Compound, composition, ink, photoelectric conversion element, and photosensor

Abstract

The present invention addresses the problem of providing a compound, a composition, an ink, a photoelectric conversion element, and an optical sensor, which each enables photoelectric conversion in a long wavelength region.　A solution is a compound represented by formula (1) wherein, in formula (1), the distance from the element on the D side of the elements forming the single bond between D and L1 to the element on the A1 side of the elements forming the single bond between A1 and L1 is at least 9 Å. A1, A2, L1, L2, D, m, and n in formula (1) are as defined in the Description. The photoelectric conversion element contains an anode, a cathode, and an active layer which is disposed between the anode and cathode and contains a p-type semiconductor material and an n-type semiconductor material. The n-type semiconductor material contains a compound represented by formula (1).

Description

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

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

[0002] 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 provided between the pair of electrodes. 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] As a compound used in a photoelectric conversion element, for example, Patent Document 1 discloses a near-infrared organic photoreceptor molecule CN5T that utilizes a 3-alkoxy-4-cyanothiophene structure. Patent Document 1 discloses that the absorption edge wavelength in the absorption spectrum of CN5T in a thin film state is around 1200 nm.

[0004] Chinese Patent Application Publication No. 114195801

[0005] However, knowledge regarding compounds that enable photoelectric conversion at wavelengths of 1400 nm or longer, which is particularly long within the SWIR (Short Wavelength Infrared) region, is currently limited.

[0006] The present disclosure has been made in view of the above, and relates to providing a compound, a composition, an ink, a photoelectric conversion element, and an optical sensor that enable photoelectric conversion in the long wavelength region.

[0007] Specific means for solving the above problems include the following embodiments: <1> A compound represented by the following formula (1), in which the distance from an element on the D side among elements forming a single bond between D and L1 to an element on the A1 side among elements forming a single bond between A1 and L1 is 9 Å or more.

[0008]

[0009] (In formula (1), D is a divalent aromatic group, the main skeleton of the monocyclic or fused ring constituting the aromatic group in D has at least one of an sp3 carbon and an sp3 silicon, and D is a monovalent side chain R bonded to the sp3 carbon or the sp3 silicon. Ｄ１ L1 is a divalent aromatic group, the main skeleton of the monocyclic or fused ring constituting the aromatic group in L1 may or may not have an sp3 carbon or an sp3 silicon, and when it has an sp3 carbon or an sp3 silicon, L1 does not have a monovalent side chain bonded to the sp3 carbon or the sp3 silicon in L1, the main skeleton of the monocyclic or fused ring constituting the aromatic group in L1 has an sp2 carbon, and L1 does not have a monovalent side chain R bonded to the sp2 carbon. Ｌ１ The aromatic group in L1 has an element capable of non-covalent interaction with an element in an adjacent unit, and R Ｄ１ and R Ｌ１each independently represents a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio 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 amido group, an optionally substituted acid imide group, an optionally substituted substituted carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group; L2 is a divalent aromatic group; m is an integer of 1 to 4, n is an integer of 0 to 4, and A1 and A2 are each independently a group represented by the following formula (A-1).

[0010]

[0011] In formula (A-1), Ar represents a carbocycle which may have a substituent, or a heterocycle which may have a substituent, and the carbocycle and the heterocycle are each independently a monocycle or a fused ring, and when the carbocycle or the heterocycle has a plurality of substituents, the plurality of substituents may be the same or different.) <2> The compound according to <1>, wherein in formula (1), D is any of groups represented by the following formulas (D-1) to (D-4):

[0012]

[0013] (In formulas (D-1) to (D-4), X is any of the groups represented by the following formulas (X-1) to (X-6):

[0014]

[0015] In formula (D-3), formula (D-4), and formulas (X-1) to (X-6), R Ｄ２ each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio 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 amido group, an optionally substituted acid imide group, an optionally substituted substituted carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group. 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 <3> The compound according to <1> or <2>, wherein in formula (1), L1 is each independently any of groups represented by the following formulas (L1-1) to (L1-7):

[0016]

[0017] (In formulas (L1-1) to (L1-7), R Ｌ１１ each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio 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 amido group, an optionally substituted acid imide group, an optionally substituted substituted carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group; further R Ｌ１１ each independently has at least one atom selected from the group consisting of a sulfur atom, an oxygen atom, a fluorine atom, a nitrogen atom, a selenium atom, and a phosphorus atom.) <4> The compound according to any one of <1> to <3>, wherein in formula (1), L2 each independently represents any group represented by the following formulas (L2-1) to (L2-9):

[0018]

[0019] (In formulas (L2-1) to (L2-9), a plurality of R Ｌ２each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio 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 amido group, an optionally substituted acid imide group, an optionally substituted substituted carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group. <5> The compound according to any one of <1> to <4>, wherein in the formula (1), m is 2 and n is 1 or 2. <6> The compound according to any one of <1> to <5>, wherein in the formula (1), A1 and A2 each independently represent any group represented by the following formulas (a-1) to (a-8):

[0020]

[0021] (In formulas (a-1) to (a-8), a plurality of R Ａ１ are each independently a hydrogen atom, a halogen atom, or a cyano group.) <7> A composition comprising a p-type semiconductor material and an n-type semiconductor material, wherein the n-type semiconductor material comprises the compound described in any one of <1> to <6>. <8> The composition according to <7>, 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):

[0022]

[0023] (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):

[0024]

[0025] In formulae (Z-1) to (Z-7), R each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio 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 carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or 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. ５represents a divalent aromatic heterocyclic group.) <9> An ink containing the compound according to any one of <1> to <6> and a solvent. <10> A photoelectric conversion element comprising an anode, a cathode, and an active layer provided between the anode and the cathode and containing a p-type semiconductor material and an n-type semiconductor material, wherein the n-type semiconductor material contains the compound according to any one of <1> to <6>. <11> The photoelectric conversion element according to <10>, which is a light detection element. <12> An optical sensor comprising the photoelectric conversion element according to <10> or <11>.

[0026] According to the present disclosure, there are provided a compound, composition, ink, photoelectric conversion element, and optical sensor that enable photoelectric conversion in the long wavelength region.

[0027] FIG. 1 is a diagram schematically illustrating an example of the configuration of a photoelectric conversion element.

[0028] 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.

[0029] 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.

[0030] In the present disclosure, when a numerical range is indicated using "to", the numerical values ​​before and after "to" are included as the lower and upper limits, respectively. In the present disclosure, when a numerical range is described in stages, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another staged numerical range. Furthermore, in the present disclosure, the upper or lower limit of that numerical range may be replaced with a value shown in the examples. In the present disclosure, when multiple substances corresponding to each component are present in the composition, the content of each component refers to 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", this does not exclude the combination of multiple elements unless a technical contradiction occurs, unless otherwise specified. In the present disclosure, when an element is described in the singular, this does not exclude the presence of multiple elements unless a technical contradiction occurs, unless otherwise specified. In the present disclosure, multiple exemplary embodiments described separately may be combined with each other to form a new embodiment, unless mutually contradictory.

[0031] The following describes commonly used terms in this disclosure. In the description of this disclosure, the following descriptions apply unless otherwise specified.

[0032] The term "non-fullerene compound" refers to a compound that is neither a fullerene nor a fullerene derivative.

[0033] The term "π-conjugated system" refers to a system in which π electrons are delocalized among multiple bonds.

[0034] The term "polymer compound" refers to a compound having a molecular weight distribution and a polystyrene-equivalent number average molecular weight of 1×10 ３ 1x10 or more ８ The total amount of structural units contained in the polymer compound is 100 mol %.

[0035] 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.

[0036] The "hydrogen atom" may be a protist atom or a deuterium atom.

[0037] Examples of "halogen atoms" include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0038] 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.

[0039] 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, when referring to the number of carbon atoms, the number of carbon atoms does not usually include the number of carbon atoms of the substituent.

[0040] In this specification, unless otherwise specified, an "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 of substituents, 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 of substituents, is usually preferably 3 to 50, more preferably 3 to 30, and even more preferably 4 to 20.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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 of the substituent, is usually preferably 3 to 30, and more preferably 12 to 19.

[0045] 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.

[0046] Specific examples of the substituted cycloalkyl group include a methylcyclohexyl group and an ethylcyclohexyl group.

[0047] 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 which 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.

[0048] The term "aryl group" refers to a monovalent aromatic carbocyclic group, which is an 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 has been substituted with a substituent such as an alkyl group, an alkyloxy group, an aryl group, or a fluorine atom.

[0050] The "alkyloxy group" (alkoxy group) may be any of linear, branched, and cyclic. The number of carbon atoms in a linear alkyloxy group, not including the number of carbon atoms of 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 of the substituent, is usually preferably 3 to 40, more preferably 4 to 10.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] The number of carbon atoms in the "aryloxy group" is usually preferably 6 to 60, more preferably 6 to 48, not including the number of carbon atoms of the substituents.

[0055] 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 the hydrogen atoms in these groups are substituted with substituents such as an alkyl group, an alkyloxy group, or a fluorine atom.

[0056] 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 of substituents, 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 of substituents, is usually preferably 3 to 40, more preferably 4 to 10.

[0057] 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.

[0058] 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 of the substituent, is usually preferably 3 to 30, and more preferably 12 to 19.

[0059] Examples of the optionally substituted cycloalkylthio group include a cyclohexylthio group.

[0060] The number of carbon atoms in the "arylthio group" is usually preferably 6 to 60, more preferably 6 to 48, not including the number of carbon atoms of the substituents.

[0061] 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.

[0062] 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.

[0063] The heterocyclic group may further have a substituent. The number of carbon atoms of the heterocyclic group is usually preferably 2 to 30, more preferably 2 to 6, not including the number of carbon atoms of the substituent.

[0064] Examples of the substituent 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."

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] The number of carbon atoms in the monovalent heterocyclic group is usually preferably 2 to 60, more preferably 4 to 20, not including the number of carbon atoms in the substituent.

[0070] 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.

[0071] 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, with an alkyl group, an aryl group, or a monovalent heterocyclic group being preferred. The number of carbon atoms in the substituted amino group is usually preferably 2 to 30.

[0072] 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.

[0073] The "acyl group" may have a substituent. The number of carbon atoms in the acyl group, not including the number of carbon atoms of 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.

[0074] 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.

[0075] The imine residue generally preferably has 2 to 20 carbon atoms, more preferably 2 to 18 carbon atoms. Examples of the imine residue include groups represented by the following structural formula: In the following structural formula, Me represents a methyl group.

[0076]

[0077] 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.

[0078] 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 an acid imide group is usually preferably 4 to 20. Specific examples of acid imide groups include groups represented by the following structural formula: In the structural formula, Me represents a methyl group.

[0079]

[0080] The term "substituted carbonyl group" refers to a group represented by -(C=O)-R Ｘ where R Ｘ represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

[0081] The "substituted oxycarbonyl group" is a group represented by -(C=O)-O-R 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] The number of carbon atoms of the substituted oxycarbonyl group is usually preferably 2 to 60, more preferably 2 to 48, not including the number of carbon atoms of the substituent.

[0083] 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.

[0084] The "substituted sulfonyl group" is a group represented by -SO ２ -R Ｘ where R Ｘ represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

[0085] The term "substituted oxysulfonyl group" refers to a group selected from the group consisting of -(SO ２ )-O-R Ｘ or -O-(SO ２ )-R Ｘ where R Ｘ represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic 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 of substituents, 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 of substituents, 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 vinyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 5-hexenyl, 7-octenyl, and groups in which hydrogen atoms in these groups are substituted with alkyl groups, alkyloxy groups, aryl groups, or fluorine atoms.

[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 of 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 any of linear, branched, and cyclic. The number of carbon atoms in a linear alkynyl group, not including the number of carbon atoms of substituents, 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 of substituents, 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 has been 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 "*" that may be attached to a chemical formula represents a bond. A dotted line in a chemical formula also represents a bond. When a chemical formula contains two symbols "*" and two dotted lines, there is no particular limitation as to which of the two units to which the bond is attached.

[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 a value expressed as a 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), in which the distance from the element on the D side among the elements forming a single bond between D and L1 to the element on the A1 side among the elements forming a single bond between A1 and L1 is 9 Å or more.

[0103]

[0104] In formula (1), D is a divalent aromatic group, the main skeleton of the monocyclic or fused ring constituting the aromatic group in D has at least one of an sp3 carbon and an sp3 silicon, and D is a monovalent side chain R bonded to the sp3 carbon or the sp3 silicon. Ｄ１L1 is a divalent aromatic group, the main skeleton of the monocyclic or fused ring constituting the aromatic group in L1 may or may not have an sp3 carbon or sp3 silicon, and when it has an sp3 carbon or sp3 silicon, L1 does not have a monovalent side chain bonded to the sp3 carbon or sp3 silicon in L1, the main skeleton of the monocyclic or fused ring constituting the aromatic group in L1 has an sp2 carbon, and L1 does not have a monovalent side chain R bonded to the sp2 carbon. Ｌ１ The aromatic group in L1 has an element capable of non-covalent interaction with an element in an adjacent unit, and R Ｄ１ and R Ｌ１ each independently represents a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio 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 amido group, an optionally substituted acid imide group, an optionally substituted substituted carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group; L2 is a divalent aromatic group; m is an integer of 1 to 4, n is an integer of 0 to 4, and A1 and A2 are each independently a group represented by the following formula (A-1).

[0105]

[0106] In formula (A-1), Ar represents a carbocycle which may have a substituent, or a heterocycle which may have a substituent, and the carbocycle and the heterocycle are each independently a monocycle or a fused ring, and when the carbocycle or the heterocycle has a plurality of substituents, the plurality of substituents may be the same or different.

[0107] The compound of the present disclosure enables photoelectric conversion in the long wavelength region. The action of the compound of the present disclosure is not clear, but is presumed as follows. In the compound of the present disclosure, represented by formula (1), the group represented by D is a core, and (L1) ｍ and (L2) ｎ The groups represented by A1 and A2 are each linkers, and the groups represented by A1 and A2 are each acceptors.

[0108] In formula (1), the main skeleton of the monocyclic or fused ring constituting the aromatic group in D has at least one of an sp3 carbon and an sp3 silicon, and D is a monovalent side chain R Ｄ１ That is, in formula (1), D has at least one side chain R Ｄ１ has a structure that protrudes perpendicularly to the main skeleton (i.e., the π plane) of the single ring or fused ring that constitutes the aromatic group in D. Therefore, in a thin film formed from the compound of the present disclosure, the side chain R protruding from the π plane in D Ｄ１ As a result, compounds of the present disclosure are less likely to form H-association between molecules, while compounds of the present disclosure are more likely to form J-association between molecules. More specifically, A1 of a certain molecule of a compound of the present disclosure is more likely to associate with A1 and A2 of another molecule of a compound of the present disclosure. Alternatively, A2 of a certain molecule of a compound of the present disclosure is more likely to associate with A1 and A2 of another molecule of a compound of the present disclosure.

[0109] Furthermore, in formula (1), the main skeleton of the monocyclic or fused ring constituting the aromatic group in L1 may or may not have an sp3 carbon or sp3 silicon, and when it has an sp3 carbon or sp3 silicon, L1 does not have a monovalent side chain bonded to the sp3 carbon or sp3 silicon. On the other hand, the main skeleton of the monocyclic or fused ring constituting the aromatic group in L1 has an sp2 carbon, and L1 does not have a monovalent side chain R bonded to the sp2 carbon. Ｌ１ The side chain R bonded to the sp2 carbon in L1 is Ｌ１ is a structure (a structure existing on the same π plane) that does not protrude from the main skeleton (i.e., the π plane) of the monocyclic or fused ring constituting the aromatic group in L1, and therefore, the side chain R Ｌ１ does not inhibit J-association of the compound of the present disclosure. That is, since L1 does not have a side chain protruding from the main skeleton (i.e., the π-plane) of the monocyclic or fused ring constituting the aromatic group in L1, it is thought that L1 does not inhibit J-association in the formed thin film.

[0110] Furthermore, in formula (1), the distance from the element on the D side among the elements forming the single bond between D and L1 to the element on the A1 side among the elements forming the single bond between A1 and L1 is 9 Å or more. ｍ When "-" has a certain length or more, the side chain R Ｄ１ The distance between A1 and D becomes longer, and the side chain R Ｄ１ does not inhibit J-association by A1 and A2. Note that, when the distance from the element on the D side among the elements forming the single bond between D and L1 to the element on the A1 side among the elements forming the single bond between A1 and L1 is less than 9 Å, D and A1 are brought into close proximity, which causes the structure in the compound of the present disclosure to become crowded, making it difficult for J-association to occur.

[0111] Furthermore, in formula (1), the aromatic group in L1 has an element that can non-covalently interact with an element in an adjacent unit. Examples of adjacent units include A1 and L1, L1 and L1, or L1 and D. When the aromatic group in L1 has an element that can non-covalently interact with an element in an adjacent unit, a non-covalent bridge is formed between the element in L1 and the unit (A1, L1, or D) adjacent to L1. In other words, the planarity of the main skeleton (i.e., the π plane) of the single ring or fused ring that constitutes the aromatic group in L1 is likely to be maintained in the formed thin film.

[0112] As explained above, in a thin film formed from the compound of the present disclosure, the compound of the present disclosure is prone to J-aggregation. When the compound J-aggregates, the compound is prone to absorbing light with long wavelengths. When the compound H-aggregates, the compound is prone to absorbing light with short wavelengths. Due to the above-mentioned estimated action, the compound of the present disclosure absorbs light with long wavelengths of 1400 nm or more, enabling photoelectric conversion in the long wavelength region. However, the present disclosure is not limited in any way to the above-mentioned estimated mechanism.

[0113] <D; Core> [Aromatic Group] In formula (1), D is a divalent aromatic group. The aromatic group in D has a monocyclic or fused ring main skeleton. The aromatic group in D may be either an aromatic heterocyclic group or an aromatic carbocyclic group, and is preferably an aromatic heterocyclic group 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 a sulfur atom, a silicon atom, a selenium atom, a nitrogen atom, and an oxygen atom, and more preferably at least one selected from the group consisting of a sulfur atom, a silicon atom, a nitrogen atom, and an oxygen atom.

[0114] [Sp3 Atom] The main skeleton of the monocyclic or fused ring constituting the aromatic group in D has at least one of sp3 carbon and sp3 silicon. It is preferable that the main skeleton of the monocyclic or fused ring constituting the aromatic group in D has sp3 carbon or sp3 silicon.

[0115] D is a monovalent side chain R bonded to the sp3 carbon or the sp3 silicon. Ｄ１D has at least one monovalent side chain R bonded to the sp3 carbon or the sp3 silicon. Ｄ１ As described above, the main skeleton of the monocyclic or fused ring constituting the aromatic group in D has at least one of an sp3 carbon and an sp3 silicon, and D has a monovalent side chain R bonded to the sp3 carbon or the sp3 silicon. Ｄ１ As a result, the compound of the present disclosure has at least one side chain R Ｄ１ Since the compound of the present disclosure has a structure in which the groups protrude in the vertical direction, it is difficult for H-aggregation to occur in the formed thin film, but is likely to J-aggregate.

[0116] [Side chain R Ｄ１ ] Side chain R in D Ｄ１ each independently represents a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio 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 amido group, an optionally substituted acid imide group, an optionally substituted substituted carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group.

[0117] Side chain R in D Ｄ１is a structure that makes it difficult for the compound of the present disclosure to undergo H-aggregation and easy for J-aggregation in the formed thin film. Ｄ１ The specific structure of the side chain R in D is not particularly limited. Ｄ１ are each independently preferably an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted monovalent heterocyclic group, more preferably an optionally substituted alkyl group or an optionally substituted aryl group, and even more preferably an alkyl group.

[0118] [Chemical Structure of D] In view of the ease with which the compound absorbs 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-4), and more preferably a group represented by the following formula (D-1), (D-2), or (D-3). In the following formulas (D-1) to (D-4), the symbol "*" represents (L1) in formula (1). ｍ Bond with or (L2) ｎ This shows the bond between .

[0119]

[0120] In formulas (D-1) to (D-4), X is any of the groups represented by the following formulas (X-1) to (X-6).

[0121]

[0122] In formula (D-3), formula (D-4), and formulas (X-1) to (X-6), R Ｄ２The definitions of each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio 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 amido group, an optionally substituted acid imide group, an optionally substituted substituted carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group.

[0123] In each of formulas (X-1) to (X-6), R Ｄ２ If there are two R Ｄ２ may be the same or different. From the viewpoint that the compound easily absorbs light of a long wavelength, X is preferably any of the groups represented by formula (X-1) to formula (X-4), and more preferably any of the groups represented by formula (X-1), formula (X-3), or formula (X-4). In formula (D-3), formula (D-4), and formula (X-1) to formula (X-6), R Ｄ２ is preferably a hydrogen atom or the above-mentioned R Ｄ１ This is the same as the preferred embodiment of

[0124] In formula (D-2) and formula (D-4), 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] Ar １ and Ar ２ The 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.

[0126] 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.

[0127] 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.

[0128] Ar １ and Ar ２Specific 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.

[0129] (Examples of D) Examples of formula (D-1) include groups represented by the following formulas (d-1-1) to (d-1-7). Examples of formula (D-2) include groups represented by the following formulas (d-2-1) to (d-2-10). Examples of formula (D-3) include groups represented by the following formulas (d-3-1) to (d-3-2). Examples of formula (D-4) include groups represented by the following formulas (d-4-1) to (d-4-9). In addition, in formulas (d-1-1) to (d-1-7), R Ｄ２ The definitions of each independently are the same as those of R Ｄ２ In the following formulas (d-2-1) to (d-2-10), (d-3-1) to (d-3-2), and (d-4-1) to (d-4-9), R Ｄ２ The definitions of each independently are the same as those of R Ｄ２ In the following formulas (d-2-1) to (d-2-10) and (d-4-1) to (d-4-9), U each independently represents CR Ｄ２ ２ , S, SiR Ｄ２ ２ , Se, NR Ｄ２ or O. U is preferably S. In the following formulas (d-1-1) to (d-1-7), (d-2-1) to (d-2-10), (d-3-1) to (d-3-2), and (d-4-1) to (d-4-9), the symbol "*" represents (L1) in formula (1). ｍ Bond with or (L2) ｎ This shows the bond between .

[0130] From the viewpoint that the compound easily absorbs light of a long wavelength, D is preferably a group represented by formula (d-1-1), formula (d-1-3) to formula (d-1-7), or formula (d-2-1) to formula (d-2-10), more preferably a group represented by formula (d-1-1) or formula (d-1-3) to formula (d-1-7), and even more preferably a group represented by formula (d-1-1), formula (d-1-3), or formula (d-1-4).

[0131]

[0132]

[0133]

[0134]

[0135] (Specific Examples of D) Specific examples of D include groups represented by the following formulae: In each formula, the symbol "*" indicates (L1) in formula (1). ｍ Bond with or (L2) ｎ This shows the bond between .

[0136]

[0137]

[0138] <(L1) ｍ (L1) in formula (1) ｍ In the formula (1), when m is 2 or more, the chemical structure of each of the L1s present in the formula (1) is independently defined. In other words, the following description of L1 is a description of each of the L1s independently.

[0139] [Aromatic Group] In formula (1), L1 is a divalent aromatic group. The aromatic group in L1 has a monocyclic or fused ring main skeleton. The aromatic group in L1 may be either an aromatic heterocyclic group or an aromatic carbocyclic group, and is preferably an aromatic heterocyclic group 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 a sulfur atom, a silicon atom, a selenium atom, a nitrogen atom, and an oxygen atom, and more preferably at least one selected from the group consisting of a sulfur atom, a nitrogen atom, and an oxygen atom.

[0140] [sp3 atom, sp2 atom] The main skeleton of the monocyclic or fused ring constituting the aromatic group in L1 may or may not have sp3 carbon or sp3 silicon. When the main skeleton of the monocyclic or fused ring constituting the aromatic group in L1 has sp3 carbon or sp3 silicon, L1 does not have a monovalent side chain bonded to the sp3 carbon or sp3 silicon in L1. Note that "not having a monovalent side chain bonded to the sp3 carbon or sp3 silicon in L1" means that in the sp3 carbon or sp3 silicon in L1, two bonds form the main skeleton of the monocyclic or fused ring constituting the aromatic group in L1, and the remaining two bonds are each bonded to a hydrogen atom. In other words, "not having a monovalent side chain bonded to the sp3 carbon or sp3 silicon in L1" means that only hydrogen atoms protrude from the main skeleton (i.e., the π plane) of the monocyclic or fused ring constituting the aromatic group in L1.

[0141] On the other hand, the main skeleton of the monocyclic or fused ring constituting the aromatic group in L1 has an sp2 carbon, and L1 has a monovalent side chain R Ｌ１ L1 has at least one monovalent side chain R Ｌ１ As a result, as described above, L1 does not have a side chain that protrudes from the main skeleton (i.e., the π plane) of the monocyclic or fused ring that constitutes the aromatic group in L1, and therefore L1 does not inhibit the J-association of the compound in the formed thin film.

[0142] [Non-covalent Interaction] The aromatic group in L1 has an element that can have a non-covalent interaction with an element in an adjacent unit. In the present disclosure, A1, L1, L2, or D is each a structural unit, and the structural unit is referred to as a unit. The adjacent units may be adjacent units on both sides, or one of the adjacent units on both sides. Examples of adjacent units include A1 and L1, L1 and D, and (L1) ｍ When m is 2 or more, adjacent L1s can be mentioned.

[0143] The element possessed by the aromatic group in L1 and capable of non-covalently interacting with an element in an adjacent unit is preferably at least one atom selected from the group consisting of a sulfur atom, an oxygen atom, a fluorine atom, a nitrogen atom, a selenium atom, and a phosphorus atom, more preferably 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 at least one of a sulfur atom and an oxygen atom.

[0144] The aromatic group in L1 preferably has an element capable of non-covalently interacting with an element in an adjacent unit, selected from the group consisting of a sulfur atom-oxygen atom, a sulfur atom-fluorine atom, a sulfur atom-nitrogen atom, a selenium atom-oxygen atom, a selenium atom-nitrogen atom, a nitrogen atom-oxygen atom, and an oxygen atom-phosphorus atom.

[0145] Similarly, the unit adjacent to L1 preferably has at least one atom selected from the group consisting of a sulfur atom, an oxygen atom, a fluorine atom, a nitrogen atom, a selenium atom, and a phosphorus atom. The unit adjacent to L1 preferably has an element capable of non-covalently interacting with the aromatic group in L1, selected from the group consisting of a sulfur atom-oxygen atom, a sulfur atom-fluorine atom, a sulfur atom-nitrogen atom, a selenium atom-oxygen atom, a selenium atom-nitrogen atom, a nitrogen atom-oxygen atom, and an oxygen atom-phosphorus atom.

[0146] From the viewpoint of enabling non-covalent interactions, when the aromatic group in L1 has a sulfur atom, the unit adjacent to L1 preferably has at least one selected from the group consisting of an oxygen atom, a fluorine atom, and a nitrogen atom. When the aromatic group in L1 has an oxygen atom, the unit adjacent to L1 preferably has at least one selected from the group consisting of a sulfur atom, a selenium atom, a nitrogen atom, and a phosphorus atom. When the aromatic group in L1 has a fluorine atom, the unit adjacent to L1 preferably has a sulfur atom. When the aromatic group in L1 has a nitrogen atom, the unit adjacent to L1 preferably has at least one selected from the group consisting of a sulfur atom, a selenium atom, and an oxygen atom. When the aromatic group in L1 has a selenium atom, the unit adjacent to L1 preferably has at least one of an oxygen atom and a nitrogen atom. When the aromatic group in L1 has a phosphorus atom, the unit adjacent to L1 preferably has an oxygen atom.

[0147] At least one atom selected from the group consisting of a sulfur atom, an oxygen atom, a fluorine 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 may be contained in a side chain bonded to the main skeleton of the monocyclic or fused ring constituting the aromatic group in L1, and the side chain R Ｌ１ The non-covalent interaction may be formed between the main skeleton of the single ring or fused ring constituting the aromatic group in L1 and a side chain bonded to the main skeleton of the unit adjacent to L1, and the side chain R bonded to the main skeleton of the single ring or fused ring constituting the aromatic group in L1 may be Ｌ１ and the main skeleton of an adjacent unit to L1, or may be formed by side chains bonded to the main skeleton of a single ring or fused ring constituting the aromatic group in L1.

[0148] As described above, when the aromatic group in L1 contains 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 and the unit (A1, L1, or D) adjacent to L1. In other words, the planarity of the main skeleton (i.e., the π plane) of the single ring or fused ring constituting the aromatic group in L1 is likely to be maintained in the formed thin film.

[0149] [Side chain R Ｌ１ ] Side chain R in L1 Ｌ１ each independently represents a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio 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 amido group, an optionally substituted acid imide group, an optionally substituted substituted carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group.

[0150] From the viewpoint that the compound is likely to absorb light of a long wavelength, the side chain R Ｌ１are each independently preferably an alkyloxy group which may have a substituent, an alkylthio group which may have a substituent, a substituted amino group which may have a substituent, an alkyl group which may have a substituent, or a halogen atom, more preferably an alkyloxy group which may have a substituent or a halogen atom, and even more preferably an alkyloxy group which may have a substituent.

[0151] [Chemical Structure of L1] From the viewpoint of the compound easily absorbing light with long wavelengths, L1 in formula (1) is preferably each independently any of the groups represented by formulas (L1-1) to (L1-7) below, more preferably any of the groups represented by formulas (L1-1) to (L1-4) below, and even more preferably a group represented by formula (L1-1) below. That is, from the viewpoint of the compound easily absorbing light with long wavelengths, L1 preferably has a thiophene structure, a thienothiophene structure, a thiazole structure, or a benzothiadiazole structure.

[0152]

[0153] In formulas (L1-1) to (L1-7), R Ｌ１１ are each independently the R Ｄ２ In addition to the definition of R, it is preferable that R further has at least one atom selected from the group consisting of a sulfur atom, an oxygen atom, a fluorine atom, a nitrogen atom, a selenium atom, and a phosphorus atom. Ｌ１１ has at least one atom selected from the group consisting of a sulfur atom, an oxygen atom, a fluorine atom, a nitrogen atom, a selenium atom, and a phosphorus atom, and R Ｌ１１ When a unit adjacent to L1 having the formula (I) has an element capable of non-covalent interaction with at least one atom selected from the group consisting of a sulfur atom, an oxygen atom, a fluorine atom, a nitrogen atom, a selenium atom, and a phosphorus atom, R Ｌ１１ And, R Ｌ１１ In other words, in the formed thin film, the planarity of the main skeleton (i.e., the π plane) of the monocyclic or fused ring constituting the aromatic group in L1 is likely to be maintained.

[0154] (Specific Examples of L1) Specific examples of L1 include groups represented by the following formulae.

[0155]

[0156] (m) In formula (1), m is an integer of 1 to 4. From the viewpoint of the compound's tendency to absorb light of a long wavelength and the ease of synthesis, m is preferably an integer of 2 to 4, more preferably 2 or 3, and even more preferably 2.

[0157] ((L1) ｍ Specific example of (L1) ｍ Specific examples of L1 include the specific examples of L1 (i.e., (L1) ｍ In addition to specific examples where m is 1, groups represented by the following formulae are also included.

[0158]

[0159]

[0160] As described above, in formula (1), L1 is preferably a thiophene structure having an alkyloxy group, a thiadiazole structure having an alkyloxy group, a thienothiophene structure having an alkyloxy group, a thiophene structure having a halogen atom, or a thiophene structure having an alkylthio group, and more preferably a thiophene structure having an alkyloxy group. ｍ Preferably, the thiophene structure has at least one alkyloxy group-containing thiophene structure, and more preferably, the thiophene structure is an oligomer having an alkyloxy group.

[0161] [Distance] In the compound of the present disclosure, the distance from the element on the D side among the elements forming the single bond between D and L1 to the element on the A1 side among the elements forming the single bond between A1 and L1 is 9 Å or more. The distance is preferably 9.1 Å or more, and more preferably 9.2 Å or more. From the viewpoint of not reducing electron mobility, the upper limit of the distance is preferably 25 Å or less, more preferably 20 Å or less, and even more preferably 15 Å or less.

[0162] As mentioned above, "-(L1) ｍ When "-" has a certain length or more, the side chain R Ｄ１ The distance between A1 and L1 becomes longer. ｍ does not inhibit J-association of the compound by A1 and A2. Note that when the distance is less than 9 Å, D and A1 are close to each other, which crowds the structure in the compound of the present disclosure, making J-association less likely to occur. In the compound of the present disclosure, from the viewpoint of making the distance from the element on the D side among the elements forming the single bond between D and L1 to the element on the A1 side among the elements forming the single bond between A1 and L1 9 Å or more, when m is 1, L1 is preferably a dithienothiophene structure having an alkyloxy group. When m is an integer of 2 to 4, L1 is preferably a thiophene structure having an alkyloxy group, a thienothiophene structure having an alkyloxy group, or a thiophene structure having a halogen atom, and more preferably a thiophene structure having an alkyloxy group.

[0163] In the present disclosure, the distance (d Ｃ１－Ｃ２ ) can be calculated by the following method.

[0164] The distance (d Ｃ１－Ｃ２ ) is calculated using the quantum chemistry calculation program Gaussian 03, and the ground state structure is optimized using the density functional theory at the B3LYP level, with 6-31g* as the basis function. The obtained ground state optimized structure is then calculated using GaussView 6. Ｃ１－Ｃ２ Calculate d Ｃ１－Ｃ２ In calculating the alkyl group contained in each compound, a propyl group (-CH ２ -CH ２ -CH ３ ) as an example. The calculated values ​​are almost the same for the compound before and after the alkyl group is changed to a propyl group.

[0165] <(L2) ｎ(L2) in formula (1) ｎ In the formula (1), when n is an integer of 2 or more, the chemical structure of each of the L2s present in the formula (1) is independently defined. In other words, the following description of L2s is a description of each of the L2s independently.

[0166] [Aromatic Group] In formula (1), L2 is a divalent aromatic group. The aromatic group in L2 has a monocyclic or fused ring main skeleton. The aromatic group in L2 may be either an aromatic heterocyclic group or an aromatic carbocyclic group, and is preferably an aromatic heterocyclic group 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 a sulfur atom, a silicon atom, a selenium atom, a nitrogen atom, and an oxygen atom, and more preferably at least one selected from the group consisting of a sulfur atom, a nitrogen atom, and an oxygen atom.

[0167] [Chemical Structure of L2] From the viewpoint of the compound's ease of absorbing long-wavelength light, in formula (1), L2 is preferably each independently any of groups represented by formulas (L2-1) to (L2-12) below, more preferably any of groups represented by formulas (L2-1) to (L2-9) below, and even more preferably any of groups represented by formulas (L2-1) to (L2-7) below. That is, from the viewpoint of the compound's ease of absorbing long-wavelength light, L2 preferably has a thiophene structure, a thienothiophene structure, a thiazole structure, or a benzothiadiazole structure. Note that, from the viewpoint of the ease of J-association of the compound of the present disclosure, the chemical structure of L2 is not more limited than the chemical structure of L1.

[0168]

[0169] In formulas (L2-1) to (L2-12), a plurality of R Ｌ２each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio 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 amido group, an optionally substituted acid imide group, an optionally substituted substituted carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group.

[0170] (Specific Examples of L2) Specific examples of L2 include the above-mentioned specific examples of L1 as well as groups represented by the following formulae.

[0171]

[0172] (n) In formula (1), n ​​is an integer of 0 to 4. When n is 0, that is, (L2) ｎ represents the absence of n, and represents that D and A2 in formula (1) are directly bonded. From the viewpoint of the compound easily absorbing light of a long wavelength and the viewpoint of ease of synthesis, n is preferably an integer of 1 or more, may be an integer of 2 or more, is more preferably an integer of 1 to 4, is further preferably an integer of 1 to 3, is particularly preferably 1 or 2, and is most preferably 1.

[0173] ((L2) ｎSpecific example of (L2) ｎ Specific examples of L2 include the specific examples of L2 (i.e., (L2) ｎ (Specific examples when n is 1) and the above-mentioned (L1) ｍ In addition to the specific examples above, groups represented by the following formulae are further included.

[0174]

[0175] In formula (1), when D in formula (1) is the center point, (L1) ｍ The chemical structure of (L2) ｎ The chemical structure of may be point symmetric or asymmetric. In view of the ease with which the compound absorbs light of a long wavelength, it is preferable that m is 2 and n is 1 or 2 in formula (1).

[0176] <A1 and A2: Acceptor> In formula (1), A1 and A2 are each independently a group represented by the following formula (A-1): In each formula, the dotted line represents (L1) in formula (1). ｍ Bond with or (L2) ｎ This shows the bond between .

[0177]

[0178] In formula (A-1), Ar represents a carbocycle which may have a substituent, or a heterocycle which may have a substituent, and the carbocycle and the heterocycle are each independently a monocycle or a fused ring, and when the carbocycle or the heterocycle has a plurality of substituents, the plurality of substituents may be the same or different.

[0179] The carbocyclic ring may be an aromatic carbocyclic ring. 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. Benzene rings and naphthalene rings are preferred, benzene rings and naphthalene rings are more preferred, and benzene rings are even more preferred. These rings may have a substituent.

[0180] The heterocycle may be an aromatic heterocycle. 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, and a dibenzophosphole ring, as well as a phenoxazine ring, a phenothiazine ring, a dibenzoborole ring, a dibenzosilole ring, and a benzopyran ring. These rings may have a substituent.

[0181] [Chemical Structure of A1 and A2] In formula (1), A1 and A2 are preferably each independently any of the groups represented by the following formulae (a-1) to (a-8). In each formula, the symbol "*" indicates (L1) in formula (1). ｍ Bond with or (L2) ｎ The chemical structures of A1 and A2 may be the same or different from each other. From the viewpoint of ease of synthesis of the compound, it is preferable that the chemical structures of A1 and A2 are the same.

[0182]

[0183] In formulas (a-1) to (a-8), a plurality of R Ａ１ are each independently a hydrogen atom, a halogen atom, or a cyano group. Ａ１ are each independently preferably a hydrogen atom, a chlorine atom, a fluorine atom, or a cyano group, and more preferably a cyano group. From the viewpoint of the compound being likely to absorb light of a long wavelength, it is preferable that A1 and A2 are each independently a group represented by formula (a-1) or any of formulas (a-4) to (a-8).

[0184] (Specific Examples of A1 and A2) Specific examples of A1 and A2 include groups represented by the following formulae. In each formula, the symbol "*" indicates (L1) in formula (1). ｍ Bond with or (L2) ｎ This shows the bond between .

[0185]

[0186] <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 compound of the present disclosure is represented by formula (1), wherein: the distance from the element on the D side among the elements forming the single bond between D and L1 to the element on the A1 side among the elements forming the single bond between A1 and L1 is 9.1 Å or more; D is any group represented by formula (D-1) or formula (D-2); L1 and L2 each independently have a thiophene structure, a thienothiophene structure, a thiazole structure, or a benzothiadiazole structure; A1 and A2 each independently are a group represented by formula (A-1); m is an integer of 2 to 4, and n is an integer of 1 to 4; the main skeleton of the monocyclic or fused ring constituting the aromatic group in L1 has an sp2 carbon, and L1 is a monovalent side chain R bonded to the sp2 carbon. Ｌ１ The aromatic group in L1 preferably has an element capable of non-covalent interaction with an element in an adjacent unit.

[0187] The compound of the present disclosure is a compound represented by formula (1), wherein the distance from the element on the D side among the elements forming the single bond between D and L1 to the element on the A1 side among the elements forming the single bond between A1 and L1 is 9.2 Å or more, D is any of the groups represented by formulas (d-1-1) to (d-1-7) or (d-2-1) to (d-2-10), L1s are each independently any of the groups represented by formulas (L1-1) to (L1-7), L2s are each independently any of the groups represented by formulas (L2-1) to (L2-12), A1 and A2 are each independently any of the groups represented by formulas (a-1) to (a-8), m is 2 or 3, n is 1 or 2, the main skeleton of the monocyclic or fused ring constituting the aromatic group in L1 has an sp2 carbon, and L1 is a monovalent side chain R bonded to the sp2 carbon. Ｌ１ and the aromatic group in L1 has an element capable of non-covalent interaction with an element in an adjacent unit.

[0188] Specific examples of suitable compounds of the present disclosure include compounds represented by the following formula:

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195] <Energy Difference (Eg) Between the Energy Level of the Lowest Exciton Singlet State and the Energy Level of the Ground State of the Compound> The compound of the present disclosure preferably has an energy difference (Eg) between the energy level of the lowest exciton singlet state and the energy level of the ground state calculated by a computational science method of 1.55 eV or less. The computational science method may be, for example, a method of calculation using a quantum chemistry calculation program.

[0196] Using the quantum chemistry calculation program Gaussian 03, the ground state structure is optimized using density functional theory at the B3LYP level, and the value obtained by calculating the optimized structure using 6-31g* as the basis function is taken as the value of the ground state energy level. Next, the energy level of the lowest exciton singlet state is determined by TD DFT calculation using B3LYP as the functional and 6-31g* as the basis function. The difference between the energy level of the lowest exciton singlet state and the energy level of the ground state is taken as the energy band gap (Eg).

[0197] When the energy band gap of the compound is 1.55 eV or less, when the compound of the present disclosure is used in a photoelectric conversion element, photoelectric conversion at longer wavelengths is easily achieved.

[0198] The energy band gap of the compound is more preferably 1.50 eV or less, even more preferably 1.40 eV or less, and particularly preferably 1.30 eV or less. The lower limit of the energy band gap of the compound is not particularly limited, but is, for example, 0.75 eV. In one embodiment of the present disclosure, the energy band gap of the compound is preferably 0.75 eV to 1.50 eV.

[0199] <Wavelength λ corresponding to the energy band gap Ｅｇ In one embodiment of the present disclosure, the compound of the present disclosure has a wavelength λ corresponding to the energy band gap. Ｅｇ It is preferable that the calculated value according to density functional theory is 800 nm or more.

[0200] In one embodiment of the present disclosure, the compounds of the present disclosure have an energy bandgap corresponding to a wavelength λ Ｅｇ The wavelength λ corresponding to the energy band gap is more preferably 826 nm or more, further preferably 885 nm or more, and particularly preferably 953 nm or more, from the viewpoint that the compound easily absorbs light of long wavelengths. Ｅｇ The upper limit of the calculated value by density functional theory is not particularly limited, but is preferably 1650 nm or less, more preferably 1400 nm or less, and even more preferably 1200 nm or less. Ｅｇ The calculated value of the wavelength range according to density functional theory is preferably 826 nm to 1650 nm.

[0201] wavelength λ Ｅｇ The calculated value of λ by density functional theory is obtained from the energy band gap (Eg) obtained above and the following (Equation 1): Ｅｇ = 1240 / Eg (Formula 1)

[0202] <Light absorption terminal wavelength (λth) of thin film> The compound of the present disclosure preferably has a light absorption terminal wavelength (λth) of 1400 nm or more in a thin film formed from the compound. A photoelectric conversion element containing the compound of the present disclosure is more likely to perform photoelectric conversion with light of longer wavelengths than conventional elements. From the viewpoint of utilizing light of longer wavelengths, the light absorption terminal wavelength (λth) is preferably a long wavelength. The light absorption terminal wavelength is preferably 1400 nm or more, more preferably 1450 nm or more, even more preferably 1500 nm or more, and even more preferably 1550 nm or more. The upper limit of the light absorption terminal wavelength is not particularly limited, and may be, for example, 2000 nm or less, 1950 nm or less, 1900 nm or less, or 1850 nm or less. In one embodiment of the present disclosure, the light absorption terminal wavelength is preferably 1400 nm to 2000 nm.

[0203] The optical absorption end wavelength is expressed as the wavelength value at the end of the optical absorption wavelength range on the long wavelength side. In the present disclosure, the numerical value of the optical absorption end wavelength is specifically expressed by a value determined by the following method.

[0204] The measurement sample was prepared as follows: The compound was added to orthodichlorobenzene to a concentration of 1.0% by mass. The mixture was heated and stirred for 4 hours at 65°C in a nitrogen atmosphere to prepare a solution. The filtrate of the solution was used as the coating liquid. The coating liquid was placed on a glass substrate whose surface had been cleaned with UV-ozone, and a film was formed by spin coating. The coating film obtained by spin coating was placed on a hot plate. The film was dried in air at 70°C for 5 minutes to obtain a thin film for UV-Vis spectrum measurement.

[0205] The light absorption wavelength is measured using a spectrophotometer that operates in the ultraviolet, visible, and near-infrared wavelength regions (for example, the ultraviolet-visible-near-infrared spectrophotometer "Cary5E" manufactured by Varian).

[0206] The absorption spectrum of a thin film is shown with the absorbance of the compound on the vertical axis and the wavelength on the horizontal axis. It is desirable to adjust the thickness of the thin film so that the absorbance of the largest absorption peak is about 0.4 to 2.

[0207] The optical absorption end wavelength can be determined from the intersection of the first reference line and the second reference line shown below.

[0208] - First reference line - The absorbance at the absorption peak point (maximum value) closest to the longest wavelength in the entire absorption waveform (absorption spectrum) is set to 100%.

[0209] Of the two intersections where the absorption waveform intersects with a line parallel to the horizontal axis (wavelength axis) showing 50% absorbance of the absorption peak point, the intersection located closer to the longer wavelength side than the absorption peak point is defined as the first point.

[0210] Of the two intersections between the absorption waveform and a line parallel to the wavelength axis showing an absorbance of 44% of the absorption peak point, the intersection located closer to the longer wavelength side than the absorption peak point is designated as the second point. The line connecting the first point and the second point is designated as the first reference line.

[0211] - Second Reference Line - The absorbance at the absorption peak point (maximum value) closest to the longest wavelength in the entire absorption waveform is set to 100%.

[0212] Of the two intersections between the absorption waveform and a line parallel to the wavelength axis showing 20% ​​absorbance of the absorption peak point, the wavelength of the intersection point that is longer than the absorption peak point is taken as the reference point, and a point on the absorption waveform that is 100 nm longer than the reference point wavelength is taken as the third point. Also, a point on the absorption waveform that is 150 nm longer than the reference point wavelength is taken as the fourth point. The line connecting the third and fourth points is taken as the second reference line.

[0213] The wavelength value at the intersection of the first reference line and the second reference line is defined as the optical absorption terminal wavelength.

[0214] <Maximum Light Absorption Wavelength (λmax) of Solution> The compound of the present disclosure preferably has a maximum light absorption wavelength (λmax) of 900 nm or more when formed from the compound. A photoelectric conversion element containing the compound of the present disclosure is more likely to perform photoelectric conversion with light of longer wavelengths than conventional elements. From the viewpoint of utilizing light of longer wavelengths, the maximum light absorption wavelength (λmax) is preferably a long wavelength. The maximum light absorption wavelength is more preferably 950 nm or more, even more preferably 980 nm or more, and even more preferably 1000 nm or more. The upper limit of the light absorption terminal wavelength is not particularly limited, and may be, for example, 1800 nm or less, 1700 nm or less, 1600 nm or less, or 1500 nm or less. In one embodiment of the present disclosure, the light absorption terminal wavelength is preferably 900 nm to 1800 nm.

[0215] The maximum light absorption wavelength of a solution is expressed as the wavelength value of the absorption peak wavelength. In the present disclosure, the maximum light absorption wavelength of a solution is specifically expressed by a value determined by the following method.

[0216] The measurement sample was prepared as follows: A compound was added to orthodichlorobenzene to a concentration of 0.025% by mass to prepare a stock solution, which was then diluted 20 times with orthodichlorobenzene to obtain a solution for UV-Vis spectrum measurement (concentration: 0.00125% by mass).

[0217] The light absorption wavelength is measured using a spectrophotometer that operates in the ultraviolet, visible, and near-infrared wavelength regions (for example, the ultraviolet-visible-near-infrared spectrophotometer "Cary5E" manufactured by Varian).

[0218] The absorption spectrum of a solution is shown with the absorbance of the compound on the vertical axis and the wavelength on the horizontal axis. It is desirable to adjust the concentration of the solution so that the absorbance of the largest absorption peak is about 0.4 to 2.

[0219] Among the absorption peaks of the absorption spectrum measured in the wavelength range of 300 nm to 2000 nm, the absorption peak point (maximum value) closest to the longest wavelength is taken as the value of the maximum light absorption wavelength.

[0220] <Composition> The composition of the present disclosure contains a p-type semiconductor material and an n-type semiconductor material, and preferably contains the compound of the present disclosure as the n-type semiconductor material.

[0221] The composition of the present disclosure may contain components other than a p-type semiconductor material and an n-type semiconductor material. Furthermore, 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. The other compounds that may be contained as the n-type semiconductor material may be low molecular weight compounds or high molecular weight compounds.

[0222] <n-Type Semiconductor Material> Examples of low molecular weight compounds that can be included as n-type semiconductor materials include oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, and phenanthrene derivatives such as bathocuproine.

[0223] 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.

[0224] The other compound may also be a fullerene derivative.

[0225] Here, the fullerene derivative is a fullerene (C ６０ Fullerene, C ７０ Fullerene, C ７６ Fullerene, C ７８ Fullerene and C ８４It 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."

[0226] 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.

[0227] C that can be included as an n-type semiconductor material ６０ Specific examples of fullerene derivatives include the following compounds.

[0228]

[0229] Above C ６０In the formula of the fullerene derivative, R represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group, a cycloalkylthio group which may have a substituent, an arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, an acyl group which may have a substituent, an imine residue which may have a substituent, an amido 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, a cycloalkenyl group which may have a substituent, an alkynyl group which may have a substituent, a cycloalkynyl group which may have a substituent, a cyano group, or a nitro group. When there are multiple R's, the multiple R's may be the same or different.

[0230] C ７０ Examples of fullerene derivatives include the following compounds:

[0231]

[0232] <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.

[0233] Here, the weight average molecular weight in terms of polystyrene refers to a weight average molecular weight calculated using a polystyrene standard sample by gel permeation chromatography (GPC).

[0234] The weight average molecular weight of the p-type semiconductor material in terms of polystyrene is preferably 3,000 or more and 500,000 or less, particularly from the viewpoint of improving solubility in a solvent.

[0235] The p-type semiconductor material is preferably a π-conjugated polymer compound (also referred to as a DA-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 one is a donor structural unit or an acceptor structural unit can be determined relatively from the energy levels of the HOMO or LUMO.

[0236] Here, a donor building block is a building block that has an excess of π electrons, and an acceptor building block is a building block that has a deficiency of π electrons.

[0237] 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).

[0238] 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.

[0239] The p-type semiconductor material is preferably 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). The structural unit represented by the following formula (3) is usually preferably a donor structural unit. The structural unit represented by the following formula (4) is usually preferably an acceptor structural unit.

[0240]

[0241] -Formula (3)- In formula (3), Ar ３and Ar ４ each independently represents a trivalent aromatic heterocyclic group which may have a substituent, and Z represents a group represented by the following formula (Z-1) to formula (Z-7):

[0242]

[0243] In formulas (Z-1) to (Z-7), R is independently defined as C ６０ The definition of R is the same as that of the fullerene derivative formula. In each of formulas (Z-1) to (Z-7), when there are two R, the two R may be the same or different.

[0244] Ar ３ and Ar ４ The 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.

[0245] 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.

[0246] 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.

[0247] 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.

[0248] The constitutional unit represented by formula (3) is preferably a constitutional unit represented by the following formula (3-1), (3-2) or (3-3).

[0249]

[0250] In formulas (3-1), (3-2) and (3-3), Ar ３ , Ar ４ and R are defined as Ar in formula (3). ３ , Ar ４ Definition of C ６０ The definition of R in the formula of the fullerene derivative is as follows.

[0251] Specific examples of suitable structural units represented by formula (3) include structural units represented by the following formulas:

[0252]

[0253] In the above formula, R is defined as C ６０ This is the same as the definition of R in the formula of the fullerene derivative. When there are two R, the two R may be the same or different.

[0254] More specific examples of preferred structural units represented by formula (3) include structural units represented by the following formulas:

[0255]

[0256] -Formula (4)- In formula (4), Ar ５ represents a divalent aromatic heterocyclic group.

[0257] Ar５ The divalent aromatic heterocyclic group represented by the 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.

[0258] Ar ５ The divalent aromatic heterocyclic group represented by the following formula (1) may have a substituent. ５ Examples 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.

[0259] As the constitutional unit represented by formula (4), constitutional units represented by the following formulae (4-1) to (4-10) are preferred.

[0260]

[0261] In formulas (4-1) to (4-10), R is C ６０ The definition of R in the formula of the fullerene derivative is as follows. ３ and X ４ each independently represents an oxygen atom or a sulfur atom. １ and Z ２ each independently represents a group represented by ═C(R)— or a nitrogen atom. When there are two R, the two R may be the same or different.

[0262] X in formula (4-1) to formula (4-10) ３ and X ４ are preferably sulfur atoms from the viewpoint of availability of raw material compounds.

[0263] As described above, the structural units represented by formulas (4-1) to (4-10) can generally function as acceptor structural units. However, without being limited thereto, the structural units represented by formulas (4-4), (4-5), and (4-7) in particular can also function as donor structural units.

[0264] 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.

[0265] Ar ５ Specific examples of the divalent aromatic heterocyclic group represented by the formula (101) include groups represented by the following formulas (101) to (191). These groups may further have a substituent.

[0266]

[0267]

[0268]

[0269]

[0270] 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.

[0271] In the polymer compound that is a p-type semiconductor material, the polymer compound that is a p-type semiconductor material may include, as a structural unit, a structure in which the structural unit represented by formula (3) and the structural unit represented by formula (4) already described are linked together.

[0272] 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).

[0273] 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 the following formula (5).

[0274]

[0275] In formula (5), Ar ６ represents an arylene group.

[0276] Ar ６ The arylene group represented by the formula (I) means an atomic group remaining after removing two hydrogen atoms from an aromatic hydrocarbon which may have a substituent. The aromatic hydrocarbon also includes a compound having a fused ring and a compound in which two or more rings selected from the group consisting of independent benzene rings and fused rings are bonded together directly or via a divalent group such as a vinylene group.

[0277] Examples of the substituent that the aromatic hydrocarbon may have include the same substituents as those exemplified as the substituent that the heterocyclic compound may have.

[0278] Ar ６ The number of carbon atoms of the arylene group represented by the formula (I) is usually preferably 6 to 60, not including the number of carbon atoms of the substituent, and more preferably 6 to 20. The number of carbon atoms of the arylene group including the substituent is usually preferably 6 to 100.

[0279] Ar ６ Examples of the arylene group represented by the formula (I) include a phenylene group (e.g., Formulas 1 to 3 below), a naphthalene-diyl group (e.g., Formulas 4 to 13 below), an anthracene-diyl group (e.g., Formulas 14 to 19 below), a biphenyl-diyl group (e.g., Formulas 20 to 25 below), a terphenyl-diyl group (e.g., Formulas 26 to 28 below), a fused ring compound group (e.g., Formulas 29 to 35 below), a fluorene-diyl group (e.g., Formulas 36 to 38 below), and a benzofluorene-diyl group (e.g., Formulas 39 to 46 below).

[0280]

[0281]

[0282]

[0283]

[0284]

[0285]

[0286]

[0287]

[0288] In the formula, R is defined as C ６０ The definition of R is the same as that of the fullerene derivative. Multiple Rs may be the same or different.

[0289] The constitutional unit represented by formula (5) is preferably a constitutional unit represented by the following formula (5-1) or formula (5-2).

[0290]

[0291] In the formula (5-1) and the formula (5-2), R is defined as C ６０ The definition of R is the same as that of R in the formula of the fullerene derivative. The two R may be the same or different.

[0292] 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.

[0293] 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%, and from the viewpoint of improving the charge transport property as a p-type semiconductor material, is more preferably 40 mol% to 100 mol%, and even more preferably 50 mol% to 100 mol%, when the amount of all constitutional units contained in the polymer compound is taken as 100 mol%.

[0294] Specific examples of polymer compounds that are p-type semiconductor materials include polymer compounds represented by the following formulas (P-1) to (P-19).

[0295]

[0296]

[0297]

[0298]

[0299]

[0300]

[0301]

[0302]

[0303] In the above formula, R is defined as C ６０ The definition of R is the same as that of the fullerene derivative. Multiple Rs may be the same or different.

[0304] 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.

[0305] <Ink> The ink of the present disclosure preferably contains the compound of the present disclosure and a solvent. The ink of the present disclosure more preferably contains a p-type semiconductor material and an n-type semiconductor material, and the n-type semiconductor material contains the compound of the present disclosure. The ink of the present disclosure 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.

[0306] 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 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, and thus it is possible to improve heat resistance.

[0307] The solvent may be, for example, a mixed solvent that combines a first solvent and a second solvent, which will be described later. 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.

[0308] The first solvent and second solvent that can be suitably used in the ink for forming the active layer and their combinations will be described below.

[0309] <First Solvent> The first solvent is preferably a solvent capable of dissolving a p-type semiconductor material. The first solvent is preferably an aromatic hydrocarbon.

[0310] Examples of aromatic hydrocarbons include toluene, xylene (e.g., o-xylene, m-xylene, p-xylene), chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, trimethylbenzene (e.g., mesitylene, 1,2,4-trimethylbenzene (pseudocumene)), butylbenzene (e.g., n-butylbenzene, sec-butylbenzene, tert-butylbenzene), methylnaphthalene (e.g., 1-methylnaphthalene), 1-chloronaphthalene, bromobenzene, tetralin, and indane.

[0311] The first solvent may be composed of one kind of aromatic hydrocarbon or two or more kinds of aromatic hydrocarbons, but is preferably composed of one kind of aromatic hydrocarbon.

[0312] 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.

[0313] <Second Solvent> The second solvent is preferably selected from the viewpoints of facilitating the implementation of the manufacturing process and further improving the characteristics 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.

[0314] The second solvent is preferably, for example, acetophenone, propiophenone, butyl benzoate, or methyl benzoate, from the viewpoint of further reducing dark current.

[0315] <Combination of First Solvent and Second Solvent> 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.

[0316] <Mass Ratio of First Solvent and Second Solvent> The mass ratio of the first solvent, which is the main solvent, to the second solvent, which is an 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.

[0317] <Optional Other Solvent> The solvent may contain any other solvent other than the first solvent and the second solvent. When the total mass of all solvents contained in the ink is taken as 100 mass%, the content of the optional other solvent is preferably 5 mass% or less, more preferably 3 mass% or less, and even more preferably 1 mass% or less. As the optional other solvent, a solvent having a higher boiling point than the second solvent is preferred.

[0318] 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.

[0319] 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.

[0320] 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.

[0321] 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.

[0322] 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.

[0323] 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.

[0324] 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 obtained mixed solvent, or by adding a p-type semiconductor material to a first solvent, adding an n-type semiconductor material to a second solvent, and then mixing the first solvent and the second solvent to which each material has been added.

[0325] The first solvent, the second solvent, the p-type semiconductor material, and the n-type semiconductor material may be mixed by heating to a temperature equal to or lower than the boiling point of the solvent.

[0326] After mixing the first solvent and the second solvent with the p-type semiconductor material and the n-type semiconductor material, 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).

[0327] <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 preferably includes the compound of the present disclosure as the n-type semiconductor material. Preferred aspects of the p-type semiconductor material and the n-type semiconductor material are as described above.

[0328] 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.

[0329] Here, an example of a configuration that the photoelectric conversion element of the present disclosure can take will be described. Fig. 1 is a diagram schematically showing the configuration of the photoelectric conversion element of the present disclosure.

[0330] 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.

[0331] 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.

[0332] Components that can be included in the photoelectric conversion element of the present disclosure will be specifically described below.

[0333] <Substrate> A photoelectric conversion element is usually formed on a substrate (support substrate). In some cases, the element is further sealed with a 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 does not chemically change, especially when a layer containing an organic compound is formed.

[0334] 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.

[0335] <Electrodes> The photoelectric conversion element includes a pair of electrodes, an anode and a cathode. At least one of the anode and the cathode is preferably a transparent or semi-transparent electrode to allow light to enter.

[0336] Examples of transparent or translucent electrode materials include conductive metal oxide films and translucent 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 translucent electrode materials are 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 translucent electrode may be an anode or a cathode.

[0337] 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 the electrode with low optical transparency include metals and conductive polymers. Specific examples of materials for the electrode 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 alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.

[0338] <Active Layer> The active layer included in the photoelectric conversion element according to 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 according to the present disclosure as the n-type semiconductor material.

[0339] 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. 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, particularly from the viewpoint of further reducing dark current. Furthermore, 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.

[0340] The active layer is preferably formed by a process including a heating treatment at a heating temperature of 200° C. or higher.

[0341] <Intermediate Layer> 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.

[0342] 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)).

[0343] As shown in Fig. 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.

[0344] 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.

[0345] The hole transport layer contains a hole transport material. Examples of the hole transport material include polythiophene and its derivatives, aromatic amine compounds, polymer compounds containing a structural unit having an aromatic amine residue, CuSCN, CuI, NiO, and tungsten oxide (WO ３ ) and molybdenum oxide (MoO ３Examples of hole transporting material products include Avantama P-10 and P-21.

[0346] 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.

[0347] The photoelectric conversion element of the present disclosure preferably has a configuration in which the intermediate layer is an electron transport layer, and a substrate (support substrate), an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode are stacked in this order so as to be in contact with each other.

[0348] As shown in Fig. 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.

[0349] The electron transport layer provided in contact with the cathode is sometimes referred to as 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.

[0350] 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.

[0351] 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 a conventional manner, and polymers obtained by chemically modifying these by reacting them with various compounds. Preferred polyalkyleneimines and derivatives thereof are polyethyleneimine (PEI) and ethoxylated polyethyleneimine (PEIE).

[0352] 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.

[0353] Examples of metal oxides include zinc oxide, gallium-doped zinc oxide, aluminum-doped zinc oxide, titanium oxide, and niobium oxide. As the metal oxide, a zinc-containing metal oxide is preferred, and zinc oxide is 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.

[0354] Other examples of electron transporting materials include poly(4-vinylphenol) and perylene diimide.

[0355] <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. An example of the sealing member is a combination of a glass substrate as a substrate (sealing substrate) and a sealing material (adhesive) such as a UV-curable resin.

[0356] The sealing member may be a sealing layer having a layer structure of one or more layers. Examples of layers constituting the sealing layer include a gas barrier layer and a gas barrier film.

[0357] The sealing layer is preferably formed from a material having a moisture-blocking property (water vapor barrier property) or an oxygen-blocking property (oxygen barrier property). Suitable examples of the sealing layer material include organic materials such as trifluoroethylene, 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.

[0358] 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.

[0359] <Applications of Photoelectric Conversion Element> Applications of the photoelectric conversion element of the present disclosure include photodetection elements and solar cells. 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 applying a voltage (reverse bias voltage) between the electrodes, and can operate as a photodetection element (photosensor). Furthermore, by integrating a plurality of photodetection elements, the element can also be used as an image sensor. In this way, the photoelectric conversion element of the present disclosure can be particularly suitably used as a photodetection element.

[0360] 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 plurality of photoelectric conversion elements can be integrated to form a solar cell module.

[0361] 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.

[0362] 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.

[0363] 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.

[0364] <Method for 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.

[0365] Hereinafter, a method for manufacturing a photoelectric conversion element having a structure 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 one another in this order will be described.

[0366] (Substrate Preparation Step) 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 may be purchased from the market, and the conductive thin film may be patterned to form an anode, as necessary, to prepare a support substrate provided with an anode.

[0367] In the method for producing a photoelectric conversion element according to the present disclosure, the method for forming an anode on a supporting substrate is not particularly limited. The anode can be formed on a structure where the anode is to be formed (e.g., a supporting substrate, an active layer, a hole transport layer) by any suitable conventional method such as vacuum deposition, sputtering, ion plating, plating, or coating using the materials already described.

[0368] (Step of Forming Hole Transport Layer) 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.

[0369] The method for forming the hole transport layer is not particularly limited. From the viewpoint of simplifying the process for forming the hole transport layer, it is preferable to form the hole transport layer by any suitable coating method known in the art. 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 as already described, or by a vacuum deposition method.

[0370] (Active Layer Forming Process) In the method for producing a photoelectric conversion element according to 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 forming process. The active layer is preferably produced by a coating method using an ink (coating liquid). Preferred aspects of the ink are as described above.

[0371] Hereinafter, steps (i) and (ii) included in the process of forming the active layer, which is a main component of the present disclosure, will be described.

[0372] Step (i) Any suitable coating method can be used as a method for applying the ink to a coating target. As the coating method, slit coating, knife coating, spin coating, microgravure coating, gravure coating, bar coating, inkjet printing, nozzle coating, or capillary coating is preferred, slit coating, spin coating, capillary coating, or bar coating is more preferred, and slit coating or spin coating is even more preferred.

[0373] 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.

[0374] Step (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 under an inert gas atmosphere such as nitrogen gas, hot air drying, infrared heating drying, flash lamp annealing drying, and reduced pressure drying.

[0375] 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).

[0376] The step of forming the active layer may include other steps in addition to the steps (i) and (ii), provided that the other steps do not impair the object and effect of the present disclosure.

[0377] The method for producing a photoelectric conversion element according to the present disclosure may be a method for producing a photoelectric conversion element including a plurality of active layers, or may be a method in which step (i) and step (ii) are repeated a plurality of times.

[0378] The method for manufacturing a photoelectric conversion element according to the present disclosure includes a step of forming an electron transport layer (electron injection layer) on an active layer.

[0379] The method for forming the electron transport layer is not particularly limited. From the viewpoint of simplifying the process for forming the electron transport layer, it is preferable to form the electron transport layer by any suitable conventional vacuum deposition method.

[0380] (Cathode Formation Process) The method for forming the cathode is not particularly limited. The cathode can be formed on the electron transport layer by, for example, applying the above-exemplified electrode materials to the electron transport layer by any suitable conventional method such as coating, vacuum deposition, sputtering, ion plating, or plating. The photoelectric conversion element of the present disclosure is manufactured by the above-described process.

[0381] (Step of forming encapsulated body) In forming the encapsulated body, any suitable conventional encapsulating material (adhesive) and substrate (encapsulating substrate) are used. Specifically, a encapsulating material such as a UV-curable resin is applied to a support substrate so as to surround the periphery of the manufactured photoelectric conversion element, and then the support substrate and the encapsulating material are bonded together without any gaps. After that, the photoelectric conversion element is encapsulated in the gap between the support substrate and the encapsulating substrate using a method suitable for the selected encapsulating material, such as UV light irradiation, to obtain a encapsulated photoelectric conversion element.

[0382] <Photodetector> As described above, the photoelectric conversion element of the present disclosure, particularly the photodetector (optical sensor), can function by being incorporated into an image sensor or a biometric authentication device (fingerprint authentication device, vein authentication device).

[0383] Examples are provided below to further explain the present disclosure, but the present disclosure is not limited to the examples described below.

[0384] A photoelectric conversion element was fabricated using a p-type semiconductor material and an n-type semiconductor material.

[0385] <p-Type Semiconductor Material (Polymer Compound P-19)> Polymer compound P-19 was commercially available under the trade name PCE-10 manufactured by 1-material Co., Ltd. and used.

[0386] (Polymer compound P-19)

[0387]

[0388] <N-type Semiconductor Material> The following compound was used as the n-type semiconductor material, the synthesis method of which will be described later.

[0389] (Compound N-1)

[0390]

[0391] (Compound N-2)

[0392]

[0393] (Compound N-3)

[0394]

[0395] (Compound N-4)

[0396]

[0397] (Compound N-5)

[0398]

[0399] (Compound N-6)

[0400]

[0401] (Compound N-7)

[0402]

[0403] (Compound N-8)

[0404]

[0405] (Compound N-9)

[0406]

[0407] (Compound N-10)

[0408]

[0409] (Compound N-11)

[0410]

[0411] (Compound N-12)

[0412]

[0413] (Compound N-13)

[0414]

[0415] (Compound N-14)

[0416]

[0417] (Synthesis of Compound N-1) Compound 2 was synthesized using Compound 1.

[0418]

[0419] In a 300 mL four-neck flask, 3-methoxythiophene (Tokyo Chemical Industry Co., Ltd., 5.00 g, 43.8 mmol), 2-hexyl-1-decanol (31.9 g, 131 mmol), p-TsOH.H２ O (0.833 g, 4.38 mmol) and toluene (100 g) were charged, purged with nitrogen, and then 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 completely concentrated 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 2 as a colorless, transparent liquid. The NMR spectrum of the resulting compound 2 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)

[0420] Compound 3 was synthesized using compound 2.

[0421]

[0422] A 200 mL four-neck flask was charged with compound 2 (4.0 g, 12.3 mmol) and THF (45 mL), and the flask was 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 flask was maintained at an internal temperature of -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 the flask was gradually added dropwise to a reaction mass whose internal temperature was -65°C. After completion of the dropwise addition, the flask was maintained at an internal temperature of -65°C for 1 hour, then heated to room temperature, and 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 3 as a crude product. The NMR spectrum of the resulting compound 3 was analyzed. The results are as follows. １H-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)

[0423] Compound 4 was synthesized using compound 3.

[0424]

[0425] A 500 mL four-neck flask was charged with crude compound 3 (5.90 g), 5-Bromo-4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde (4.60 g, 14.4 mmol) (manufactured by JiangSu GR-Chem Co., Ltd.), and THF (149 mL), and nitrogen bubbling was performed for 30 minutes. ２ (dba) ３ (0.600g, 0.655mmol), P(tBu ３ )HBF ４ (0.399g, 1.38mmol), 3mol / L of K ３ P.O. ４ The mixture was charged with an aqueous solution (60.6 g) and then heated 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 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 3.72 g of compound 4 as a yellow-brown liquid. The NMR spectrum of the resulting compound 4 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 5 was synthesized using compound 4.

[0427]

[0428] A 100 mL four-neck flask was charged with compound 4 (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 5 as a yellow-brown liquid. The NMR spectrum of the resulting compound 5 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 7 was synthesized using compound 6.

[0430]

[0431] 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) and THF (11.2 mL), and after purging with nitrogen, the flask was cooled to -73°C. nBuLi (1.56 mol / L in hexane, 1.75 mL, 2.73 mmol) was then charged, and the flask was kept at an internal temperature of -65°C for 1 hour. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.85 mL, 3.72 mmol) and THF (5.6 mL) were charged into a dropping funnel and added dropwise little by little to the reaction mass at an internal temperature of -65°C. After completion of the addition, the internal temperature was maintained at -65°C for 1 hour, then the temperature was raised to room temperature and stirred for 1 hour. After quenching by pouring 20% ​​aqueous ammonium chloride solution (5.3 mL), the aqueous layer was removed from the resulting mass by separation, dried over magnesium sulfate, filtered, and then totally concentrated using a rotary evaporator to obtain 1.49 g of crude compound 7.

[0432] Compound 8 was synthesized using Compound 7 and Compound 5.

[0433]

[0434] A 100 mL four-neck flask was charged with crude compound 7 (1.49 g), compound 5 (2.05 g, 3.20 mmol), and THF (29.6 g), and nitrogen bubbling was carried out for 30 minutes. ２ (dba) ３ (0.113g, 0.123mmol), P(tBu ３ )HBF ４ (0.0749g, 0.258mmol), 3mol / L of K ３ P.O. ４The mixture was charged with toluene and then an aqueous solution (11.4 g) of toluene, and then heated 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 completely concentrated using 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 8 as a red liquid. The NMR spectrum of the resulting compound 8 was analyzed. 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)

[0435] Compound 9 was synthesized using compound 8.

[0436]

[0437] In a 50 mL four-neck flask, compound 8 (1.25 g, 1.30 mmol), 5-Bromo-4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde (0.497 g, 1.56 mmol) (manufactured by JiangSu GR-Chem Co., Ltd.), and Pd(OAc) were placed. ２ (0.0364g, 0.162mmol), [(tBu) ２ MePH]BF ４ (0.0644 g, 0.259 mmol), pivalic acid (0.133 g, 1.30 mmol), K ２ CO ３(0.538 g, 3.89 mmol) and DMF (12.5 g) were charged and 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, it was diluted with toluene and washed twice with water, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The obtained 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 9 as a deep red-purple liquid. The NMR spectrum of the obtained compound 9 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)

[0438] Compound 9 was used to synthesize compound N-1.

[0439]

[0440] In a 50 mL four-neck flask, compound 9 (0.600 g, 0.499 mmol), compound 10 (0.366 g, 1.50 mmol) synthesized according to the method described in WO 2020 / 109823, p-TsOH·H ２ O (0.285 g, 1.50 mmol), EtOH (5.5 g), toluene (11.0 g), MgSO ４ (0.300 g) was charged and kept warm in an oil bath heated to 65°C. After stirring for 2 hours, it was removed from the oil bath and allowed to cool to room temperature. ４ After removing the solvent, the precipitate was dissolved and washed with chloroform. After concentrating with an evaporator, a crude product was obtained by repulping and washing with methanol. The obtained crude product was purified with a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 0.632 g (yield 78%) of compound N-1 as a black solid. The NMR spectrum of the obtained compound N-1 was analyzed. The results are as follows. １H-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)

[0441] (Synthesis of Compound N-2) Compound 12 was synthesized using compound 11.

[0442]

[0443] In a 50 mL four-neck flask, 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), tBu-bpy (16.0 mg, 0.0596 mmol) were charged and the mixture was purged with nitrogen, after which 15.0 g of cyclohexane was charged and the mixture was immersed in an oil bath heated to 60°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 cooled mass was poured into water for quenching. The aqueous layer was removed from the resulting mass by separation, dried over magnesium sulfate, filtered while passing the liquid through silica gel, and then the entire amount was concentrated using a rotary evaporator to obtain 2.30 g of crude compound 12.

[0444] Compound 13 was synthesized using compound 12 and compound 5.

[0445]

[0446] A 50 mL four-neck flask was charged with crude compound 12 (1.13 g), compound 5 (1.80 g, 2.81 mmol), and THF (18.2 g), and nitrogen was bubbled through the flask for 30 minutes. ２ (dba) ３ (0.0560g, 0.0612mmol), P(tBu ３ ) HBF ４ (0.0372 g, 0.128 mmol), 3 mol / L K３ P.O. ４ The mixture was charged with toluene and then an aqueous solution (5.66 g), and then heated 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 completely 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 1.19 g of compound 13 as a deep red viscous liquid. The NMR spectrum of the resulting compound 13 was analyzed. 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)

[0447] Compound 13 was used to synthesize compound N-2.

[0448]

[0449] In a 100 mL four-neck flask, compound 13 (1.15 g, 0.754 mmol), compound 10 (0.553 g, 2.26 mmol), and p-TsOH.H ２ O (0.431 g, 2.26 mmol), EtOH (10.5 g), toluene (23.0 g), MgSO ４ (0.575 g) was charged and kept warm in an oil bath heated to 65°C. After stirring for 2 hours, it was removed from the oil bath and allowed to cool to room temperature. ４ After removing the solvent, the precipitate was dissolved and washed with chloroform. After concentrating using an evaporator, a crude product was obtained by repulping and washing with methanol. The obtained crude product was purified using a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 0.890 g (yield 60%) of compound N-2 as a black solid. The NMR spectrum of the obtained compound N-2 was analyzed. The results are as follows. １H-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)

[0450] (Synthesis of Compound N-3) Compound 13 was synthesized using Compound 1.

[0451]

[0452] In a 300 mL four-neck flask, 3-methoxythiophene (Tokyo Chemical Industry Co., Ltd., 4.50 g, 39.4 mmol), 2-ethyl-1-hexanol (15.4 g, 118 mmol), p-TsOH.H ２ O (0.750 g, 3.94 mmol) and toluene (90 g) were charged, purged with nitrogen, and then heated to 110°C. After stirring for 7 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 completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane = 100 wt%) to obtain 8.08 g of compound 13 as a colorless, transparent liquid. The NMR spectrum of the resulting compound 13 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 7.16 (1H), 6.75 (1H), 6.22 (1H), 3.83 (2H), 1.74-1.64 (1H), 1.54-1.27 (m, 8H), 0.95-0.86 (m, 6H)

[0453] Compound 14 was synthesized using compound 13.

[0454]

[0455] A 100 mL four-neck flask was charged with compound 13 (2.0 g, 9.42 mmol) and THF (22.5 mL), and the flask was purged with nitrogen and then cooled to -73°C. LDA (1 M in THF / Hexane, 11.3 mL, 11.3 mmol) was charged, and the flask was maintained at an internal temperature of -65°C for 1 hour. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.2 mL, 14.1 mmol) and THF (11.2 mL) were charged into a dropping funnel, and the flask was gradually added dropwise to a reaction mass whose internal temperature was -65°C. After completion of the dropwise addition, the flask was maintained at an internal temperature of -65°C for 1 hour, then heated to room temperature, and stirred for 2 hours. After quenching by pouring in 20% aqueous ammonium chloride solution (20 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 3.13 g of compound 14 as a crude product. The NMR spectrum of the resulting compound 14 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 7.26 (1H), 6.57 (1H), 3.83 (2H), 1.73-1.63 (1H), 1.54-1.20 (m, 20H), 00.95-0.86 (m, 6H)

[0456] Compound 15 was synthesized using compound 14.

[0457]

[0458] Crude compound 14 (3.10 g), 5-Bromo-4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde (3.22 g, 10.1 mmol) (manufactured by JiangSu GR-Chem Co., Ltd.), and THF (31.4 mL) were placed in a 100 mL four-neck flask, and nitrogen bubbling was carried out for 30 minutes. ２ (dba) ３ (0.420g, 0.458mmol), P(tBu ３ )HBF ４ (0.279g, 0.962mmol), 3mol / L of K ３ P.O. ４The mixture was charged with toluene and then an aqueous solution (17.0 g) of toluene, and then heated 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 completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 15 / 1 (volume ratio)) to obtain 2.81 g of compound 15 as a yellow-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 9.76 (1H), 7.46 (1H), 7.09 (1H), 6.29 (1H), 4.06 (2H), 3.85 (2H), 1.85-1.27 (m, 18H), 0.98-0.86 (m, 12H)

[0459] Compound 16 was synthesized using compound 15.

[0460]

[0461] A 100 mL four-neck flask was charged with compound 15 (1.15 g, 2.55 mmol) and chloroform (40.3 g). The flask was purged with nitrogen and then cooled to 0°C. NBS (0.450 g, 2.53 mmol) was added and stirred at 0°C. After stirring for 2 hours, water (28.8 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 = 15 / 1 (volume ratio)) to obtain 1.28 g of compound 16 as a yellow liquid. The NMR spectrum of the resulting compound 16 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 9.77 (1H), 7.45 (1H), 7.03 (1H), 4.07 (2H), 3.95 (2H), 1.84-1.27 (m, 18H), 0.99-0.86 (m, 12H)

[0462] Compound 18 was synthesized using Compound 17 and Compound 16.

[0463]

[0464] Compound 17 was synthesized with reference to the method described in International Publication No. 2014 / 112656. Compound 17 (0.720 g, 0.915 mmol), compound 16 (1.12 g, 2.11 mmol), and THF (16.4 g) were placed in a 50 mL four-neck flask, and nitrogen bubbling was performed for 30 minutes. ２ (dba) ３ (0.0419g, 0.0458mmol), P(tBu ３ )HBF ４ (0.0279g, 0.0961mmol), 3mol / L of K ３ P.O. ４ The mixture was charged with toluene and then an aqueous solution (4.24 g), and then heated 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 completely 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 1.25 g of compound 18 as a blue-purple viscous liquid. The NMR spectrum of the resulting compound 18 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 9.76 (2H), 7.47 (1H), 7.46 (1H), 7.20 (1H), 7.17 (1H), 6.90 (1H), 6.80 (1H), 4.11-4.06 (m, 8H), 1.63-0.83 (m, 110H)

[0465] Compound 18 was used to synthesize compound N-3.

[0466]

[0467] In a 100 mL four-neck flask, compound 18 (1.20 g, 0.840 mmol), compound 10 (0.616 g, 2.52 mmol), and p-TsOH.H ２ O (0.480 g, 2.52 mmol), EtOH (10.9 g), toluene (24.0 g), MgSO ４(0.600 g) was charged and kept warm in an oil bath heated to 65°C. After stirring for 2 hours, it was removed from the oil bath and allowed to cool to room temperature. ４ After removing the solvent, the precipitate was dissolved and washed with chloroform. After concentrating with an evaporator, a crude product was obtained by repulping and washing with methanol. The obtained crude product was purified with a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 1.23 g (yield 78%) 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 8.41 (1H), 8.29-8.27 (m, 3H), 8.21 (1H), 7.95 (1H), 7.87 (1H), 7.73 (1H), 7.35 (1H), 7.25 (1H), 7.05 (1H), 6.69 (1H), 4.61-4.00 (m, 8H), 2.35-0.81 (m, 110H)

[0468] (Synthesis of Compound N-4) Compound 19 was synthesized using compound 8.

[0469]

[0470] Compound 8 (2.27 g, 2.35 mmol), neopentyl glycol (0.43 g, 4.15 mmol), 10-camphorsulfonic acid (0.05 g, 0.21 mmol), and toluene (50 ml) were charged into a 100 mL four-neck flask, and after replacing with nitrogen, the internal temperature was raised to 80°C and stirred for 3 hours. After cooling to room temperature, the flask was diluted with 5% K ３ P.O. ４ The reaction mixture was quenched with an aqueous solution. The mixture was washed twice with water, and the organic layer was dried over magnesium sulfate. After removing the magnesium sulfate by filtration, the mixture was completely concentrated using 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 2.20 g of compound 19 as a red liquid (yield 89%). The NMR spectrum of the resulting compound 19 was analyzed. The results are as follows. １H-NMR (300 MHz, CHLOROFORM-D) δ7.07 (1H), 6.95 (2H), 6.89 (2H), 5.54 (1H), 4.01 (4H), 3.75 (2H), 3.62 (2H), 1.85 (6H), 0.55-1.60 (80H)

[0471] Compound 20 was synthesized using compound 19.

[0472]

[0473] In a 100 mL four-neck flask, compound 19 (1.769 g, 1.685 mmol), bis(pinacolato)diboron (0.535 g, 2.106 mmol), 4,4′-di-tert-butyl-2,2′-dipyridyl (0.022 g, 0.0008 mmol), [Ir(OMe)(cod)] ２ (0.0027 g, 0.0004 mmol) and cyclohexane (34 ml) were charged and purged with nitrogen. The internal temperature was then raised to 80°C and stirred for 2 hours. 8.48 g of water was charged into a separate 100 ml four-neck flask, and the reaction mass, cooled to room temperature, was added dropwise. The aqueous layer was removed by separation, and the organic layer was dried over magnesium sulfate and then filtered through silica gel. The resulting filtrate was completely concentrated using a rotary evaporator, yielding 1.98 g of compound 20 (yield 84%). The NMR spectrum of the resulting compound 20 was analyzed. The results are as follows: １ H-NMR (300 MHz, CHLOROFORM-D) δ7.42 (1H), 6.98 (2H), 6.91 (1H), 5.54 (1H), 4.01 (4H), 3.76 (2H), 3.64 (2H), 1.84 (6H), 0.55-1.60 (80H)

[0474] Compound 22 was synthesized using compound 20.

[0475]

[0476] Compound 20 (0.70 g, 0.595 mmol), compound 21 (0.28 g, 0.714 mmol, manufactured by Chem Shuttle), and THF (17.9 ml) were placed in a 50 mL four-neck flask, and nitrogen bubbling was carried out for 30 minutes.２ (dba) ３ (0.027g, 0.030mmol), P(tBu ３ )HBF ４ (0.018g, 0.063mmol), 3mol / L of K ３ P.O. ４ The mixture was then charged with an aqueous solution (1.9 ml) and heated to 60°C. After stirring for 2 hours, the mixture was cooled to room temperature. The reaction mass was diluted with toluene, washed twice with water, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The resulting crude product was purified by recycling GPC to obtain 0.82 g of compound 22 (yield: 50%). The NMR spectrum of the resulting compound 22 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ9.81 (1H), 8.12 (1H), 7.38 (1H), 7.02 (1H), 6.99 (1H), 6.93 (1H), 5.55 (1H), 4.29 (2H), 4.04 (4H), 3.78 (2H), 3.64 (2H), 1.84-1.94 (7H), 0.55-1.60 (94H)

[0477] Compound 22 was used to synthesize compound 23.

[0478]

[0479] A 50 mL four-neck flask was purged with nitrogen and charged with compound 22 (0.39 g, 0.289 mmol), THF (18.5 mL), water (4.5 mL), and trifluoroacetic acid (0.45 mL). The mixture was stirred at room temperature for 3 hours. The reaction mass was diluted with heptane, quenched with a 5% aqueous solution of disodium hydrogen phosphate, and then washed twice with water. The organic layer was dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator to obtain a crude product. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 20 / 1 → 10 / 1 (volume ratio)) to obtain 0.32 g of compound 23 (yield 87%). The NMR spectrum of the resulting compound 23 was analyzed. The results are as follows. １H-NMR (300 MHz, CHLOROFORM-D) δ9.84 (1H), 9.78 (1H), 8.12 (1H), 7.49 (1H), 7.40 (1H), 7.22 (1H), 7.13 (1H), 4.30 (2H), 4.16 (4H), 1.60-1.94 (7H), 0.55-1.60 (88H)

[0480] Compound N-4 was synthesized using compound 23.

[0481]

[0482] Compound 23 (0.32 g, 0.247 mmol), compound 10 (0.181 g, 0.742 mmol), p-TsOH・H in a 50 mL four-necked flask. ２ O (0.141 g, 0.742 mmol), EtOH (3.6 ml), toluene (7.3 ml), MgSO ４ (0.141 g) was charged and kept warm in an oil bath heated to 65°C. After stirring for 2 hours, it was removed from the oil bath and allowed to cool to room temperature. ４ After removing the solvent, the precipitate was dissolved and washed with chloroform. After concentration using an evaporator, a crude product was obtained by repulping and washing with methanol. The obtained crude product was purified by recycling GPC to obtain 0.342 g (yield 79%) of compound N-4 as a black solid. The NMR spectrum of the obtained compound N-4 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ8.99 (1H), 8.91 (1H), 8.90 (1H), 8.79 (1H), 8.20 (1H), 8.17 (1H), 8.09 (1H), 7.78 (1H), 7.50 (2H), 7.31 (1H), 4.34 (2H), 4.21 (4H), 1.84-1.94 (7H), 0.55-1.60 (88H)

[0483] (Synthesis of Compound N-5) Compound 24 was synthesized using Compound 2.

[0484]

[0485] A 1 L four-neck flask was charged with compound 2 (15.35 g, 47.3 mmol) and THF (460.5 g), and the flask was purged 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, 3% aqueous sodium sulfite solution (249 g) was added and the mixture was heated 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) to obtain 18.53 g of compound 24 as a colorless liquid.

[0486] Compound 25 was synthesized using compound 24.

[0487]

[0488] A 3 L four-neck flask was charged with compound 24 (92.28 g, 228.7 mmol) and THF (1038 mL), and the flask was purged with nitrogen and then cooled to -73 °C. LDA (1 M in THF / Hexane, 228.7 mL, 228.7 mmol) was slowly added dropwise, and after the addition was completed, the mixture was kept at an internal temperature of -73 °C for 2 hours. DMF (35.3 mL, 457.4 mmol) was slowly added dropwise to the reaction mass at an internal temperature of -73 °C, and after the addition was completed, the mixture was warmed to room temperature and stirred for 2 hours. After quenching by pouring 20% ​​aqueous ammonium chloride solution (489 mL), the aqueous layer was removed from the resulting mass by liquid separation, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The obtained crude product was purified using a silica gel column (developing solvent: hexane / ethyl acetate = 70 / 1 (volume ratio)) to obtain 45.00 g of compound 25 as a yellow liquid. The NMR spectrum of the obtained compound 25 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 9.70 (1H), 7.37 (1H), 3.95 (2H), 1.80-1.72 (m, 1H), 1.57-1.27 (m, 24H), 0.90-0.86 (m, 6H)

[0489] Compound 26 was synthesized using compound 8.

[0490]

[0491] In a 50 mL four-neck flask, compound 8 (0.964 g, 1.00 mmol), compound 25 (0.518 g, 1.20 mmol), and Pd(OAc) were added. ２ (0.0561g, 0.250mmol), [(tBu) ２ MePH]BF ４ (0.0992 g, 0.400 mmol), pivalic acid (0.102 g, 1.00 mmol), K ２ CO ３ (0.415 g, 3.00 mmol) and DMF (9.5 g) were charged and nitrogen bubbling was performed for 30 minutes. After nitrogen substitution, the internal temperature was raised to 120°C and stirred for 5 hours. After cooling to room temperature, it was diluted with toluene and washed twice with water, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The obtained crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 8 / 1 (volume ratio)) to obtain 0.280 g of compound 26 as a deep red-purple liquid. The NMR spectrum of the obtained compound 26 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 9.76 (1H), 9.73 (1H), 7.46 (2H), 7.33 (1H), 7.20 (1H), 7.12 (1H), 4.12 -4.06 (m, 6H), 1.89-0.60 (m, 111H)

[0492] Compound 26 was used to synthesize compound N-5.

[0493]

[0494] In a 50 mL four-neck flask, compound 26 (0.280 g, 0.204 mmol), compound 10 (0.150 g, 0.613 mmol) synthesized according to the method described in WO 2020 / 109823, p-TsOH.H ２ O (0.117 g, 0.613 mmol), EtOH (2.5 g), toluene (5.5 g), MgSO ４(0.140 g) was charged and kept warm in an oil bath heated to 65°C. After stirring for 2 hours, it was removed from the oil bath and allowed to cool to room temperature. ４ After removing the solvent, the precipitate was dissolved and washed with chloroform. After concentrating with an evaporator, a crude product was obtained by repulping and washing with methanol. The obtained crude product was purified with a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 0.220 g (yield 59%) of compound N-5 as a black solid. The NMR spectrum of the obtained compound N-5 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 8.99-8.96 (m, 2H), 8.77-8.72 (m, 2H), 8.15-8.11 (m, 2H), 7.74 (1H), 7.50-7.33 (m, 4H), 4.21-4.18 (m, 6H), 1.98-0.63 (m, 111H)

[0495] (Synthesis of Compound N-6) Compound 27 was synthesized using Compound 8.

[0496]

[0497] A 50 mL four-neck flask was charged with Compound 8 (2.89 g), 5-Bromo-4-(2-ethylhexyl)thiophene-2-carbaldehyde (1.34 g), and Pd(OAc). ２ (0.126g), [(tBu) ２ MePH]BF ４ (0.223 g), pivalic acid (0.306 g), K ２ CO ３ (1.24 g) and DMF (20 mL) were charged and 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, it was diluted with heptane, washed twice 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 / ethyl acetate = 9 / 1 (volume ratio)) to obtain 3.32 g of compound 27.

[0498] Compound 27 was used to synthesize compound N-6.

[0499]

[0500] A 100 mL four-neck flask was charged with compound 27 (1.30 g, 1.10 mmol), compound 10 (0.767 g, 3.14 mmol) synthesized according to the method described in WO 2020 / 109823, and p-TsOH.H ２ O (0.597 g, 1.50 mmol), EtOH (12 g), toluene (26 g), MgSO ４ (0.65 g) was charged and kept warm in an oil bath heated to 65°C. After stirring for 2 hours, it was removed from the oil bath and allowed to cool to room temperature. ４ After removing the solvent, the precipitate was dissolved and washed with chloroform. After concentrating with an evaporator, a crude product was obtained by repulping and washing with methanol. The obtained crude product was purified with a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 1.26 g (yield 70%) of compound N-6 as a black solid. The NMR spectrum of the obtained compound N-6 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 9.03 (1H), 9.00 (1H), 8.85 (1H), 8.78 (1H), 8.19 (1H), 8.15 (1H), 7.71 (1H), 7.61-7.51 (m, 3H), 7.31 (1H), 4.19 (t, 4H), 2.85 (2H), 0.64-1.99 (m, 95H)

[0501] (Synthesis of Compound N-11) Compound 28 was synthesized using compound 12.

[0502]

[0503] Crude compound 12 (0.775 g), 5-Bromo-4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde (0.870 g, 2.72 mmol), and THF (7.0 g) were placed in a 50 mL three-neck flask, and nitrogen bubbling was carried out for 30 minutes. ２ (dba)３ (0.054g, 0.06mmol), P(tBu ３ )HBF ４ (0.034g, 0.12mmol), 3mol / L of K ３ P.O. ４ The mixture was charged with toluene and then an aqueous solution (2.19 g), and then heated 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 completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 100 / 0 to 75 / 25 (mass ratio)) to obtain 0.521 g of compound 28 as a reddish-purple viscous liquid. The NMR spectrum of the resulting compound 28 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 9.75 (2H), 7.47 (2H), 7.32 (2H), 4.11 (4H), 1.96-1.79 (m, 6H), 1.71-1.37 (m, 16H), 1.02-0.88 (m, 28H), 0.73-0.60 (m, 14H)

[0504] Compound 28 was used to synthesize compound N-11.

[0505]

[0506] In a 50 mL four-neck flask, compound 28 (0.521 g, 0.59 mmol), compound 10 (0.434 g, 1.78 mmol), and p-TsOH.H ２ O (0.338 g, 1.78 mmol), EtOH (4.7 g), toluene (10.4 g), MgSO ４ (0.26 g) was charged and kept warm in an oil bath heated to 65°C. After stirring for 2 hours, it was removed from the oil bath and allowed to cool to room temperature. ４After removing the solvent, the precipitate was dissolved and washed with chloroform. After concentration using an evaporator, a crude product was obtained by repulping and washing with methanol. The obtained crude product was purified using a silica gel column (developing solvent: chloroform = 100 wt%) and then repulping and washing with acetone to obtain 0.432 g (yield 55%) of compound N-11 as a blue-green black solid. The NMR spectrum of the obtained compound N-11 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 9.00 (2H), 8.79 (2H), 8.17 (2H), 7.73 (2H), 7.54 (2H), 4.21 (4H), 2.08-1.89 (m, 6H), 1.73-1.40 (m, 16H), 1.06-0.95 (m, 28H), 0.74-0.64 (m, 14H)

[0507] (Synthesis of Compound N-12) Compound 29 was synthesized using compound 17.

[0508]

[0509] Compound 17 (1.00 g, 12.7 mmol), 5-Bromo-4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde (0.934 g, 29.3 mmol) (manufactured by JiangSu GR-Chem Co., Ltd.), and THF (9.0 g) were placed in a 100 mL three-neck flask, and nitrogen bubbling was performed for 30 minutes. ２ (dba) ３ (0.058g, 0.06mmol), P(tBu ３ ) HBF ４ (0.037g, 0.13mmol), 3mol / L of K ３ P.O. ４The mixture was charged with an aqueous solution (2.36 g) and then heated to 60°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 amount was then concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane / toluene = 80 / 20 to 0 / 100 (mass ratio)) to obtain 0.53 g (yield 41%) of compound 29 as a blue-purple solid. The NMR spectrum of the resulting compound 29 was analyzed. The results are as follows. １ H-NMR (300MHz, CHLOROFORM-D) δ 9.75 (2H), 7.46 (2H), 7.09 (1H), 6.99 (1H), 4.09 (4H), 1.95-1.78 (m, 6H), 1.64-1.22 (m, 56H), 1.02-0.84 (m, 18H)

[0510] Compound 29 was used to synthesize compound N-12.

[0511] In a 30 mL three-neck flask, compound 29 (0.266 g, 0.264 mmol), compound 10 (0.194 g, 0.793 mmol), and p-TsOH.H ２ O (0.151 g, 0.0793 mmol), EtOH (2.4 g), toluene (5.3 g), MgSO ４ (0.13 g) was charged and kept warm in an oil bath heated to 65°C. After stirring for 2 hours, it was removed from the oil bath and allowed to cool to room temperature. ４ After removing the solvent, the precipitate was dissolved and washed with chloroform. After concentrating using an evaporator, a crude product was obtained by repulping and washing with methanol. The obtained crude product was purified using a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 0.265 g (yield 72%) of compound N-12 as a blue-green black solid. The NMR spectrum of the obtained compound N-12 was analyzed. The results are as follows. １H-NMR (300MHz, CHLOROFORM-D) δ 8.96 (1H), 8.78 (2H), 8.67 (1H), 8.17 (2H), 7.54 (1H), 7.46 (2H), 7.13 (1H), 4.24 (4H), 1.94-2.05 (m, 6H), 1.23-1.76 (m, 56H), 0.84-1.12 (m, 18H)

[0512] (Synthesis of Compound N-13) Compound 31 was synthesized using compound 30.

[0513]

[0514] A 50 mL four-neck flask was charged with magnesium turnings (0.353 g, 14.5 mmol), diethyl ether (10.0 mL), and iodine (small amount). After replacing the atmosphere with nitrogen, the flask 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 little by little at an internal temperature of 30°C or less. After the addition was complete, the bath temperature was raised to 43°C and the mixture was heated to reflux for 2 hours. After keeping the temperature for 2 hours, the mixture was cooled to room temperature to obtain the Grignard reagent. A 100 mL four-neck flask was charged with 2,5-Dibromothiophene (1.76 g, 7.27 mmol), PdCl ２ Dppf (0.200 g, 0.273 mmol) and diethyl ether (20.0 mL) were charged, and the mixture was purged with nitrogen and stirred at an internal temperature of 0°C. 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 hours. After quenching by pouring water (40 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: heptane = 100 wt%) to obtain 1.48 g of compound 31 as a yellow liquid. The NMR spectrum of the resulting compound 31 was analyzed. The results are as follows. １H-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)

[0515] Compound 32 was synthesized using compound 17.

[0516]

[0517] Compound 17 (1.40 g, 1.78 mmol), compound 31 (1.46 g, 4.09 mmol), and THF (52.7 g) were placed in a 100 mL three-neck flask, and nitrogen was bubbled through the flask for 30 minutes. ２ (dba) ３ (0.0813g, 0.089mmol), P(tBu ３ ) HBF ４ (0.103g, 0.355mmol), 3mol / L K ３ P.O. ４ The mixture was charged with an aqueous solution (8.22 g) and then 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 amount was then concentrated using 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 32 as a red liquid. The NMR spectrum of the obtained compound 32 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)

[0518] Compound 33 was synthesized using compound 32.

[0519]

[0520] Compound 32 (1.79 g, 1.65 mmol) and dichloromethane (109 g) were charged into a 200 mL four-neck flask. After nitrogen substitution, (chloromethylene) dimethylmininium chloride (0.845 g, 6.60 mmol) was charged and the mixture was kept warm in an oil bath heated to 49 °C. After stirring for 24 hours, the mixture was removed from the oil bath and allowed to cool to room temperature. After washing twice with water, the mixture was dehydrated with magnesium sulfate. The magnesium sulfate was removed by filtration, and the entire amount was 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)), yielding 1.72 g (yield 92%) of compound 33 as a dark red liquid. The NMR spectrum of the resulting compound 33 was analyzed. The results are as follows. 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)

[0521] Compound N-13 was synthesized using compound 33.

[0522]

[0523] In a 100 mL four-neck flask, compound 33 (0.627 g, 0.550 mmol), compound 10 (0.322 g, 1.32 mmol), and p-TsOH.H ２O (0.209 g, 1.10 mmol), EtOH (21.7 g), and toluene (23.8 g) were charged and kept warm in an oil bath heated to 89°C. After stirring for 3 hours, the mixture was removed from the oil bath and allowed to cool to room temperature, and then added dropwise to methanol (115 g). The precipitate was collected by filtration to obtain a crude product. Chloroform (50 g) was added to the obtained crude product, and the internal temperature was raised to 60°C, followed by heating and stirring 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 (yield 30%) of compound N-13 as a black solid. The NMR spectrum of the obtained compound N-13 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ9.03 (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)

[0524] (Synthesis of Compound N-14) Compound 35 was synthesized using compound 34.

[0525]

[0526] A 50 mL four-neck flask was charged with 4,8-Bis(3,5-dioctyl-2-thienyl)-2,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzo[1,2-b:4,5-b']dithiophene (0.956 g, 0.906 mmol), compound 16 (1.20 g, 2.27 mmol), and THF (21.8 g), and nitrogen bubbling was performed for 30 minutes. ２ (dba) ３ (0.0415g, 0.045mmol), P(tBu ３ ) HBF ４ (0.0276g, 0.095mmol), 3mol / L of K ３ P.O.４ The mixture was charged with toluene and then an aqueous solution (4.19 g), and then heated 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 completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 7 / 1 (volume ratio)) to obtain 0.90 g of compound 35 as a red viscous liquid. The NMR spectrum of the resulting compound 35 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ9.75 (2H), 7.46 (2H), 7.40-7.39 (2H), 7.18 (2H), 6.78 (2H), 4.13-3.98 (m, 8H), 2.27 (4H), 2.45-2.37 (m, 4H), 1.85-0.70 (m, 120H)

[0527] Compound 35 was used to synthesize compound N-14.

[0528]

[0529] In a 50 mL four-neck flask, compound 35 (0.500 g, 0.294 mmol), compound 10 (0.215 g, 0.882 mmol), and p-TsOH.H ２ O (0.168 g, 0.882 mmol), EtOH (4.6 g), toluene (10.0 g), MgSO ４ (0.250 g) was charged and kept warm in an oil bath heated to 65°C. After stirring for 2 hours, it was removed from the oil bath and allowed to cool to room temperature. ４ After removing the solvent, the precipitate was dissolved and washed with chloroform. After concentrating with an evaporator, a crude product was obtained by repulping and washing with methanol. The obtained crude product was purified with a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 0.46 g (yield 73%) of compound N-14 as a black solid. The NMR spectrum of the obtained compound N-14 was analyzed. The results are as follows. １H-NMR (300 MHz, CHLOROFORM-D) δ8.93-8.70 (4H), 8.13 (2H), 7.53-7.23 (6H), 6.81 (2H), 4.14 (8H), 3.01-2.88 (m, 4H), 2.44-2.21 (m, 4H), 1.91-0.61 (m, 120H)

[0530] (Synthesis of Compound N-7) Compound 37 was synthesized using compound 36.

[0531]

[0532] A 100 mL four-neck flask was purged with nitrogen, charged with 60% sodium hydride (3.68 g, 92.06 mmol) and THF (23.3 ml), and then 2-hexyl-1-decanol (26.6 ml, 92.06 mmol) was added dropwise. After stirring at room temperature for 2 hours, the temperature was raised to 70°C. Compound 36 (5.43 g, 60.97 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise at 70°C, and the mixture was stirred for 2 hours. The reaction solution was cooled to room temperature and quenched with saturated aqueous ammonium chloride. The solid matter was removed by filtration through Celite while rinsing with heptane. The filtrate was washed three times with water and then concentrated using a rotary evaporator to obtain a crude product. The resulting crude product was purified by silica gel column chromatography (heptane / ethyl acetate = 5 / 1), yielding 22.86 g of compound 37 (yield 14%). The NMR spectrum of compound 37 was analyzed. The results are as follows: １ H-NMR (300 MHz, CHLOROFORM-D) δ 8.54 (1H), 6.10 (1H), 3.98 (2H), 1.76 (1H), 0.80-1.56 (30H)

[0533] Compound 37 was used to synthesize compound 38.

[0534]

[0535] A 500 ml four-neck flask was purged with nitrogen and charged with compound 37 (4.70 g, 14.43 mmol) and THF (105.7 ml). The flask was cooled to -75 °C in a dry ice / acetone bath. A 1.6 M nBuLi hexane solution (9.53 ml, 15.15 mmol) was added dropwise at -75 °C and stirred for 1.5 hours. N-formylpiperidine (16.01 ml, 14.43 mmol) was then added dropwise and the mixture was warmed to room temperature. After stirring at room temperature for 2 hours, the reaction vessel was placed in an ice bath and quenched with 20% aqueous ammonium chloride solution. Heptane was added, the aqueous layer was removed, and the mixture was washed once with water. The organic layer was dried over magnesium sulfate, filtered to remove the magnesium sulfate, and then concentrated on a rotary evaporator to obtain 4.42 g of crude product. The crude product obtained was used in the next reaction without purification. The NMR spectrum of compound 38 was analyzed. The results are as follows: １ H-NMR (300 MHz, CHLOROFORM-D) δ 9.87 (1H), 6.62 (1H), 4.11 (2H), 1.83 (1H), 0. 80-1.56 (30H)

[0536] Compound 39 was synthesized using compound 38.

[0537]

[0538] A 100 mL four-neck flask was purged with nitrogen, and compound 38 (5.10 g) and chloroform (53.7 ml) were charged and cooled to 2°C in an ice bath. N-bromosuccinimide (2.96 g, 16.63 mmol) was then added in three portions and stirred for 1 hour. The reaction solution was quenched with a 3% aqueous sodium sulfite solution, and the organic layer was extracted with chloroform and then washed with water. The organic layer was dried over magnesium sulfate, filtered to remove the magnesium sulfate, and then concentrated on a rotary evaporator to obtain a crude product. The resulting crude product was purified by silica gel column chromatography (heptane / ethyl acetate = 20 / 1) to obtain 4.94 g of compound 39. The NMR spectrum of compound 39 was analyzed. The results are as follows. １H-NMR (300 MHz, CHLOROFORM-D) δ 9.74 (1H), 4.31 (2H), 1.81 (1H) 0.80- 1.56 (30H)

[0539] Compound 40 was synthesized using compound 20 and compound 39.

[0540]

[0541] A 100 mL four-neck flask was purged with nitrogen, and compound 20 (1.00 g, 0.752 mmol), compound 39 (0.390 g, 0.902 mmol), and THF (22.6 ml) were charged, followed by bubbling with nitrogen for 30 minutes. ２ (dba) ３ (0.0344g, 0.0376mmol), P(tBu ３ )HBF ４ (0.0229g, 0.0789mmol), 3mol / L of K ３ P.O. ４ The mixture was then charged with an aqueous solution (2.51 ml) and heated to 60°C. After stirring for 2 hours, the mixture was cooled to room temperature. The reaction mass was diluted with heptane, washed twice with water, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The resulting crude product was purified by recycled GPC (chloroform) to obtain 0.421 g of compound 40 (yield 40%). The NMR spectrum of the resulting compound 40 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ9.77 (1H), 7.31 (1H), 7.03 (1H), 6.98 (1H), 6.93 (1H), 5.56 (1H), 4.45 (2H), 4.03 (4H), 3.77 (2H), 3.64 (2H), 1.88 (7H), 0.55-1.60 (110H)

[0542] Compound 41 was synthesized using compound 40.

[0543]

[0544] A 50 mL four-neck flask was purged with nitrogen and charged with compound 40 (0.323 g, 0.230 mmol), THF (15.1 ml), water (3.78 ml), and trifluoroacetic acid (0.353 ml). The mixture was cooled in an ice bath and stirred for 3 hours. The reaction solution was diluted with heptane, quenched with a 5% aqueous solution of disodium hydrogen phosphate, and then washed twice with water. The organic layer was dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator to obtain a crude product. The resulting crude product was purified using recycled GPC (chloroform) to obtain 0.386 g of compound 41 (yield 97%). The NMR spectrum of the resulting compound 41 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ9.78 (1H), 9.76 (1H), 7.48 (1H), 7.32 (1H), 7.20 (1H), 7.12 (1H), 4.47 (2H), 4.11 (2H), 4.06 (2H), 1.88 (7H), 0.55-1.70 (104H)

[0545] Compound 41 was used to synthesize compound N-7.

[0546]

[0547] In a 50 mL three-neck flask, compound 41 (0.363 g, 0.276 mmol), compound 10 (0.202 g, 0.828 mmol), and p-TsOH.H ２ O (0.157 g, 0.828 mmol), EtOH (4.1 ml), toluene (8.4 ml), MgSO ４ (0.182 g) was charged and kept warm in an oil bath heated to 65°C. After stirring for 2 hours, it was removed from the oil bath and allowed to cool to room temperature. ４ After removing the solvent, the precipitate was dissolved and washed with chloroform. After concentrating with an evaporator, a crude product was obtained by repulping and washing with methanol. The obtained crude product was purified by recycling GPC to obtain 0.210 g (yield 43%) of compound N-7 as a black solid. The NMR spectrum of the obtained compound N-7 was analyzed. The results are as follows. １H-NMR (300 MHz, CHLOROFORM-D) δ8.99 (2H), 8.89 (1H), 8.78 (1H), 8.14 (2H), 7.71 (1H), 7.50 (2H), 7.32 (1H), 4.58 (2H), 4.19 (4H), 1.99 (7H), 0.55-1.70 (104H)

[0548] (Synthesis of Compound N-8) Compound 48 was synthesized according to the following scheme. The NMR spectrum of the obtained compound 48 was analyzed. The results are as follows. １ H-NMR (300 MHz, DMSO-d6) δ 8.36 (1H), 8.18 (1H), 6.05 (1H)

[0549]

[0550] Compound N-8 was synthesized using Compound 27 and Compound 48.

[0551]

[0552] In a 100 mL four-neck flask, compound 27 (0.300 g, 0.25 mmol), compound 48 (0.399 g, 1.26 mmol), and p-TsOH.H ２ O (0.336 g, 1.77 mmol), EtOH (19.5 g), and toluene (8.1 g) were charged and kept warm in an oil bath heated to 65°C. After stirring for 2 hours, the mixture was removed from the oil bath and allowed to cool to room temperature. The precipitated solid was recovered by filtration and washed with methanol, ethanol, and heptane to obtain a crude product. The obtained crude product was purified by recycling GPC (developing solvent: chloroform = 100 wt%) to obtain 0.297 g of compound N-8 as a black solid. The NMR spectrum of the obtained compound N-8 was analyzed. The results are as follows. １H-NMR (300 MHz, CHLOROFORM-D) δ8.90 (s, 1H), 8.73 (s, 1H), 8.48 (m, 1H), 8.42 (s, 1H), 8.32-8.24 (m, 2H), 7.77 (s, 1H), 7.68-7.64 (m, 1H), 7.36-7.24 (m, 3H), 4.25-4.10 (m, 4H), 2.88 (d, 2H), 2.03-0.68 (m, 95H)

[0553] (Synthesis of Compound N-9) Compound 49 was synthesized using Compound 1.

[0554]

[0555] A 200 ml four-neck flask was purged with nitrogen, and pTsOH monohydrate (0.42 g, 2.19 mmol), 2-ethyl-1-hexanethiol (9.42 ml, 54.7 mmol), compound 1 (2.16 ml, 21.9 mmol), and toluene (43.2 ml) were added, followed by stirring at 100°C for 2.5 hours. After allowing to cool to room temperature, the mixture was washed twice with water. The organic layer was dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (developing solvent: heptane), yielding 4.05 g of compound 49. The NMR spectrum of the obtained compound 49 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 7.31 (1H), 7.08 (1H), 7.00 (1H), 2.84 (2H), 1.20-1.55 (9H), 0.83-0.95 (6H)

[0556] Compound 50 was synthesized using compound 49.

[0557]

[0558] A 200 ml four-neck flask was purged with nitrogen, and Compound 49 (1.99 g, 8.76 mmol) and chloroform (21.1 ml) were added. The flask was cooled in an ice bath, and N-bromosuccinimide (1.50 g, 8.42 mmol) was added in three portions. After stirring for 4 hours, 3% Na ２ SO３ The mixture was quenched with an aqueous solution, warmed to room temperature, and the aqueous layer was removed. After washing with water once more, the organic layer was dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator to obtain a crude product. The obtained crude product was dissolved in heptane, filtered through a 10 mm layer of silica gel in a Kiriyama funnel, and concentrated again to obtain 2.45 g of compound 50. The NMR spectrum of the obtained compound 50 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ7.25 (1H), 6.93 (2H), 2.83 (2H), 1.20-1.55 (9H), 0. 83-0.95 (6H)

[0559] Compound 51 was synthesized using compound 12 and compound 24.

[0560]

[0561] A 100 mL four-neck flask was purged with nitrogen, and Compound 12 (1.375 g, 2.10 mmol), Compound 24 (1.86 g, 4.62 mmol), and THF (30.9 ml) were added. After bubbling with nitrogen for 30 minutes, Pd ２ (dba) ３ (0.096g, 0.11mmol), [(tBu) ３ PH]BF ４ (0.061g, 0.21mmol), 3M K ３ P.O. ４ An aqueous solution (7.00 ml) was added, and the temperature was raised to 60°C. After keeping the temperature for 1 hour, the reaction solution was cooled to room temperature, diluted with 25 ml of heptane, and washed twice with 12.5 ml of water. The solution was dried over magnesium sulfate, filtered to remove the magnesium sulfate, and then concentrated using a rotary evaporator to obtain a 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 51 as a red liquid. The NMR spectrum of the obtained compound 51 was analyzed. The results are as follows. １H-NMR (300 MHz, CHLOROFORM-D) δ 7.08 (2H), 6.99 (2H), 6.84 (2H), 4.01 (4H), 1.84 (4H), 0.50-1.60 (H)

[0562] Compound 52 was synthesized using compound 51.

[0563]

[0564] A 300 ml four-neck flask was purged with nitrogen, and compound 51 (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, followed by stirring for 1 hour. A THF (33.4 ml) solution of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.58 g, 8.50 mmol) 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 solution (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 a crude product of Compound 52.

[0565] Compound 53 was synthesized using compound 50 and compound 52.

[0566]

[0567] Compound 50 (0.524 g, 1.70 mmol), the crude product of Compound 52 (3.83 g), and tetrahydrofuran (51.3 ml) were placed in a 100 mL four-neck flask, and the flask was purged with nitrogen. ２ (dba) ３ (0.0781g, 0.085mmol manufactured by Strem Chemicals), [(tBu) ３ PH]BF ４ (Tokyo Chemical Industry Co., Ltd., 0.0495 g, 0.171 mmol), 3M K ３ P.O. ４An aqueous solution (5.7 ml) was charged and heated to 60°C. After stirring and maintaining the temperature for 1 hour, the reaction solution was cooled to room temperature, diluted with heptane, and washed twice with water. The mixture was dried over magnesium sulfate, filtered to remove the magnesium sulfate, and then concentrated using a rotary evaporator to obtain a crude product. The obtained crude product was purified using a silica gel column (developing solvent: heptane → heptane / ethyl acetate = 10 / 1 (v / v)) to obtain 1.19 g of compound 53 as an orange oil. The NMR spectrum of the obtained compound 53 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 7.10-7.17 (3H), 7.08 (1H), 7.03 (2H), 6.84 (1H), 4.00-4.06 (4H), 2.85 (2H), 1.85 (6H), 0.50-1.65 (105H)

[0568] Compound 54 was synthesized using compound 53.

[0569]

[0570] In a 50 mL four-neck flask, compound 53 (1.04 g, 0.823 mmol), CHCl ３ (10.0 ml) was added and the atmosphere was replaced with nitrogen, (Chloromethylene) dim ethylmininium chloride (Tokyo Chemical Industry Co., Ltd., 0.969 g, 7.57 mmol) was added, the temperature was raised to 60 ° C, and the mixture was stirred while maintaining the temperature. After stirring for 5 hours, the mixture was removed from the oil bath and allowed to cool to room temperature. Water (4.9 ml), 5 wt % NaHCO ３ The reaction mixture was quenched by pouring 9.9 ml of aq. into the cooled mass with stirring, and the aqueous layer was removed from the resulting mass by separation. The mixture was washed with water, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator to obtain a crude product of compound 54. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 10 / 1 (v / v)) to obtain 1.09 g of compound 54 as a reddish-purple oil. The NMR spectrum of the resulting compound 54 was analyzed. The results are as follows. １H-NMR (300 MHz, CHLOROFORM-D) δ 9.81 (1H), 9.73 (1H), 7.67 (1H), 7.45 (1H), 7.34 (2H), 7.20 (1H), 4.08 (4H), 2.89 (2H), 1.90 (6H), 0.50-1.65 (105H)

[0571] Compound N-9 was synthesized using compound 54 and compound 48.

[0572]

[0573] In a 100 mL four-neck flask, compound 54 (0.400 g, 0.301 mmol), compound 48 (0.237 g, 0.752 mmol), and p-TsOH.H ２ O (0.200 g, 1.05 mmol), EtOH (26.0 g), and toluene (10.8 g) were added, and the mixture was kept warm in an oil bath heated to 65°C. After stirring for 2 hours, the mixture was removed from the oil bath and allowed to cool to room temperature. The precipitated solid was recovered by filtration and washed with methanol, ethanol, and heptane to obtain a crude product. The obtained crude product was purified by recycling GPC (developing solvent: chloroform = 100 wt%) to obtain 0.359 g of compound N-9 as a black solid. The NMR spectrum of the obtained compound N-9 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 8.84 (1H), 8.78 (1H), 8.44 (2H), 8.38 (2H), 7.85 (1H) 7.78 (1H), 7.53 (1H), 7.41 (1H), 7.34 (1H), 4.19 (4H), 3.07 (2H), 2.01 (5H), 0.60-1.85 (104H)

[0574] (Synthesis of Compound N-10) Compound N-10 was synthesized using Compound 54 and Compound 10.

[0575]

[0576] In a 100 mL four-neck flask, compound 54 (0.300 g, 0.23 mmol), compound 10 (0.165 g, 0.68 mmol), and p-TsOH.H ２O (0.129 g, 0.68 mmol), EtOH (3.4 ml), toluene (6.9 ml), MgSO ４ (0.150 g) was charged and replaced with nitrogen, then heated to 65°C and stirred while keeping the temperature. After stirring for 3 hours, the mixture was removed from the oil bath and allowed to cool to room temperature. ４ After removing the solvent, the precipitate was washed with chloroform while dissolving it. The solution obtained using an evaporator was concentrated, and then washed with methanol using a Kiriyama filter to obtain a crude product. The obtained crude product was purified using recycle GPC to obtain 0.29 g of compound N-10 as a black solid (yield 72%). The NMR spectrum of the obtained compound N-10 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ9.84 (1H), 9.04 (1H), 8.96 (1H), 8.82 (1H), 8.71 (1H), 8.21 (1H), 8.11 (1H), 7.84 (1H), 7.75 (1H), 7.60 (1H), 7.39 (1H), 7.33 (1H), 4.21 (2H), 4.19 (2H), 3.03 (2H), 1.99-0.5 (118H)

[0577] <Measurement of Optical Absorption Terminal Wavelength of Thin Film> Compounds N-1, N-2, N-3, N-4, N-5, N-6, N-7, N-9, N-10, N-11, N-12, N-13, and N-14 were each added to orthodichlorobenzene to a concentration of 1.0% by mass. Compound-8 was also added to 1,2,4-trimethylbenzene to a concentration of 1.0% by mass. The mixture was heated and stirred at 65°C for 4 hours under a nitrogen atmosphere to prepare a solution. The filtrate was used as a 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 coating film obtained by spin coating was placed on a hot plate. The film was dried under atmospheric conditions at 70°C for 5 minutes to obtain a thin film for UV-Vis spectrum measurement. The optical absorption terminal wavelength (λth) was measured using this thin film. The details of the measurement method are as described above.

[0578] Compound N-1: 1567nm Compound N-2: 1804nm Compound N-3: 1620nm Compound N-4: 1480nm Compound N-5: 1546nm Compound N-6: 1437nm Compound N-7: 1630nm Compound N-8: 1502nm Compound N-9: 1624 nm Compound N-10: 1531 nm Compound N-11: 1355 nm Compound N-12: 1354 nm Compound N-13: 1175 nm Compound N-14: 1314 nm

[0579] From the above results, it was found that Compounds N-1 to N-10 can absorb light of 1400 nm or more, which is a particularly long wavelength in the SWIR region.

[0580] <Measurement of Maximum Light Absorption Wavelength of Solution> Compounds N-1, N-2, N-3, N-4, N-5, N-6, N-7, N-9, N-10, N-11, N-12, N-13, and N-14 were each added to orthodichlorobenzene to a concentration of 0.00125% by mass to obtain a solution for UV-Vis spectrum measurement. Compound N-8 was also added to 1,2,4-trimethylbenzene to a concentration of 0.00125% by mass to obtain a solution for UV-Vis spectrum measurement. The maximum light absorption wavelength (λmax) was measured using this solution. Details of the measurement method are as described above.

[0581] Compound N-1: 1052 nm Compound N-2: 1130 nm Compound N-3: 1133 nm Compound N-4: 1027 nm Compound N-5: 1051 nm Compound N-6: 991 nm Compound N-7: 1092 nm Compound N-8: 1001 nm Compound N-9: 1111 nm Compound N-10: 1013 nm Compound N-11: 962 nm Compound N-12: 927 nm Compound N-13: 814 nm Compound N-14: 930 nm

[0582] <Difference between Light Absorption Terminal Wavelength of Thin Film and Light Absorption Maximum Wavelength of Solution> The difference between the light absorption terminal wavelength of the thin film and the light absorption maximum wavelength of the solution was calculated for each of Compound N-1, Compound N-2, Compound N-3, Compound N-4, Compound N-5, Compound N-6, Compound N-7, Compound N-8, Compound N-9, Compound N-10, Compound N-11, Compound N-12, Compound N-13, and Compound N-14.

[0583] Compound N-1: 515 nm Compound N-2: 674 nm Compound N-3: 487 nm Compound N-4: 453 nm Compound N-5: 495 nm Compound N-6: 446 nm Compound N-7: 538 nm Compound N-8: 501 nm Compound N-9: 513 nm Compound N-10: 518 nm Compound N-11: 393 nm Compound N-12: 427 nm Compound N-13: 361 nm Compound N-14: 384 nm

[0584] As described above, the difference between the light absorption terminal wavelength of the thin film and the light absorption maximum wavelength of the solution was large for Compounds N-1 to N-10. That is, Compounds N-1 to N-10 existed in a monomolecular state in the solution, but in the thin film, the compounds associated with each other, making them more susceptible to absorbing light of long wavelengths.

[0585] <Distance from group D to group A1 (d Ｃ１－Ｃ２ )> Next, for Compounds N-1, N-2, N-3, N-4, N-5, N-6, N-7, N-8, N-9, N-10, N-11, N-12, N-13, and N-14, the distance (d Ｃ１－Ｃ２ ) was calculated.

[0586] d Ｃ１－Ｃ２ 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 GaussView 6. Ｃ１－Ｃ２ was calculated.Ｃ１－Ｃ２ In calculating the alkyl group contained in each compound, a propyl group (-CH ２ -CH ２ -CH ３ The calculated values ​​are almost the same for the compound before and after the alkyl group is changed to a propyl group.

[0587]

[0588]

[0589]

[0590]

[0591]

[0592] <Preparation of Ink> (Preparation of Ink (I-1)) The following components were mixed and stirred at room temperature for 12 hours. The resulting mixture was filtered using a filter to obtain Ink (I-1). P-type semiconductor material: polymer compound P-19...0.8% by mass N-type semiconductor material: compound N-1...0.56% by mass N-type semiconductor material: C60PCBM...0.24% by mass Solvent: chloroform / 1-chloronaphthalene=98 wt% / 2 wt%...the balance to make the total ink 100% by mass

[0593] C60PCBM ([6,6]-Phenyl C61 butylic acid methyl ester) was commercially available under the trade name "E100" manufactured by Frontier Carbon Corporation and used.

[0594] (Preparation of Ink (I-11)) Ink (I-11) was obtained in the same manner as in the preparation of Ink (I-1), except that Compound N-1 was changed to Compound N-11.

[0595] <Production of Photoelectric Conversion Element and Sealed Body Thereof> 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.

[0596] Next, a solution prepared by diluting 80% ethoxylated polyethyleneimine aqueous solution (manufactured by Sigma-Aldrich, 37% by mass aqueous solution) 500 times with water was applied to the cleaned glass substrate by spin coating to form a coating film, and the substrate was then placed on a hot plate and dried in the air at 120°C for 10 minutes to form an electron transport layer.

[0597] 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 using a hot plate heated to 70°C in the atmosphere (pre-bake step), and then heated for 10 minutes at 100°C on a hot plate in a nitrogen atmosphere (post-bake step) to form an active layer. The thickness of the formed active layer was approximately 350 nm.

[0598] Next, molybdenum oxide (MoO ３ A ) layer was formed to a thickness of about 30 nm to serve as a hole transport layer.

[0599] 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.

[0600] 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.

[0601] [Evaluation of Photoelectric Conversion Element] With a reverse bias voltage of 3 V applied to the obtained photoelectric conversion element, monochromatic light of 1500 nm (number of photons: 1×10) was measured using a spectral sensitivity measurement device (manufactured by Bunkoukeiki Co., Ltd., product name: CEP-25SC type). １４The photodiode drive test was carried out by a known method, and the photoelectric conversion element was irradiated with light of a wavelength of 1000 nm or more, and the generated current value was measured. In this test, a case where a photoelectric conversion effect was confirmed was judged as Y, and a case where no photoelectric conversion was performed was judged as N.

[0602]

[0603] As described above, it has been 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 a longer wavelength range compared to a photoelectric conversion element using a conventional n-type semiconductor material.

[0604] REFERENCE SIGNS LIST 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), in which the distance from the element on the D side among the elements forming a single bond between D and L1 in formula (1) to the element on the A1 side among the elements forming a single bond between A1 and L1 is 9 Å or more. In formula (1), D is a divalent aromatic group, the main skeleton of the monocyclic or condensed ring constituting the aromatic group in D has at least one of sp3 carbon and sp3 silicon, and D is a monovalent side chain R bonded to the sp3 carbon or sp3 silicon. Ｄ１ L1 is a divalent aromatic group, the main skeleton of a monocyclic or fused ring constituting the aromatic group in L1 may or may not have an sp3 carbon or sp3 silicon, and when it has an sp3 carbon or sp3 silicon, L1 does not have a monovalent side chain bonded to the sp3 carbon or sp3 silicon in L1, the main skeleton of a monocyclic or fused ring constituting the aromatic group in L1 has an sp2 carbon, and L1 has a monovalent side chain R bonded to the sp2 carbon. Ｌ１ The aromatic group in L1 has an element capable of non-covalent interaction with an element in an adjacent unit, R Ｄ１ and R Ｌ１ each independently represents a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio 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 substituted carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group; L2 is a divalent aromatic group, m is an integer of 1 to 4; n is an integer of 0 to 4; and A1 and A2 are each independently a group represented by the following formula (A-1). In formula (A-1), Ar represents a carbocycle which may have a substituent, or a heterocycle which may have a substituent, and the carbocycle and the heterocycle are each independently a monocycle or a condensed ring, and when the carbocycle or the heterocycle has a plurality of substituents, the plurality of substituents may be the same or different.

2. The compound according to claim 1, wherein in the formula (1), D is any of groups represented by the following formulas (D-1) to (D-4): In formulas (D-1) to (D-4), X is any of the groups represented by the following formulas (X-1) to (X-6). In the formulas (D-3), (D-4), and (X-1) to (X-6), R Ｄ２ The definitions of each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, a cycloalkylthio group which may have a substituent, an arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, an acyl group which may have a substituent, 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, a cycloalkenyl group which may have a substituent, an alkynyl group which may have a substituent, a cycloalkynyl group which may have a substituent, a cyano group, or a nitro group. 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.) 3. The compound according to claim 1 or 2, wherein in formula (1), L1 is each independently any of groups represented by formulas (L1-1) to (L1-7) below. (In formulas (L1-1) to (L1-7), R Ｌ１１ each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio 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 carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group; further R Ｌ１１ each independently has at least one atom selected from the group consisting of a sulfur atom, an oxygen atom, a fluorine atom, a nitrogen atom, a selenium atom, and a phosphorus atom.

4. The compound according to claim 1 or 2, wherein in formula (1), L2 is each independently any of groups represented by formulas (L2-1) to (L2-9) below. (In formula (L2-1) to formula (L2-9), a plurality of R Ｌ２ each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group, a cycloalkylthio group which may have a substituent, an arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, an acyl group which may have a substituent, 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, a cycloalkenyl group which may have a substituent, an alkynyl group which may have a substituent, a cycloalkynyl group which may have a substituent, a cyano group, or a nitro group.

5. The compound according to claim 1 or 2, wherein in formula (1), m is 2 and n is 1 or 2.

6. The compound according to claim 1 or 2, wherein in formula (1), A1 and A2 are each independently any of groups represented by the following formulas (a-1) to (a-8): (In formula (a-1) to formula (a-8), a plurality of R Ａ１ are each independently a hydrogen atom, a halogen atom, or a cyano group.

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

8. The composition according to claim 7, 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): (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): In formulae (Z-1) to (Z-7), R each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group, a cycloalkylthio group which may have a substituent, an arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, an acyl group which may have a substituent, 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, a cycloalkenyl group which may have a substituent, an alkynyl group which may have a substituent, a cycloalkynyl group which may have a substituent, a cyano group, or a nitro group; In each of formulas (Z-1) to (Z-7), when there are two R's, the two R's may be the same or different. ５ represents a divalent aromatic heterocyclic group.

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

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

11. The photoelectric conversion element according to claim 10, which is a photodetection element.

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

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