13.4 g of compound 8 as a colorless, transparent liquid. The NMR spectrum of the resulting compound 8 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 7.16 (1H), 6.75 (1H), 6.21 (1H), 3.81 (2H), 1.77-1.71 (1H), 1.46-1.28 (m, 24H), 0.90-0.86 (m, 6H)

[0373] Compound 9 was synthesized using compound 8.

[0374] [ka]

[0375] A 1 L four-neck flask was charged with compound 8 (15.4 g, 47.3 mmol) and THF (461 g). The atmosphere was replaced with nitrogen and then cooled to 0°C. NBS (8.33 g, 46.8 mmol) was added and stirred at 0°C. After stirring for 2 hours, the mixture was quenched by adding 3 wt% aqueous sodium sulfite solution (249 g). After warming to room temperature, the aqueous layer was removed from the resulting mass by separation, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: hexane = 100 wt%) to obtain 18.5 g of compound 9 as a colorless, transparent liquid.

[0376] Compound 10 was synthesized using compound 9.

[0377] [ka]

[0378] A 50 mL four-neck flask was charged with compound 9 (18.5 g, 45.9 mmol) and THF (185 g). The atmosphere was purged with nitrogen and then cooled to -73 °C. LDA (1 M in THF / hexane, 45.9 mL, 45.9 mmol) was added and the mixture was kept at -73 °C for 2 hours. DMF (7.1 mL, 91.9 mmol) was slowly added, and the mixture was warmed to room temperature and stirred for 2 hours. After quenching by adding 20% ​​aqueous ammonium chloride solution (98 mL), the aqueous layer was separated from the resulting mass, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: hexane / ethyl acetate = 70 / 1 (volume ratio)) to obtain 5.26 g of compound 10 as a yellow liquid. The NMR spectrum of the resulting compound 10 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.70 (1H), 7.37 (1H), 3.95 (2H), 1.80-1.74 (1H), 1.49-1.27 (m, 24H), 0.90-0.86 (m, 6H)

[0379] Compound 11 was synthesized using compounds 6 and 10.

[0380] [ka]

[0381] Crude compound 6 (1.52 g), compound 10 (1.10 g, 2.55 mmol), and THF (31.0 mL) were charged into a 100 mL four-neck flask and subjected to nitrogen bubbling for 30 minutes. Pd2(dba)3 (0.0531 g, 0.0579 mmol), P(tBu3)HBF4 (0.0336 g, 0.116 mmol), and 3 mol / L K3PO4 aqueous solution (5.37 g) were added in that order and the temperature was raised to 65 °C. After stirring for 2 hours, the mixture was cooled to room temperature. It was diluted with heptane, washed twice with water, dried over magnesium sulfate, filtered, and then concentrated to the full volume using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 7 / 3 (volume ratio)) to obtain 1.73 g of compound 11. The NMR spectrum of the obtained compound 11 was analyzed, and the results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.77 (2H), 7.48 (2H), 7.26 (4H), 7.01 (2H), 4.08 (4H), 2.74 (4H), 1.90 (6H), 1.72 (2H), 0.50-1.50 (118H)

[0382] Compound N-1 was synthesized using compound 11 and compound 12.

[0383] [ka]

[0384] A 50 mL four-neck flask was charged with compound 11 (0.377 g, 0.253 mmol), compound 12 (0.185 g, 0.758 mmol), synthesized according to the method described in International Publication No. 2020 / 109823, p-TsOH·HO (0.144 g, 0.758 mmol), EtOH (3.4 g), toluene (7.5 g), and MgSO (0.188 g). The mixture was then placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, the mixture was removed from the oil bath and allowed to cool to room temperature. The MgSO was removed by filtration, and the precipitate was dissolved and washed with chloroform. The mixture was concentrated using an evaporator and repulped with methanol to obtain a crude product. The resulting crude product was purified using a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 0.28 g of compound N-1 as a black solid. The NMR spectrum of the obtained compound N-1 was analyzed, and the results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.00(2H), 8.81(2H), 8.16(2H), 7.71 (2H), 7.51(2H), 7.18(2H), 4.17 (4H), 2.82(4H), 1.97(6H), 1.77(2H), 0.50-1.50 (118)

[0385] (Synthesis of Compound N-2) Compound 13 was synthesized using compound 9.

[0386] [ka]

[0387] A 200 mL four-neck flask was charged with compound 9 (4.0 g, 12.3 mmol) and THF (45 mL), purged with nitrogen, and then cooled to -73°C. LDA (1 M in THF / Hexane, 13.6 mL, 13.6 mmol) was charged and the internal temperature was maintained at -65°C for 1 hour. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.2 mL, 18.5 mmol) and THF (22.5 mL) were charged into a dropping funnel and added dropwise to the reaction mass at an internal temperature of -65°C. After the addition was complete, the internal temperature was maintained at -65°C for 1 hour, then the temperature was raised to room temperature and the mixture was stirred for 2 hours. After quenching by pouring in 20% aqueous ammonium chloride solution (26 mL), the aqueous layer was separated from the resulting mass, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator to obtain 5.91 g of compound 13 as a crude product. The NMR spectrum of the resulting compound 13 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 7.26 (1H), 6.56 (1H), 3.82 (2H), 1.74-1.72 (1H), 1.57-1.19 (m, 36H), 00.88 (6H)

[0388] Compound 14 was synthesized using compound 13.

[0389] [ka]

[0390] Crude compound 13 (7.80 g), 5-Bromo-4-(2-ethylhexyl)thiophene-2-carbaldehyde (5.51 g, 18.1 mmol), and THF (197 mL) were charged into a 500 mL four-neck flask and subjected to nitrogen bubbling for 30 minutes. Pd2(dba)3 (0.792, 0.866 mmol), P(tBu3)HBF4 (0.527 g, 1.81 mmol), and 3 mol / L K3PO4 aqueous solution (80.1 g) were added in that order, and the temperature was raised to 65 °C. After stirring for 2 hours, the mixture was cooled to room temperature. The mixture was diluted with heptane, washed twice with water, dried over magnesium sulfate, filtered, and then concentrated to the full volume using a rotary evaporator. The obtained crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 20 / 1 (volume ratio)) to obtain 7.78 g of compound 14 as a brown liquid. The NMR spectrum of the obtained compound 14 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.83 (1H), 7.51 (1H), 6.93 (1H), 6.32 (1H), 3.84 (2H), 2.73 (2H), 0.83-1.77 (m, 46H)

[0391] Compound 15 was synthesized using compound 14.

[0392] [ka]

[0393] A 500 mL four-neck flask was charged with compound 14 (6.60 g, 12.0 mmol) and chloroform (231.0 g). The flask was purged with nitrogen and then cooled to 0°C. NBS (2.12 g, 11.9 mmol) was added and stirred at 0°C. After stirring for 2 hours, water (165.0 g) was added and the mixture was warmed to room temperature. The aqueous layer was removed from the resulting mass by separation, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 25 / 1 (volume ratio)) to obtain 5.13 g of compound 15 as a brown liquid. The NMR spectrum of the resulting compound 15 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.83 (1H), 7.53 (1H), 6.89(1H), 3.94 (2H), 2.69 (2H), 0.84-1.77 (m, 46H)

[0394] Compound 17 was synthesized using compound 1.

[0395] [ka]

[0396] A 100 mL four-neck flask was charged with 4-Bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b']dithiophene (Tokyo Chemical Industry Co., Ltd., 2.29 g, 5.67 mmol) and THF (25.7 mL). The flask was purged with nitrogen and then cooled to -73 °C. nBuLi (1.56 mol / L in hexane, 4.00 mL, 6.24 mmol) was added and the internal temperature was maintained at -65 °C for 1 hour. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.58 g, 8.50 mmol) and THF (12.9 mL) were added to the dropping funnel and added dropwise to the reaction mass at an internal temperature of -65 °C. After the addition was complete, the internal temperature was maintained at -65 °C for 1 hour, then the temperature was raised to room temperature and the mixture was stirred for 1 hour. After quenching by pouring in 20% aqueous ammonium chloride solution (12.1 mL), the aqueous layer was separated from the resulting mass, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator to obtain 3.20 g of crude compound 17.

[0397] Compound 18 was synthesized using compound 17 and compound 15.

[0398] [ka]

[0399] Crude compound 17 (3.00 g), compound 15 (3.19 g, 5.10 mmol), and THF (68.3 g) were charged into a 200 mL four-neck flask and subjected to nitrogen bubbling for 30 minutes. Pd2(dba)3 (0.259 g, 0.284 mmol), P(tBu3)HBF4 (0.172 g, 0.596 mmol), and 3 mol / L K3PO4 aqueous solution (26.2 g) were added in that order and the temperature was raised to 60 °C. After stirring for 2 hours, the mixture was cooled to room temperature. It was diluted with heptane, washed twice with water, dried over magnesium sulfate, filtered, and then concentrated to the full volume using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane / toluene = 1 / 1 (volume ratio)) to obtain 3.37 g of compound 18 as a red liquid. The NMR spectrum of the obtained compound 18 was analyzed, and the results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.82 (1H), 7.54 (1H), 7.10-7.19 (2H),7.04 (1H), 6.91-6.94 (1H), 4.05 (2H), 2.78 (2H), 0.57-1.94 (m, 80H)

[0400] Compound 19 was synthesized using compound 18 and compound 10.

[0401] [ka]

[0402] A 100 mL four-neck flask was charged with compound 18 (3.35 g, 3.53 mmol), compound 10 (2.13 g, 4.4 mmol), Pd(OAc) (0.149 g, 0.665 mmol), [(tBu)MePH]BF (0.263 g, 1.06 mmol), pivalic acid (0.361 g, 3.53 mmol), KCO (1.46 g, 10.6 mmol), and DMF (33.5 g). Nitrogen bubbling was performed for 30 minutes. After nitrogen replacement, the internal temperature was raised to 120 °C and stirred for 1 hour. After cooling to room temperature, the mixture was diluted with heptane, washed twice with water, dried over magnesium sulfate, filtered, and then completely concentrated on a rotary evaporator. The obtained crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 10 / 1 (volume ratio)) to obtain 3.53 g of compound 19 as a reddish-purple liquid. The NMR spectrum of the obtained compound 19 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.83 (1H), 9.74 (1H), 7.54 (1H), 7.46 (1H), 7.33 (1H), 7.14 (1H), 7.04 (1H), 4.06 -4.09 (m, 4H), 2.79( 2H),0.60-1.90 (m, 111H)

[0403] Compound 26 was synthesized according to the following scheme. The NMR spectrum of the obtained compound 26 was analyzed. The results are as follows. 1 H-NMR (300 MHz, DMSO-d6) δ 8.36(1H), 8.18(1H), 6.05(1H)

[0404] [ka]

[0405] Compound N-2 was synthesized using compound 19 and compound 26.

[0406] [ka]

[0407] A 100 mL four-neck flask was charged with compound 19 (0.272 g, 0.210 mmol), compound 26 (0.330 g, 1.04 mmol), p-TsOH·HO (0.279 g, 1.46 mmol), EtOH (17.7 g), and toluene (7.4 g). The mixture was then placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, the mixture was removed from the oil bath and allowed to cool to room temperature. The mixture was then filtered and washed with methanol to obtain a crude product. The resulting crude product was purified by recycled GPC (eluent: chloroform). 0.25 g of the purified recycled GPC product was dissolved in chloroform (4.0 g), and methanol (17.5 g) was added at room temperature to crystallize the product. The crystals were then filtered and dried to obtain 0.240 g of compound N-2. The NMR spectrum of the resulting compound N-2 was analyzed. The results are shown below. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 8.93(1H),8.79 (1H), 8.38-8.48 (4H), 7.75-7.78(2H), 7.27-7.43 (3H), 4.20 (4H),2.88(4H),0.65-2.01 (111H)

[0408] (Synthesis of Compound N-3) As shown in the following formula, compound 27 was synthesized using compound 2 and compound 9.

[0409] [ka]

[0410] A 100 mL four-neck flask was purged with nitrogen and charged with compound 2 (1.375 g, 2.10 mmol), compound 9 (1.86 g, 4.62 mmol), and THF (30.9 mL). After 30 minutes of nitrogen bubbling, Pd(dba) (0.096 g, 0.11 mmol), [(tBu)PH]BF (0.061 g, 0.21 mmol), and 3M aqueous KPO (7.00 mL) were added and the temperature was raised to 60 °C. After 1 hour of incubation, the reaction solution was cooled to room temperature, diluted with 25 mL of heptane, and washed twice with 12.5 mL of water. The mixture was dried over magnesium sulfate, filtered to remove the magnesium sulfate, and then concentrated on a rotary evaporator to obtain the crude product. The obtained crude product was purified using a silica gel column (developing solvent: hexane / ethyl acetate = 9 / 1 (v / v)) to obtain 2.15 g of Compound 27 as a red liquid (yield 97%).

[0411] As shown in the following formula, compound 28 was synthesized using compound 27.

[0412] [ka]

[0413] A 50 mL four-neck flask was charged with compound 27 (1.06 g, 1.02 mmol), bis(pinacolato)diboron (0.72 g, 2.80 mmol), [Ir(OMe)(cod)]2 (8.1 mg, 0.012 mmol), and tBu-bpy (6.5 mg, 0.024 mmol). After purging with nitrogen, 20.5 mL of cyclohexane was added and the mixture was placed in an oil bath heated to 80 °C. After stirring for 1 hour, the mixture was removed from the oil bath and allowed to cool to room temperature. The cooled mass was quenched by pouring it into water. The aqueous layer was removed from the resulting mass by separation, dried over magnesium sulfate, and filtered while passing through silica gel. The mixture was then completely concentrated on a rotary evaporator to obtain 1.77 g of crude compound 28.

[0414] Compound 29 was synthesized using compound 28.

[0415] [ka]

[0416] A 100 mL four-neck flask was charged with compound 28 (1.77 g, 1.04 mmol), 5-Bromo-4-(2-ethylhexyl)thiophene-2-carbaldehyde (0.76 g, 2.50 mmol), and THF (30.9 mL). After 30 minutes of nitrogen bubbling, Pd(dba) (0.048 g, 0.052 mmol), [(tBu)PH]BF (0.030 g, 0.10 mmol), and 3M aqueous KPO (3.48 mL) were added and the temperature was raised to 60 °C. After 1.5 hours of incubation, the reaction solution was cooled to room temperature, diluted with heptane (36 mL), washed twice with water (31 mL), dried over magnesium sulfate, filtered, and then concentrated to the full volume using a rotary evaporator. The obtained crude product was purified by silica gel column (developing solvent: heptane / ethyl acetate = 9 / 1 (volume ratio)) and further by recycled GPC (chloroform) to obtain 0.50 g of compound 29 (yield 32%).

[0417] Compound 29 was used to synthesize compound N-3.

[0418] [ka]

[0419] A 100 mL four-neck flask was charged with compound 29 (0.250 g, 0.17 mmol), compound ICO-2CN (0.123 g, 0.50 mmol), p-TsOH·HO (0.095 g, 0.50 mmol), EtOH (5.0 mL), toluene (10.1 mL), and MgSO (0.125 g). After 30 minutes of nitrogen bubbling, the flask was placed in an oil bath heated to 65 °C. After stirring for 2 hours, compound 12 (0.62 g, 0.25 mmol) was added and stirred for an additional hour. The flask was then removed from the oil bath and allowed to cool to room temperature. The MgSO was removed by filtration, and the precipitate was dissolved and washed with chloroform. The mixture was concentrated by evaporation and repulped with methanol to obtain a crude product. The obtained crude product was purified by recycling GPC to obtain 0.25 g (71% yield) of compound N-3 as a black solid. The NMR spectrum of the obtained compound N-3 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.03 (2H), 8.85 (2H), 8.20 (2H), 7.69 (2H), 7.39 (2H), 7.30 (2H), 4.16 (4H), 2.86 (4H),1.95−0.50 (m, 126H)

[0420] (Synthesis of Compound N-4) Compound N-4 was synthesized using compound 29 and compound 26.

[0421] [ka]

[0422] A 200 mL four-neck flask was charged with compound 29 (0.440 g, 0.30 mmol), compound 26 (0.464 g, 1.47 mmol), p-TsOH·HO (0.39 g, 2.06 mmol), EtOH (36.2 mL), and toluene (13.7 mL). After 20 minutes of nitrogen bubbling, the flask was placed in an oil bath heated to 65 °C. After stirring for 1 hour, compound 26 (0.62 g, 0.25 mmol) was added and stirred for an additional hour. The mixture was then removed from the oil bath and allowed to cool to room temperature. The residue was filtered and washed sequentially with methanol (44 mL), ethanol (44 mL), and heptane (44 mL) to obtain a crude product. The crude product was purified by recycling GPC using chloroform as the mobile phase to obtain 0.44 g (72% yield) of compound N-4 as a black solid. The NMR spectrum of the obtained compound N-4 was analyzed, and the results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 8.88 (2H), 8.46 (2H), 8.40 (2H), 7.73 (2H), 7.42 (2H), 7.33 (2H), 4.17 (4H), 2.87(4H), 1.98−0.50 (m, 126H)

[0423] (Synthesis of compound RN-1) Compound 30 was synthesized using compound 13.

[0424] [ka]

[0425] Crude compound 13 (5.90 g), 5-Bromo-4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde (4.60 g, 14.4 mmol) (JiangSu GR-Chem Co., Ltd.), and THF (149 mL) were charged into a 500 mL four-neck flask and subjected to nitrogen bubbling for 30 minutes. Pd2(dba)3 (0.600 g, 0.655 mmol), P(tBu3)HBF4 (0.399 g, 1.38 mmol), and 3 mol / L K3PO4 aqueous solution (60.6 g) were added in that order, and the temperature was raised to 65 °C. After stirring for 2 hours, the mixture was cooled to room temperature. The mixture was diluted with toluene, washed twice with water, dried over magnesium sulfate, filtered, and then concentrated to the full volume using a rotary evaporator. The obtained crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 20 / 1 (volume ratio)) to obtain 3.72 g of compound 30 as a yellow-brown liquid. The NMR spectrum of the obtained compound 30 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.75 (1H), 7.46 (1H), 7.08 (1H), 6.29 (1H), 4.06 (2H), 3.83 (2H), 1.85-1.27 (m, 34H), 0.98-0.86 (m, 12H)

[0426] Compound 31 was synthesized using compound 30.

[0427] [ka]

[0428] A 100 mL four-neck flask was charged with compound 30 (1.60 g, 2.84 mmol) and chloroform (56.0 g). The flask was purged with nitrogen and then cooled to 0 °C. NBS (0.501 g, 2.81 mmol) was added and stirred at 0 °C. After stirring for 2 hours, water (40.0 g) was added and the mixture was warmed to room temperature. The aqueous layer was removed from the resulting mass by separation, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 20 / 1 (volume ratio)) to obtain 1.84 g of compound 31 as a yellow-brown liquid. The NMR spectrum of the resulting compound 31 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.77 (1H), 7.45 (1H), 7.02 (1H), 4.07 (2H), 3.93 (2H), 1.86-1.27 (m, 34H), 0.99-0.86 (m, 12H)

[0429] Compound 32 was synthesized using compound 17 and compound 31.

[0430] [ka]

[0431] Crude compound 17 (1.49 g), compound 31 (2.05 g, 3.20 mmol), and THF (29.6 g) were charged into a 100 mL four-neck flask and subjected to nitrogen bubbling for 30 minutes. Pd2(dba)3 (0.113 g, 0.123 mmol), P(tBu3)HBF4 (0.0749 g, 0.258 mmol), and 3 mol / L K3PO4 aqueous solution (11.4 g) were added in that order and the temperature was raised to 60 °C. After stirring for 2 hours, the mixture was cooled to room temperature. The mixture was diluted with toluene, washed twice with water, dried over magnesium sulfate, filtered, and then concentrated on a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 10 / 1 (volume ratio)) to obtain 1.27 g of compound 32 as a red liquid. The NMR spectrum of the obtained compound 32 was analyzed, and the results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.75 (1H), 7.46 (1H), 7.20 (1H), 7.13-7.10 (m, 2H), 6.93-6.91 (m, 1H), 4.10 (2H), 4.05 (2H), 1.93-0.57 (m, 80H)

[0432] Compound 32 was used to synthesize compound 33.

[0433] [ka]

[0434] A 50 mL four-neck flask was charged with compound 32 (1.25 g, 1.30 mmol), 5-Bromo-4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde (0.497 g, 1.56 mmol) (JiangSu GR-Chem), Pd(OAc) (0.0364 g, 0.162 mmol), [(tBu)MePH]BF (0.0644 g, 0.259 mmol), pivalic acid (0.133 g, 1.30 mmol), KCO (0.538 g, 3.89 mmol), and DMF (12.5 g). Nitrogen bubbling was performed for 30 minutes. After nitrogen replacement, the internal temperature was raised to 120 °C and stirred for 5 hours. After cooling to room temperature, the mixture was diluted with toluene, washed twice with water, dried over magnesium sulfate, filtered, and then concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 8 / 1 (volume ratio)) to obtain 0.620 g of compound 33 as a deep red-purple liquid. The NMR spectrum of the resulting compound 33 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.76 (1H), 9.74 (1H), 7.47 (2H), 7.32 (1H), 7.20 (1H), 7.12 (1H), 4.13 -4.06 (m, 6H), 1.89-0.60 (m, 95H)

[0435] Compound RN-1 was synthesized using compound 33.

[0436] [ka]

[0437] A 50 mL four-neck flask was charged with compound 33 (0.600 g, 0.499 mmol), compound 12 (0.366 g, 1.50 mmol), synthesized according to the method described in International Publication No. 2020 / 109823, p-TsOH·HO (0.285 g, 1.50 mmol), EtOH (5.5 g), toluene (11.0 g), and MgSO (0.300 g). The mixture was then placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, the mixture was removed from the oil bath and allowed to cool to room temperature. The MgSO was removed by filtration, and the precipitate was dissolved and washed with chloroform. The mixture was concentrated using an evaporator and repulped with methanol to obtain a crude product. The resulting crude product was purified using a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 0.632 g (78% yield) of compound RN-1 as a black solid. The NMR spectrum of the resulting compound RN-1 was analyzed, and the results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 8.98-8.95 (m, 2H), 8.76-8.72 (m, 2H), 8.14-8.11 (m, 2H), 7.74 (1H), 7.50-7.32 (m, 4H), 4.19 (6H), 2.06-0.64 (m, 95H)

[0438] (Synthesis of compound RN-2) Compound 34 was synthesized using compound 2 and compound 31.

[0439] [ka]

[0440] Crude compound 2 (1.13 g), compound 31 (1.80 g, 2.81 mmol), and THF (18.2 g) were charged into a 50 mL four-neck flask and subjected to nitrogen bubbling for 30 minutes. Pd2(dba)3 (0.0560 g, 0.0612 mmol), P(tBu3)HBF4 (0.0372 g, 0.128 mmol), and 3 mol / L K3PO4 aqueous solution (5.66 g) were added in that order and the temperature was raised to 60 °C. After stirring for 2 hours, the mixture was cooled to room temperature. The mixture was diluted with toluene, washed twice with water, dried over magnesium sulfate, filtered, and then concentrated on a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 8 / 1 (volume ratio)) to obtain 1.19 g of compound 34 as a dark red viscous liquid. The NMR spectrum of the obtained compound 34 was analyzed, and the results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.75 (2H), 7.46 (2H), 7.20 (2H), 7.13 (2H), 4.10 (4H), 4.06 (2H), 1.94-0.61 (m, 126H)

[0441] Compound RN-2 was synthesized using compound 34.

[0442] [ka]

[0443] A 100 mL four-neck flask was charged with compound 34 (1.15 g, 0.754 mmol), compound 12 (0.553 g, 2.26 mmol), p-TsOH·HO (0.431 g, 2.26 mmol), EtOH (10.5 g), toluene (23.0 g), and MgSO (0.575 g) and kept warm in an oil bath heated to 65 °C. After stirring for 2 hours, the flask was removed from the oil bath and allowed to cool to room temperature. The MgSO was removed by filtration, and the precipitate was dissolved and washed with chloroform. The mixture was concentrated using an evaporator and repulped with methanol to obtain a crude product. The resulting crude product was purified using a silica gel column (eluent: chloroform = 100 wt%) to obtain 0.890 g (60% yield) of compound RN-2 as a black solid. NMR spectra of the resulting compound RN-2 were analyzed. The results are as follows: 1 H-NMR (300 MHz, CHLOROFORM-D) δ 8.94-8.93 (m, 2H), 8.69 (2H), 8.10 (2H), 7.50-7.35 (m, 6H), 4.19-4.15 (m, 8H), 1.94-0.64 (m, 126H)

[0444] (Synthesis of compound RN-3) Compound 35 was synthesized using compound 3.

[0445] [ka]

[0446] A 50 mL four-neck flask was charged with magnesium turnings (0.353 g, 14.5 mmol), diethyl ether (10.0 mL), and a small amount of iodine. The atmosphere was replaced with nitrogen and the mixture was stirred at room temperature. 2-Bromo-3-(2-ethylhexyl)thiophene (2.00 g, 7.27 mmol) and diethyl ether (10.0 mL) were charged into a dropping funnel, and the mixture was added dropwise at an internal temperature of 30°C or less. After the addition was complete, the oil bath temperature was raised to 43°C and the mixture was heated to reflux for 2 hours. After maintaining the temperature for 2 hours, the mixture was cooled to room temperature to obtain a Grignard reagent. A 100 mL four-neck flask was charged with 2,5-dibromothiophene (1.76 g, 7.27 mmol), PdCl2dppf (0.200 g, 0.273 mmol), and diethyl ether (20.0 mL). The atmosphere was replaced with nitrogen and the mixture was stirred at an internal temperature of 0 °C. The Grignard reagent was added dropwise at an internal temperature of 0 °C, and the mixture was stirred at an internal temperature of 0 °C for 2 h. After quenching by adding water (40 mL), the aqueous layer was separated from the resulting mass, dried over magnesium sulfate, filtered, and then concentrated to the full volume using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane = 100 wt%) to obtain 1.48 g of compound 35 as a yellow liquid. The NMR spectrum of the resulting compound 35 was analyzed. The results are shown below. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 7.19 (1H), 7.00 (1H), 6.89 (1H), 6.84 (1H), 2.64 (2H), 1.62-1.51 (m, 1H), 1.33-1.16 (m, 8H), 0.90-0.80 (m, 6H)

[0447] Compound 37 was synthesized using compounds 35 and 36.

[0448] [ka]

[0449] A 100 mL three-neck flask was charged with compound 36 (1.40 g, 1.78 mmol) (synthesized with reference to the method described in International Publication No. 2014 / 112656), compound 35 (1.46 g, 4.09 mmol), and THF (52.7 g), followed by 30 minutes of nitrogen bubbling. Pd(dba) (0.0813 g, 0.089 mmol), P(tBu)HBF (0.103 g, 0.355 mmol), and 3 mol / L KPO aqueous solution (8.22 g) were added in that order, and the mixture was heated to 65 °C. After stirring for 2 hours, the mixture was cooled to room temperature (25 °C). The mixture was diluted with toluene, washed twice with water, dehydrated with magnesium sulfate, and the magnesium sulfate was removed by filtration. The total volume was then concentrated on a rotary evaporator. The obtained crude product was purified using a silica gel column (developing solvent: heptane = 100 wt%) to obtain 1.81 g (yield 94%) of compound 37 as a red liquid. The NMR spectrum of the obtained compound 37 was analyzed. The results are as follows. 1 H-NMR (300MHz,CHLOROFORM-D) δ 7.18 (2H), 7.09 (1H), 7.07 (1H), 7.01 (2H), 6.91 (2H), 6.78 (1H), 6.76 (1H), 2.72 (4H), 1.95-1.81 (m, 4H), 1.68-1.64 (m, 2H), 1.42-1.23 (m, 56H), 0.91-0.83 (m, 18H)

[0450] Compound 37 was used to synthesize compound 38.

[0451] [ka]

[0452] A 200 mL four-neck flask was charged with compound 37 (1.79 g, 1.65 mmol) and dichloromethane (109 g). After purging with nitrogen, (chloromethylene)dimethyliminium chloride (0.845 g, 6.60 mmol) was added and the flask was placed in an oil bath heated to 49 °C to maintain the temperature. After stirring for 24 hours, the flask was removed from the oil bath and allowed to cool to room temperature. The mixture was washed twice with water, dehydrated over magnesium sulfate, and filtered to remove the magnesium sulfate. The entire volume was then concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 100 / 0 to 20 / 1 (volume ratio)) to obtain 1.72 g (92% yield) of compound 38 as a dark red liquid. The NMR spectrum of the resulting compound 38 was analyzed. The results are shown below. 1 H-NMR (300MHz,CHLOROFORM-D) δ 9.84 (2H), 7.56 (1H), 7.55 (1H), 7.19 (2H), 7.13 (1H), 7.11 (1H), 6.83 (1H), 6.81 (1H), 2.77 (4H), 1.96-1.82 (m, 4H), 1.70-1.68 (m, 2H), 1.40-1.23 (m, 56H), 0.90-0.84 (m, 18H)

[0453] Compound RN-3 was synthesized using compound 38.

[0454] [ka]

[0455] A 100 mL four-neck flask was charged with compound 38 (0.627 g, 0.550 mmol), compound 12 (0.322 g, 1.32 mmol), p-TsOH·HO (0.209 g, 1.10 mmol), EtOH (21.7 g), and toluene (23.8 g) and kept warm in an oil bath heated to 89 °C. After stirring for 3 hours, the flask was removed from the oil bath and allowed to cool to room temperature. The mixture was then added dropwise to methanol (115 g) and the precipitate was collected by filtration to obtain a crude product. Chloroform (50 g) was added to the crude product, and the mixture was heated to 60 °C and stirred for 10 minutes. After cooling to room temperature, heptane (50 g) was added and the precipitate was collected by filtration to obtain 0.230 g (30% yield) of compound RN-3 as a black solid. NMR spectroscopy of the resulting compound RN-3 was performed. The results are shown below. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.03 (1H), 9.02 (1H), 8.89 (1H), 8.87 (1H), 8.23 ​​(2H), 7.72 (2H), 7.56-7.54 (m, 2H), 7.25-7.22 (m, 2H), 6.93 (1H), 6.91 (1H), 2.83 (4H), 1.94-1.92 (m, 4H), 1.77 (2H), 1.43-1.23 (m, 56H), 0.95-0.83 (m, 18H)

[0456] (Synthesis of Compound N-5) As shown in the following formula, compound 40 was synthesized using compound 39.

[0457] [ka]

[0458] Compound 39 (Tokyo Chemical Industry Co., Ltd., 1.76 g, 7.0 mmol) and tetrahydrofuran (9.9 ml) were added to a 50 ml four-necked recovery flask. After purging with nitrogen, 1,3-Dibromo-5,5-dimethylhydantoin (Tokyo Chemical Industry Co., Ltd., 1.20 g, 3.5 mmol) was added and the mixture was placed in an oil bath heated to 30 °C. After stirring for 1 hour, the mixture was removed from the oil bath and allowed to cool to room temperature. 40.8 ml of heptane was added to the reaction mass, and the precipitated solid was removed by filtration. The filtrate was dried over magnesium sulfate, filtered, and then completely concentrated on a rotary evaporator to obtain crude compound 40. The resulting crude product was purified using a silica gel column (eluent: heptane) to obtain 1.47 g of compound 40 as a transparent liquid (yield: 63%).

[0459] Compound 41 was synthesized using compound 27.

[0460] [ka]

[0461] A 300 ml four-neck flask was purged with nitrogen, and compound 27 (5.93 g, 5.66 mmol) and THF (66.8 ml) were added. The mixture was cooled to an internal temperature of -78 °C in a dry ice / acetone bath. A 1.6 M nBuLi hexane solution (4.17 ml, 6.51 mmol) was added dropwise and stirred for 1 hour. A solution of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.58 g, 8.50 mmol) in THF (33.4 ml) was prepared and added dropwise over 20 minutes. After the addition, the mixture was stirred at -78 °C for 1 hour, warmed to room temperature, and left overnight. The reaction vessel was cooled in an ice bath and quenched with 20% aqueous ammonium chloride (12.1 ml). The reaction solution was diluted with heptane, the aqueous layer was removed, and the mixture was separated and washed twice with water. The organic layer was dried over magnesium sulfate, filtered, and then concentrated using an evaporator to obtain 5.89 g of crude compound 41.

[0462] As shown in the following formula, compound 42 was synthesized using compound 41 and compound 40.

[0463] [ka]

[0464] Compound 40 (0.239 g, 0.72 mmol), compound 41 (1.86 g, 0.79 mmol), and tetrahydrofuran (10.7 mL) were added to a 100 mL four-neck flask, which was then purged with nitrogen. Pd(dba) (Strem Chemicals, 0.033 g, 0.04 mmol), [(tBu)PH]BF (Tokyo Chemical Industry, 0.021 g, 0.07 mmol), and 3M aqueous KPO (2.4 mL) were then added and heated to 60 °C. After stirring for 1 hour, the reaction solution was cooled to room temperature, diluted with heptane (16.5 mL), and washed twice with water (9.5 mL). The mixture was dried over magnesium sulfate, filtered to remove the magnesium sulfate, and concentrated on a rotary evaporator to obtain the crude product. The obtained crude product was purified using a silica gel column (developing solvent: heptane / toluene=95 / 5 (v / v)) to obtain 0.37 g of Compound 42 as a red liquid (yield: 40%).

[0465] As shown in the following formula, compound 43 was synthesized using compound 42.

[0466] [ka]

[0467] Compound 42 (0.36 g, 0.28 mmol) and CHCl3 (10.5 mL) were added to a 50 mL four-neck flask, and the atmosphere was replaced with nitrogen. (Chloromethylene)dimethyliminium Chloride (Tokyo Chemical Industry Co., Ltd., 0.18 g, 1.40 mmol) was then added, and the mixture was heated to 60 °C and stirred while maintaining the temperature. After stirring for 1 hour, the mixture was removed from the oil bath and allowed to cool to room temperature. Water (14.5 mL) and 5 wt% NaHCO3 aqueous solution (10.5 mL) were poured into the cooled mass with stirring to quench the reaction. The aqueous layer was removed from the resulting mass by separation, and the organic layer was washed with water (14.5 mL), dried over magnesium sulfate, filtered, and then completely concentrated on a rotary evaporator to obtain crude compound 43. The obtained crude product was purified using a silica gel column (developing solvent: heptane / toluene=7 / 3 (v / v)) to obtain 0.24 g of Compound 43 as a red liquid (yield 63%).

[0468] Compound N-5 was synthesized using compound 43 and compound 26.

[0469] [ka]

[0470] A 100 mL four-neck flask was charged with compound 43 (0.24 g, 0.18 mmol), compound 26 (0.215 g, 0.44 mmol), p-TsOH·HO (0.118 g, 0.62 mmol), EtOH (19.7 mL), and toluene (7.5 mL). After 30 minutes of nitrogen bubbling, the mixture was heated to 65 °C and stirred. After 1 hour, compound 26 (0.106 g, 0.22 mmol) and p-TsOH·HO (0.60 g, 0.31 mmol) were added. The mixture was stirred for an additional 2 hours and then cooled to room temperature. The precipitated solid was filtered, washed sequentially with methanol (24.2 mL), ethanol (24.3 mL), and heptane (23.8 mL), and air-dried to obtain the crude product. The mixture was purified by recycling GPC using CHCl3 as the mobile phase, and the concentrated fraction was washed with methanol through a Kiriyama filter. The residue was dried to obtain compound N-5 (yield 81%). The NMR spectrum of the obtained compound N-5 was analyzed. The results are as follows: 1 H-NMR (300 MHz, CHLOROFORM-D)δ9.16(1H), 8.80(1H), 8.51(1H), 8.46(1H), 8.42(1H), 8.39(1H), 7.78(1H), 7.46(1H), 7.33(1H), 4.20(4H), 2.97(4H), 2.00(4H), 1.9-0.5(114H)

[0471] (Synthesis of polymer compound P-1) Polymer compound P-1 was synthesized with reference to the method described in WO 2011 / 052709.

[0472] (Synthesis of polymer compound P-2) Polymer compound P-2 was synthesized with reference to the method described in WO 2013 / 051676.

[0473] (Synthesis of polymer compound P-20) Compound 46 was synthesized using compounds 44 and 45.

[0474] [ka]

[0475] Magnesium (1.61 g, 0.066 mol), THF (47 g), and iodine (32 mg) were added to a 1 L four-neck flask purged with nitrogen and stirred. After the purple color of the iodine disappeared, a solution of compound 45 (19.8 g, 0.063 mmol) in THF (36 g) was added dropwise to generate a Grignard reagent. A solution containing compound 44 (5.21 g, 0.025 mol), synthesized by the method described in WO 2011 / 136311, and THF (107 g) was added dropwise to the four-neck flask, ensuring that the internal temperature did not exceed 40°C. The reaction mixture was then stirred for 1 hour, and the reaction was quenched by adding aqueous ammonium chloride solution to the reaction mixture, followed by separation. The organic layer was dehydrated over magnesium sulfate, the magnesium sulfate was removed by filtration, and the filtrate was concentrated on a rotary evaporator. The residue was purified by silica gel column chromatography (using hexane and ethyl acetate as the developing solvent) to obtain 14.21 g (20.7 mmol, yield 83%) of Compound 46.

[0476] Compound 46 1 The H-NMR measurement results are as follows: δ(ppm):7.82-7.76 (m, 1H), 7.64 (s, 2H), 7.43 (m, 2H), 7.31 (m, 10H), 7.25 (m, 2H), 7.21 (m, 1H), 7.13 (m, 2H), 6.91 (d, 1H), 6.64 (d, 1H), 6.43 (d, 1H), 3.72-3.64 (m, 1H), 2.63 (t, 4H), 1.61 (m, 4H), 1.22-1.34 (m, 12H), 0.86 (t, 6H)

[0477] Compound 47 was synthesized using compound 46.

[0478] [ka]

[0479] A 500 mL four-neck flask was charged with compound 46 (14.21 g, 0.0208 mmol) and heptane (130 g). The atmosphere in the reaction vessel was replaced with nitrogen, and trifluoroacetic acid (0.409 g, 0.0036 mmol) was added. The mixture was heated to 60 °C, stirred for 30 minutes, and then cooled to room temperature to obtain a reaction solution. The reaction solution was washed twice with water, and the organic layer was dehydrated with magnesium sulfate. The mixture was then passed through a Kiriyama funnel filled with silica gel. The filtrate was concentrated on a rotary evaporator to obtain 13.37 g of compound 47 (96.6% yield).

[0480] Compound 47 1 The H-NMR measurement results are as follows: δ(ppm):7.73 (s, 2H), 7.64 (s, 2H), 7.45-7.43 (m, 7H), 7.33-7.31 (m, 2H), 7.26 (s, 2H), 7.22 (s, 1H), 7.16-7.13 (m, 1H), 6.93 (d, 1H), 6.65 (d, 1H), 6.44 (d, 1H), 2.64 (t, 4H), 1.67-1.58 (m, 4H), 1.34-1.26 (m, 12H), 0.86 (t, 6H)

[0481] Compound 47 was used to synthesize compound 48.

[0482] [ka]

[0483] Compound 47 (25.0 g), tetraethylethylenediamine (5.6 mL), and dehydrated tetrahydrofuran (436 mL) were placed in an argon-purged flask and stirred to dissolve. The solution was then cooled to -65 °C in a cooling bath containing dry ice and acetone. A 1.6 mol / L nBuLi hexane solution (58.9 mL) was then added dropwise to the flask and stirred at -65 °C for 2 hours. While maintaining the temperature at -65 °C, a solution of triisopropoxyborane (19.74 g) in 40 mL of THF was added dropwise to the flask. The mixture was stirred at -65 °C for an additional hour, and then warmed to room temperature to obtain a reaction solution. Next, 290 mL of 2% hydrochloric acid was added to the reaction solution, and the mixture was separated. Magnesium sulfate and trimethylolethane (13.5 g) were added to the organic layer and stirred at room temperature for 1 hour. The magnesium sulfate was removed by filtration, and the filtrate was obtained. The solvent was removed from the filtrate under reduced pressure, toluene (700 mL) was added, the precipitated solid was removed by filtration, hexane was added, the supernatant was removed, and the solvent was removed under reduced pressure to obtain 37.7 g of compound 48 (yield 109%).

[0484] Compound 49 was synthesized using compound 44.

[0485] [ka]

[0486] Magnesium (12.37 g), THF (360 mL), and iodine (two grains) were added to an argon-purged flask and stirred. After the purple color of the iodine disappeared, a solution containing 1-bromo-3,5-diphenylbenzene (148.48 g) and THF (280 mL) was added dropwise to generate a Grignard reagent. A THF (820 mL) solution of compound 44 (35.88 g), synthesized by the method described in WO 2011 / 136311, was added dropwise so that the internal temperature did not exceed 40°C, yielding a reaction solution. The mixture was then stirred overnight, and the reaction was quenched by adding 10% aqueous ammonium chloride solution (450 mL) to the reaction solution, followed by separation. The organic layer was dehydrated over magnesium sulfate, the magnesium sulfate was removed by filtration, and the filtrate was concentrated on a rotary evaporator. The residue was purified by silica gel column chromatography (using hexane and ethyl acetate as the developing solvent) to obtain 128.6 g of Compound 49 (yield 99%).

[0487] Compound 50 was synthesized using compound 49.

[0488] [ka]

[0489] Compound 49 (128.6 g) and toluene (1376 mL) were charged into an argon-purged flask. The atmosphere in the reaction vessel was purged with nitrogen, and then p-toluenesulfonic acid monohydrate (5.39 g) was added. The temperature was raised to 100 °C, stirred for 1.5 hours, and then cooled to room temperature to obtain a reaction solution. The reaction solution was washed with water, and the organic layer was dehydrated over magnesium sulfate. The magnesium sulfate was removed by filtration, and the filtrate was concentrated on a rotary evaporator. Hexane (150 mL) was added to precipitate a solid, followed by the addition of toluene (50 mL) and hexane (50 mL). The mixture was then ice-cooled for 60 minutes, after which the precipitated solid was filtered and dried to obtain 106 g of compound 50 (96% yield).

[0490] Compound 51 was synthesized using compound 50.

[0491] [ka]

[0492] Compound 50 (28.38 g), tetraethylethylenediamine (6.5 mL), and 568 mL of anhydrous THF were placed in an argon-purged flask and stirred to dissolve. The solution was then cooled to -65 °C in a cooling bath containing dry ice and acetone, and a 1.6 mol / L nBuLi hexane solution (69.9 mL) was added dropwise and stirred at -65 °C for 1 hour. While maintaining the temperature at -65 °C, a solution of triisopropoxyborane (22.96 g) dissolved in 11.4 mL of THF was added dropwise, and the mixture was stirred at -65 °C for an additional 1 hour, after which the mixture was allowed to warm to room temperature. Next, 329 mL of 10% hydrochloric acid was added to the reaction mixture, and the mixture was separated. Magnesium sulfate and trimethylolethane (15.72 g) were added to the organic layer, and the mixture was stirred at room temperature for 1 hour. The magnesium sulfate was removed by filtration. The filtrate was evaporated under reduced pressure, chloroform (480 mL) was added, and the mixture was refrigerated overnight. The precipitated solid was removed, and the filtrate was evaporated under reduced pressure to give a crude product. The crude product was recrystallized from ethanol and hexane to give 36.18 g (yield 91.5%) of compound 51.

[0493] Compound 52 was synthesized according to the procedure described in the literature (Patent No. 6070722).

[0494] [ka]

[0495] Compound 48 (0.39 mmol), compound 51 (0.39 mmol), compound 52 (1.18 mmol), 4,7-dibromo-5,6-difluoro-2,1,3-benzothiadiazole (0.40 mmol), 4,7-dibromo[1,2,5]thiadiazolo[3,4-c]pyridine (1.60 mmol), water (59.5 g), 40% by weight potassium phosphate aqueous solution (10.5 mL), THF (42 mL), tetralin (20 mL), and bis(tri-tert-butylphosphine)palladium(0) (0.02 mmol) were added to a glass reaction vessel equipped with a cooling device at room temperature and stirred for 1 hour at 65 ° C. A mixture of phenylboronic acid (2 mmol) and a 40% by weight potassium phosphate aqueous solution (7.2 mL) was added to the reaction vessel and stirred for 1 hour at 65 ° C. The resulting organic layer was washed with an aqueous solution of sodium diethyldithiocarbamate, aqueous acetic acid, and water, and then added to methanol to collect the precipitated solid by filtration as a crude polymer. The resulting crude polymer was dissolved in tetralin and passed through 5B (JIS P 3801: 5 type B) filter paper, and then added to methanol again to collect the precipitated solid by filtration, yielding polymer compound P-20.

[0496] <Solubility test> Compounds N-1, N-2, N-3, N-4, N-5, RN-1, and RN-2 were each weighed out in amounts of 1 mg to 5 mg, and solutions in 1,2,4-tetramethylbenzene (TMB) were prepared to concentrations of 3.0 mass%, 2.5 mass%, 2.0 mass%, and 1.5 mass%. The prepared solutions were stirred at 300 rpm for 15 minutes, and the dissolution of the compounds was visually confirmed. The concentrations at which dissolution was confirmed are listed in the table below. Compounds that were confirmed to dissolve in the 3 wt% TMB solution were deemed to have a solubility of greater than 3 mass% and are listed as >3 mass%.

[0497] [Table 1]

[0498] The compounds of the present disclosure have been found to have superior solubility compared to conventional compounds.

[0499] <Measurement of optical absorption spectrum of thin films> Compounds N-1, N-2, N-3, N-4, N-5, and RN-3 were each added to orthodichlorobenzene to a concentration of 1.0% by mass. The mixture was heated and stirred for 4 hours at 65°C under a nitrogen atmosphere to prepare a solution. The filtrate was used as the coating solution. The coating solution was placed on a glass substrate whose surface had been cleaned with UV-ozone, and a film was formed by spin coating. The spin-coated coating film was placed on a hot plate. It was then dried in air at 70°C for 5 minutes to obtain a thin film for UV-Vis spectrum measurement. The optical absorption spectrum was measured using this thin film, and the case where absorption was confirmed at 1350 nm was judged as Y, and the case where no absorption was confirmed was judged as N.

[0500] [Table 2]

[0501] It was found that thin films prepared using the compounds of the present disclosure can absorb light of longer wavelengths than thin films prepared using conventional compounds.

[0502] <Ink Preparation> (Preparation of Ink I-1) The following components were mixed and stirred for 8 hours at 60° C. The resulting mixture was filtered using a filter to obtain ink I-1. P-type semiconductor material: polymer compound P-20...2.3% by mass N-type semiconductor material: Compound N-1...2.3% by mass Solvent: 1,2,4-trimethylbenzene / 1,2-dimethoxybenzene = 90% by mass / 10% by mass...the remaining amount that makes up 100% of the total ink

[0503] (Preparation of Ink I-2) The following components were mixed and stirred for 8 hours at 60° C. The resulting mixture was filtered using a filter to obtain ink I-2. P-type semiconductor material: polymer compound P-2...2.3% by mass N-type semiconductor material: Compound N-2...2.3% by mass Solvent: 1,2,4-trimethylbenzene / 1,2-dimethoxybenzene = 90% by mass / 10% by mass...the remaining amount that makes up 100% of the total ink

[0504] (Preparation of Ink I-3) The following components were mixed and stirred for 8 hours at 60° C. The resulting mixture was filtered using a filter to obtain ink I-3. P-type semiconductor material: polymer compound P-1...2.3% by mass N-type semiconductor material: Compound N-3...2.3% by mass Solvent: 1,2,4-trimethylbenzene / 1,2-dimethoxybenzene = 90% by mass / 10% by mass...the remaining amount that makes up 100% of the total ink

[0505] (Preparation of Inks I-4 and I-5) Inks I-4 and I-5 were obtained in the same manner as for Ink I-3, except that Compound N-3 was changed to Compounds N-4 and N-5.

[0506] <Production of photoelectric conversion element and its sealed body> (Preparation of Sample 1) A glass substrate on which a thin film of ITO (anode) was formed to a thickness of 45 nm by sputtering was prepared, and this glass substrate was subjected to ozone UV treatment as a surface treatment.

[0507] Next, a zinc oxide dispersion (Avantama, product name N-10) was applied to the cleaned glass substrate by spin coating to form a coating film, and then the substrate was placed on a hot plate and dried in the atmosphere at 100°C for 10 minutes to form an electron transport layer.

[0508] Next, Ink I-1 was applied onto the electron transport layer by spin coating to form a coating film, which was then dried by heating for 5 minutes on a hot plate heated to 70°C in air (pre-bake step), and then heated for 10 minutes on a hot plate at 100°C in a nitrogen atmosphere (post-bake step) to form an active layer. The thickness of the formed active layer was approximately 400 nm.

[0509] Next, a molybdenum oxide (MoO3) layer was formed on the formed active layer to a thickness of about 30 nm to serve as a hole transport layer.

[0510] Next, a silver (Ag) layer was formed on the formed hole transport layer to a thickness of about 60 nm to serve as a cathode. Through the above steps, a photoelectric conversion element was manufactured on the glass substrate.

[0511] Next, a UV-curable sealant was applied to the outer periphery of a glass substrate serving as a sealing substrate, and the glass substrate serving as a sealing substrate was attached to the center of the glass substrate serving as a support substrate. The glass substrate was then irradiated with UV light to seal the photodetector in the gap between the support substrate and the sealing substrate, thereby obtaining a sealed photoelectric conversion element. The photoelectric conversion element sealed in the gap between the support substrate and the sealing substrate had a planar shape of 2 mm x 2 mm square when viewed from the thickness direction. The resulting sealed element was designated Sample 1.

[0512] (Preparation of Samples 2 to 5) The sealed bodies Samples 2, 3, 4, and 5 were obtained in the same manner as Sample 1, except that Ink I-1 was changed to Inks I-2, I-3, I-4, and I-5.

[0513] [Evaluation of photoelectric conversion elements] With a reverse bias voltage of 3 V applied to the obtained photoelectric conversion element, a spectral sensitivity measurement device (manufactured by Bunkoukeiki Co., Ltd., product name: CEP-25SC type) was used to measure the photoelectric conversion element with monochromatic light of 1500 nm (photon count: 1 × 10 14) was irradiated onto the photoelectric conversion element, the generated current value was measured, and a photodiode drive test was performed using a known method. In this test, if photoelectric conversion was confirmed at 1350 nm, it was judged as Y, and if photoelectric conversion was not confirmed, it was judged as N.

[0514] [Table 3]

[0515] <The distance between two atoms that can interact non-covalently (d A1-A2 )> Next, for Compound N-1 and Compound N-2, the distance (d A1-A2 ) was calculated.

[0516] d A1-A2 The quantum chemistry calculation program Gaussian 03 was used to perform ground state structural optimization using the density functional theory at the B3LYP level, with 6-31g* as the basis function. The obtained ground state optimized structure was then calculated using GaussVeiw 6. A1-A2 was calculated. In addition, d A1-A2 In calculating the alkyl group contained in each compound, a propyl group (-CH2-CH2-CH3) was used as an example. The calculated values ​​for the compound before and after the alkyl group was changed to a propyl group are almost the same.

[0517] [Table 4]

[0518] It was found that a photoelectric conversion element using the compound of the present disclosure as an n-type semiconductor material is capable of photoelectric conversion up to long wavelengths. [Explanation of symbols]

[0519] 10 Photoelectric conversion element 11 Support substrate 12 Anode 13 Hole transport layer 14 Active layer 15 Electron transport layer 16 Cathode 17 Sealing member

Claims

1. A compound represented by the following formula (1): 【Chemistry 1】 (In formula (1), D is a divalent aromatic group having two bonds, and the conjugated structure connecting the two bonds in D by the shortest distance contains three or more double bonds; L1 and L2 each independently represent a divalent aromatic group different from D, and among all units represented by L1 and L2, at least one unit has a side chain that is incapable of non-covalently interacting with an element in another adjacent unit, but does not have a side chain that is capable of non-covalently interacting with an element in another adjacent unit, and at least one other unit different from the at least one unit has a side chain that is capable of non-covalently interacting with an element in another adjacent unit, L1 and L2 may be the same or different, m is 2 or 3, and n is an integer from 1 to 3; A1 and A2 each independently represent an electron-withdrawing monovalent group having at least one aromatic ring.

2. 2. The compound of claim 1, wherein m is 2 and n is 1 or 2.

3. The compound according to claim 1 or 2, wherein L1 and L2 are each independently any of groups represented by the following formulas (L1-1) to (L1-8): 【Chemistry 2】 (In formulas (L1-1) to (L1-8), R Ｌ１ are each independently hydrogen atoms, halogen atoms, an alkyl group which may have a substituent, an optionally substituted cycloalkyl group, an optionally substituted aryl group; an alkyloxy group which may have a substituent; an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an alkylthio group which may have a substituent; an optionally substituted cycloalkylthio group, an optionally substituted arylthio group; an optionally substituted monovalent heterocyclic group, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted carbonyl group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; a substituted sulfonyl group which may have a substituent; a substituted oxysulfonyl group which may have a substituent; an alkenyl group which may have a substituent; an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group; an optionally substituted cycloalkynyl group, a cyano group, or represents a nitro group, Furthermore, R Ｌ１ is a side chain capable of non-covalent interactions, R Ｌ１ each independently has at least one atom selected from the group consisting of a halogen atom, a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, and a phosphorus atom.

4. The compound according to claim 1 or 2, wherein D is any of the structures represented by the following formulas (D-1) to (D-7): 【Transformation 3】 In formulas (D-1), (D-2), (D-6), and (D-7), X is any of the groups represented by the following formulas (X-1) to (X-6): 【Chemistry 4】 In formulas (D-3) to (D-7) and formulas (X-1) to (X-6), R ｄ are each independently hydrogen atoms, halogen atoms, an alkyl group which may have a substituent, an optionally substituted cycloalkyl group, an optionally substituted aryl group; an alkyloxy group which may have a substituent; an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an alkylthio group which may have a substituent; an optionally substituted cycloalkylthio group, an optionally substituted arylthio group; an optionally substituted monovalent heterocyclic group, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted carbonyl group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; a substituted sulfonyl group which may have a substituent; a substituted oxysulfonyl group which may have a substituent; an alkenyl group which may have a substituent; an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group; an optionally substituted cycloalkynyl group, a cyano group, or represents a nitro group, In formula (D-2), formula (D-5) and formula (D-7), Ar １ and Ar ２ are each independently an aromatic carbocyclic ring which may have a substituent and may be further condensed with a plurality of ring structures, or an aromatic heterocyclic ring which may have a substituent and may be further condensed with a plurality of ring structures. １ and Ar ２ Either one of them may not be present.)

5. The compound according to claim 1 or claim 2, wherein A1 and A2 are each independently any of groups represented by the following formulas (a-1) to (a-5): 【Transformation 5】 (In the above formulas (a-1) to (a-5), T represents a carbocyclic ring which may have a substituent, or a heterocyclic ring which may have a substituent. The carbocyclic ring and heterocyclic ring may be a single ring or a condensed ring. When these rings have a plurality of substituents, the plurality of substituents may be the same or different. X ４ , X ５ , and X ６ are each independently an oxygen atom, a sulfur atom, an alkylidene group, ═C(—CN) ２ or =C(-CN)-CR ａ represents a group represented by R ａ represents an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an aromatic alkyl group having 5 to 30 carbon atoms, an aromatic alkenyl group having 5 to 30 carbon atoms, or an aromatic alkynyl group having 5 to 30 carbon atoms, and the alkyl group, alkenyl group, alkynyl group, aromatic alkyl group, aromatic alkenyl group, and aromatic alkynyl group may have a substituent and may be linear, branched, or cyclic.

6. A composition comprising a p-type semiconductor material and an n-type semiconductor material, wherein the n-type semiconductor material comprises the compound according to claim 1 or 2.

7. The composition according to claim 6, wherein the p-type semiconductor material is a polymer compound containing at least one selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4): 【Transformation 6】 (In formula (3), Ar ３ and Ar ４ each independently represents a trivalent aromatic heterocyclic group which may have a substituent, and Z represents any of the groups represented by the following formulas (Z-1) to (Z-7): 【Transformation 7】 In formulas (Z-1) to (Z-7), Each R is independently hydrogen atoms, halogen atoms, an alkyl group which may have a substituent, an optionally substituted cycloalkyl group, an optionally substituted aryl group; an alkyloxy group which may have a substituent; an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an alkylthio group which may have a substituent; an optionally substituted cycloalkylthio group, an optionally substituted arylthio group; an optionally substituted monovalent heterocyclic group, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; an alkenyl group which may have a substituent; an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group; an optionally substituted cycloalkynyl group, an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, a cyano group, or represents a nitro group, In each of formulas (Z-1) to (Z-7), when there are two R, the two R may be the same or different, In formula (4), Ar ５ represents a divalent aromatic heterocyclic group.

8. An ink comprising the compound according to claim 1 or 2 and a solvent.

9. an anode, a cathode, and an active layer provided between the anode and the cathode and including a p-type semiconductor material and an n-type semiconductor material; A photoelectric conversion element comprising the compound according to claim 1 or 2 as the n-type semiconductor material.

10. The photoelectric conversion element according to claim 9 , which is a photodetector element.

11. An optical sensor comprising the photoelectric conversion element according to claim 10.

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