Compound, composition, ink, photoelectric transducer and photosensor

Abstract

To provide a compound, a composition, an ink, a photoelectric transducer and a photosensor, enabling photoelectric conversion at a long wavelength region.SOLUTION: A compound is expressed by a formula (1). In the formula (1), 9Å or more is a distance from a chemical element on a D side from among chemical elements forming a single bond of D and L1, to a chemical element on an A1 side from among chemical elements forming a single bond of A1 and L1. In the formula (1), A1, A2, L1, L2, D, m and n are as defined in the description.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to compounds, compositions, inks, photoelectric conversion elements, and optical sensors.

Background Art

[0002] A photoelectric conversion element is an element comprising 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 extremely useful devices, for example, from the viewpoints of energy saving and reduction of carbon dioxide emissions, and have attracted attention.

[0003] As a compound used in a photoelectric conversion element, for example, in Patent Document 1, a near-infrared organic photoreceptor molecule CN5T applying a 3-alkoxy-4-cyanothiophene structure is disclosed. Patent Document 1 discloses that the absorption edge wavelength in the absorption spectrum of CN5T in a thin film state was around 1200 nm.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, knowledge regarding compounds enabling photoelectric conversion at wavelengths of 1400 nm or more, which are particularly long wavelengths in the SWIR (Short Wavelength Infrared) region, is currently limited.

[0006] The present disclosure has been made in view of the above, and the present disclosure relates to the provision of compounds, compositions, inks, photoelectric conversion elements, and optical sensors enabling photoelectric conversion in the long wavelength region.

Means for Solving the Problems

[0007] Specific means for solving the above problems include the following aspects. <1> A compound represented by the following formula (1), In formula (1), 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.

[0008] [Chemical formula]

[0009] (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 has at least one monovalent side chain R D1 bonded to the sp3 carbon or the sp3 silicon, L1 is a divalent aromatic group, The main skeleton of the monocyclic or condensed ring constituting the aromatic group in L1 may or may not have sp3 carbon or sp3 silicon. When it has sp3 carbon or 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 condensed ring constituting the aromatic group in L1 has sp2 carbon, and L1 has at least one monovalent side chain R L1 bonded to the sp2 carbon, 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 are each independently 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 substitutedoxysulfonyl 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, represents, L2 is a divalent aromatic group, m is an integer of any one of 1 to 4, n is an integer of any one of 0 to 4, A1 and A2 are each independently a group represented by the following formula (A-1).

[0010]

Chemical formula

[0011] In formula (A-1), Ar represents a carbocyclic ring which may have a substituent or a heterocyclic ring which may have a substituent. The carbocyclic ring and the heterocyclic ring are each independently a monocyclic ring or a condensed ring. When the carbocyclic ring or the heterocyclic ring has a plurality of substituents, the plurality of substituents may be the same or different.) <2> In the formula (1), The compound according to <1>, wherein D is any one of the groups represented by the following formula (D-1) to formula (D-4).

[0012]

Chemical formula

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

[0014]

Chemical formula

[0015] In formula (D-3), formula (D-4), and formula (X-1) to formula (X-6), R D2 are each independently 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 substitutedoxysulfonyl 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 carbon ring which may have a substituent and in which a plurality of ring structures may be further fused, or an aromatic heterocyclic ring which may have a substituent and in which a plurality of ring structures may be further fused. Either Ar 1 or Ar 2 may not be present.) <3> In the formula (1), L1 is each independently any group represented by the following formula (L1-1) to formula (L1-7), the compound according to <1> or <2>.

[0016]

Chemical formula

[0017] (In the formula (L1-1) to formula (L1-7), R L11 are each independently 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 substitutedoxysulfonyl 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, and further, each R 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.) <4> In the formula (1), L2 is any group represented by the following formula (L2-1) to formula (L2-9), and is the compound according to any one of <1> to <3>.

[0018]

Chemical formula

[0019] (In formulas (L2-1) to (L2-9), a plurality of Rs 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 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 substitutedoxysulfonyl 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> In the formula (1), m is 2, and n is 1 or 2. The compound according to any one of <1> to <4>. <6> In the formula (1), A1 and A2 are each independently any group represented by the following formula (a-1) to formula (a-8). The compound according to any one of <1> to <5>.

[0020]

Chemical formula

[0021] (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, wherein the n-type semiconductor material contains the compound according to 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]

Chemical formula

[0023] (In formula (3), Ar 3 and Ar 4 each independently represent a trivalent aromatic heterocyclic group which may have a substituent, and Z represents any group represented by the following formula (Z-1) to formula (Z-7).

[0024]

Chemical formula

[0025] In formula (Z-1) to formula (Z-7), R are each independently 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, represents, In each of Formula (Z-1) to Formula (Z-7), when there are two Rs, the two Rs may be the same as or different from each other. In Formula (4), Ar 5 represents a divalent aromatic heterocyclic group.) <9> An ink containing the compound according to any one of <1> to <6> and a solvent. <10> 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. A photoelectric conversion element, 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 photodetector. <12> An optical sensor including the photoelectric conversion element according to <10> or <11>.

Advantages of the Invention

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

Brief Description of the Drawings

[0027]

Figure 1

Embodiments for Carrying Out the Invention

[0028] Hereinafter, an embodiment of the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following disclosure, its components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values and their ranges, which do not limit the present disclosure.

[0029] Hereinafter, the compound of the present disclosure will be described, and further, the photoelectric conversion element using the compound of the present disclosure will be described with reference to the drawings. Note that the drawings only schematically 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 changed without departing from the gist of the present disclosure. Also, the configuration of the present disclosure is not necessarily manufactured or used in the arrangement shown in the drawings.

[0030] In the present disclosure, in the numerical range indicated using "~", the numerical values described before and after "~" are included as the lower limit value and the upper limit value, respectively. In the numerical ranges described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in other stepwise descriptions. Further, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. In the present disclosure, the content rate of each component in the composition means the total content rate of the plurality of substances corresponding to each component in the composition, unless otherwise specified, when there are a plurality of substances corresponding to each component in the composition. In the present disclosure, when a plurality of elements are listed using "or" or "alternatively", unless otherwise specified, the selection of combining a plurality of elements is not excluded as long as there is no technical contradiction. In the present disclosure, even when an element is represented in the singular form, unless otherwise specified, the existence of a plurality is not excluded as long as there is no technical contradiction. In the present disclosure, a plurality of separately described exemplary embodiments may be combined with each other to form a new embodiment as long as they do not contradict each other.

[0031] In the present disclosure, commonly used terms are explained. In the description of the present disclosure, the following explanations apply unless otherwise specified individually.

[0032] "Non-fullerene compound" means a compound that is neither a fullerene nor a fullerene derivative.

[0033] "π-conjugated system" means a system in which π electrons are delocalized over a plurality of bonds.

[0034] "Polymer compound" means a polymer having a molecular weight distribution and a number average molecular weight in terms of polystyrene of 1×10 3 or more and 1×10 8 or less. Note that the constituent units included in the polymer compound are 100 mol% in total.

[0035] The "structural unit" means a residue derived from a raw material compound (monomer) that is present in one or more in a compound and a polymer compound.

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

[0037] Examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0038] The aspect of "optionally having a substituent" includes both aspects where all hydrogen atoms constituting a compound or a group are unsubstituted and where some or all of one or more hydrogen atoms are substituted by 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 the present specification, when referring to the number of carbon atoms, usually the number of carbon atoms of the substituent is not included in the number of carbon atoms.

[0040] In the present specification, unless otherwise specified, the "alkyl group" may be linear, branched, or cyclic. The number of carbon atoms of the linear alkyl group, excluding the number of carbon atoms of the substituent, is usually preferably 1 to 50, more preferably 1 to 30, and still more preferably 1 to 20. The number of carbon atoms of the branched or cyclic alkyl group, excluding the number of carbon atoms of the substituent, is usually preferably 3 to 50, more preferably 3 to 30, and still 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 alkyl group having a substituent 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 of the cycloalkyl group, excluding the number of carbon atoms of the substituent, is usually preferably 3 to 30, more preferably 12 to 19.

[0045] Examples of the cycloalkyl group include an alkyl group having no substituent such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and an adamantyl group, and a group in which a hydrogen atom in these groups is substituted with a substituent such as an alkyl group, an alkyloxy group, an aryl group, or a fluorine atom.

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

[0047] The "aromatic carbocyclic group" means a group remaining after removing any number of hydrogen atoms directly bonded to the carbon atoms constituting the ring from an aromatic hydrocarbon which may have a substituent. The aromatic carbocyclic group may further have a substituent. The "aromatic carbocyclic ring" includes a structure in which two or more carbocyclic rings (aromatic rings) are bridged by a group (substituent) containing a heteroatom, for example.

[0048] The "aryl group" is a monovalent aromatic carbocyclic group, and means a 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, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 2-phenylphenyl group, 3-phenylphenyl group, 4-phenylphenyl group, and groups in which hydrogen atoms in these groups are substituted with substituents such as an alkyl group, an alkyloxy group, an aryl group, and a fluorine atom.

[0050] The "alkyloxy group" (alkoxy group) may be linear, branched, or cyclic. The number of carbon atoms of the linear alkyloxy group, excluding the number of carbon atoms of the substituent, is usually preferably 1 to 40, more preferably 1 to 10. The number of carbon atoms of the branched or cyclic alkyloxy group, excluding 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 of the "cycloalkyloxy group" may be a monocyclic group or a polycyclic group. The cycloalkyloxy group may have a substituent. The number of carbon atoms of the cycloalkyloxy group, excluding the number of carbon atoms of the substituent, is usually preferably 3 to 30, more preferably 12 to 19.

[0053] Examples of the cycloalkyloxy group include cycloalkyloxy groups having no substituent, such as a cyclopentyloxy group, a cyclohexyloxy group, and a cycloheptyloxy group, and groups in which a hydrogen atom in these groups is substituted with a fluorine atom or an alkyl group.

[0054] The number of carbon atoms of the "aryloxy group", excluding the number of carbon atoms of the substituent, is usually preferably 6 to 60, more preferably 6 to 48.

[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 a hydrogen atom in these groups is substituted with a substituent 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 the linear alkylthio group, excluding the carbon atoms of the substituent, is usually preferably 1 to 40, more preferably 1 to 10. The number of carbon atoms in the branched and cyclic alkylthio groups, excluding the carbon atoms of the substituent, 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 methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, tert-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group, and trifluoromethylthio group.

[0058] The cycloalkyl group of 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, excluding the carbon atoms of the substituent, is usually preferably 3 to 30, more preferably 12 to 19.

[0059] An example of the cycloalkylthio group that may have a substituent is the cyclohexylthio group.

[0060] The number of carbon atoms in the "arylthio group", excluding the carbon atoms of the substituent, is usually preferably 6 to 60, more preferably 6 to 48.

[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 number of carbon atoms in the group described immediately after is 1-12. The same applies hereinafter), a C1-C12 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a pentafluorophenylthio group.

[0062] The "heterocyclic group" means a group remaining after removing any number of hydrogen atoms directly bonded to a carbon atom or a heteroatom constituting the ring from a heterocyclic compound which may have a substituent.

[0063] The heterocyclic group may further have a substituent. The number of carbon atoms in the heterocyclic group, excluding the number of carbon atoms in the substituent, is usually preferably 2-30, more preferably 2-6.

[0064] Examples of the substituent that the heterocyclic compound may have include, for example, 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 "aromatic heterocyclic group" means a group remaining after removing any number of hydrogen atoms directly bonded to a carbon atom or a heteroatom constituting the ring from an aromatic heterocyclic compound which may have a substituent. The aromatic heterocyclic group may further have a substituent.

[0066] The aromatic heterocyclic compounds include, in addition to compounds in which the heterocyclic ring itself exhibits aromaticity, compounds in which the heterocyclic ring itself does not exhibit aromaticity but an aromatic ring is fused to the heterocyclic ring.

[0067] Among aromatic heterocyclic compounds, specific examples of compounds in which the heterocyclic ring 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 heterocyclic ring itself does not exhibit aromaticity and an aromatic ring is fused to the heterocyclic ring include phenoxazine, phenothiazine, dibenzoborole, dibenzosilole, and benzopyran.

[0069] The number of carbon atoms of the monovalent heterocyclic group, excluding the number of carbon atoms of the substituent, is usually preferably 2 to 60, more preferably 4 to 20.

[0070] The monovalent heterocyclic group may have a substituent. Specific examples of the monovalent heterocyclic group include, for example, thienyl group, pyrrolyl group, furyl group, pyridyl group, piperidyl group, quinolyl group, isoquinolyl group, pyrimidinyl group, 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 "substituted amino group" means an amino group having a substituent. Examples of the substituent of the amino group include an alkyl group, an aryl group, and a monovalent heterocyclic group, and an alkyl group, an aryl group, or a monovalent heterocyclic group is preferred. The number of carbon atoms of the substituted amino group is usually preferably 2 to 30.

[0072] Examples of the substituted amino group include dialkylamino groups such as dimethylamino group and diethylamino group; diarylamino groups such as diphenylamino group, bis(4-methylphenyl)amino group, bis(4-tert-butylphenyl)amino group, and 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, excluding the number of carbon atoms in the substituent, is usually preferably 2 to 20, 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 "imine residue" means the remaining atomic group obtained by removing one hydrogen atom directly bonded to the carbon atom or nitrogen atom constituting the carbon atom-nitrogen atom double bond from an imine compound. The "imine compound" means an organic compound having a carbon atom-nitrogen atom double bond in the molecule. Examples of the imine compound include aldimine, ketimine, and a compound in which the hydrogen atom bonded to the nitrogen atom constituting the carbon atom-nitrogen atom double bond in aldimine is substituted with an alkyl group or the like.

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

[0076]

Chemical formula

[0077] The "amide group" means the remaining atomic group obtained by removing one hydrogen atom bonded to the nitrogen atom from an amide. The number of carbon atoms in the amide group is usually preferably 1 to 20, more preferably 1 to 18. Specific examples of the amide group include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group, a dibenzamide group, a ditrifluoroacetamide group, and a dipentafluorobenzamide group.

[0078] "Acid imide group" means the remaining atomic group after removing one hydrogen atom bonded to the nitrogen atom from acid imide. The number of carbon atoms in the acid imide group is usually preferably 4 to 20. Specific examples of the acid imide group include groups represented by the following structural formulas. In the following structural formulas, Me represents a methyl group.

[0079]

Chemical formula

[0080] "Substituted carbonyl group" means a group represented by -(C=O)-R X Here, R X represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

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

[0082] The number of carbon atoms in the substituted oxycarbonyl group, excluding the number of carbon atoms in the substituent, is usually preferably 2 to 60, more preferably 2 to 48.

[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" means a group represented by -SO2-R. X Here, R X represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

[0085] The "substituted oxysulfonyl group" means a group represented by -(SO2)-O-R X or -O-(SO2)-R X Here, 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 of the linear alkenyl group, excluding the carbon atoms of the substituent, is usually preferably 2 to 30, more preferably 3 to 20. The number of carbon atoms of the branched or cyclic alkenyl group, excluding the carbon atoms of the substituent, is usually preferably 3 to 30, more preferably 4 to 20.

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

[0088] The "cycloalkenyl group" may be a monocyclic group or a polycyclic group. The cycloalkenyl group may have a substituent. The number of carbon atoms of the cycloalkenyl group, excluding the number of carbon atoms of the substituent, is usually preferably 3 to 30, more preferably 12 to 19.

[0089] Examples of the cycloalkenyl group include cycloalkenyl groups having no substituent such as a cyclohexenyl group, and groups in which a hydrogen atom in these groups is substituted with an alkyl group, an alkyloxy group, an aryl group, or a fluorine atom.

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

[0091] The "alkynyl group" may be linear, branched, or cyclic. The number of carbon atoms of the linear alkynyl group, excluding the number of carbon atoms of the substituent, is usually preferably 2 to 20, more preferably 3 to 20. The number of carbon atoms of the branched or cyclic alkynyl group, excluding the number of carbon atoms of the substituent, is usually preferably 4 to 30, more preferably 4 to 20.

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

[0093] The "cycloalkynyl group" may be a monocyclic group or a polycyclic group. The cycloalkynyl group may have a substituent. The number of carbon atoms in the cycloalkynyl group, excluding the number of carbon atoms in the substituent, is usually preferably 4 to 30, more preferably 12 to 19.

[0094] Examples of the cycloalkynyl group include cycloalkynyl groups having no substituent such as a cyclohexynyl group, and groups in which a hydrogen atom in these groups is substituted with an alkyl group, an alkyloxy group, an aryl group, or a fluorine atom.

[0095] Examples of the cycloalkynyl group having a substituent 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, excluding 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 can be attached to a chemical formula represents a bond. The dotted line in the chemical formula also indicates a bond. When two "*" and dotted lines are included in the chemical formula, the bond to which of the two units that are the bonding destinations is not particularly limited.

[0098] "Ink" means a liquid substance used in a coating method and is not limited to a colored liquid. Further, the "coating method" includes a method of forming a film (layer) using a liquid substance. Examples thereof include a slot die coating method, a slit coating method, a knife coating method, a spin coating method, a casting method, a microgravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a spray coating method, a screen printing method, a gravure printing method, a flexographic printing method, an offset printing method, an inkjet coating method, a dispenser printing method, a nozzle coating method, and a capillary coating method.

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

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

[0101] The "external quantum efficiency", also referred to as EQE (External Quantum Efficiency), is a value indicating, as a ratio (%), the number of electrons that could be extracted outside the photoelectric conversion element out of the number of electrons generated with respect to the number of photons irradiated to the photoelectric conversion element.

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

Chemical formula

[0104] In formula (1), D is a divalent aromatic group, and 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. D has a monovalent side chain R D1 bonded to the sp3 carbon or the sp3 silicon, L1 is a divalent aromatic group, and the main skeleton of the monocyclic or condensed ring constituting the aromatic group in L1 may or may not have sp3 carbon or sp3 silicon. When having sp3 carbon or 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 condensed ring constituting the aromatic group in L1 has sp2 carbon, and L1 has at least one monovalent side chain R L1 bonded to the sp2 carbon, and the aromatic group in L1 has an element capable of non-covalent interaction with elements in adjacent units, R D1 and R L1 are each independently 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, An optionally substituted carbonyl group, An optionally substituted oxycarbonyl group, An optionally substituted sulfonyl group, An optionally 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 any one of 1 to 4, n is an integer of any one of 0 to 4, A1 and A2 are each independently a group represented by the following formula (A-1).

[0105]

Chemical formula

[0106] In formula (A-1), Ar represents an optionally substituted carbocyclic ring or an optionally substituted heterocyclic ring, and the carbocyclic ring and the heterocyclic ring are each independently a monocyclic ring or a condensed ring. When the carbocyclic ring or the heterocyclic ring has a plurality of substituents, the plurality of substituents may be the same or different.

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

[0108] In formula (1), 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 the sp3 silicon. D1 It has at least one. That is, in formula (1), the side chain R D1 possessed by D has a structure protruding in a direction perpendicular to the main skeleton (i.e., the π plane) of the monocyclic or condensed ring constituting the aromatic group in D. Therefore, in the thin film formed by the compound of the present disclosure, in D, the side chain R protruding from the π plane D1 makes it difficult for the compounds of the present disclosure to undergo H association between molecules, while the compounds of the present disclosure are likely to undergo J association between molecules. More specifically, A1 of a certain molecule of the compound of the present disclosure is likely to associate with A1 and A2 of another molecule of the compound of the present disclosure. Or, A2 of a certain molecule of the compound of the present disclosure is likely to associate with A1 and A2 of another molecule of the compound of the present disclosure.

[0109] Furthermore, in formula (1), L1 may or may not have an sp3 carbon or sp3 silicon in the main skeleton of the monocyclic or condensed ring constituting the aromatic group in L1. When it has an sp3 carbon or sp3 silicon, L1 does not have a monovalent side chain bonded to the sp3 carbon or the sp3 silicon. On the other hand, the main skeleton of the monocyclic or condensed ring constituting the aromatic group in L1 has sp2 carbon, and L1 has at least one monovalent side chain R L1 bonded to the sp2 carbon. Note that the side chain R L1 bonded to the sp2 carbon in L1 has a structure that does not protrude from the main skeleton (i.e., the π plane) of the monocyclic or condensed ring constituting the aromatic group in L1 (a structure existing on the same π plane). Therefore, the side chain R L1 in L1 does not inhibit the J association of the compound of the present disclosure. That is, since L1 has no side chain protruding from the main skeleton (i.e., the π plane) of the monocyclic or condensed ring constituting the aromatic group in L1, it is considered that L1 does not inhibit the 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. That is, when "[-(L1) m -]" has a certain length or more, the distance between the side chain R in D D1 and A1 becomes long, and the side chain R in D D1 does not inhibit the J-aggregation by A1 and A2. In addition, 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 in length, D and A1 are close to each other, whereby the structure in the compound of the present disclosure becomes crowded and it becomes difficult for J-aggregation to occur.

[0111] Furthermore, in formula (1), the aromatic group in L1 has an element capable of non-covalent interaction with an element in an adjacent unit. The adjacent units include, for example, A1 and L1, L1 and L1, or L1 and D. When the aromatic group in L1 has an element capable of non-covalent interaction with an element in an adjacent unit, a non-covalent crosslink is formed between the element in L1 and the unit (A1, L1, or D) present next to L1. That is, in the formed thin film, the planarity of the main skeleton (i.e., the π-plane) of the monocyclic or condensed ring constituting the aromatic group in L1 is likely to be maintained.

[0112] As described above, in the thin film formed from the compound of the present disclosure, the compound of the present disclosure is likely to form J-aggregates. When the compound forms J-aggregates, the compound is likely to absorb light of a long wavelength. When the compound forms H-aggregates, the compound is likely to absorb light of a short wavelength. Due to the above presumed actions, the compound of the present disclosure absorbs light of a long wavelength of 1400 nm or more and enables photoelectric conversion in the long wavelength region. Note that the present disclosure is not limited to the above presumed mechanism at all.

[0113] <D; core> [Aromatic group] In formula (1), D is a divalent aromatic group. The aromatic group in D has a monocyclic or condensed ring main skeleton. The aromatic group in D may be either an aromatic heterocyclic group or an aromatic carbocyclic group, and an aromatic heterocyclic group is preferred from the viewpoint of being likely to absorb light with a long wavelength. 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 monocyclic or condensed ring main skeleton constituting the aromatic group in D has at least one of sp3 carbon and sp3 silicon. The monocyclic or condensed ring main skeleton constituting the aromatic group in D preferably has sp3 carbon or sp3 silicon.

[0115] D has at least one monovalent side chain R bonded to the sp3 carbon or the sp3 silicon D1 D preferably has 1 to 4 monovalent side chains R bonded to the sp3 carbon or the sp3 silicon, more preferably 1 or 2, and even more preferably 2. D1 As described above, the monocyclic or condensed ring main skeleton constituting the aromatic group in D has at least one of sp3 carbon and sp3 silicon, and D has at least one monovalent side chain R bonded to the sp3 carbon or the sp3 silicon. D1 D1 Thus, the compound of the present disclosure has a structure in which the side chain R D1 protrudes in the vertical direction with respect to the main skeleton (i.e., the π plane) of D. Therefore, the compound of the present disclosure is less likely to form H aggregates and more likely to form J aggregates in the formed thin film.

[0116] [Side chain R D1 The side chain R in D D1 are each independently 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 substitutedoxysulfonyl 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 Represents a nitro group.

[0117] The side chain R in D D1 Since the side chain R in D is a structure for making the compound of the present disclosure in the formed thin film difficult to undergo H aggregation and easy to undergo J aggregation, D1 The specific structure of R is not particularly limited. The side chain R in D D1is preferably, independently of one another, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a monovalent heterocyclic group which may have a substituent, more preferably an alkyl group which may have a substituent or an aryl group which may have a substituent, and even more preferably an alkyl group.

[0118] [Chemical structure of D] From the viewpoint that the compound easily absorbs light of a long wavelength, in the formula (1), D is preferably any group represented by the following formula (D-1) to formula (D-4), and more preferably a group represented by the following formula (D-1), the following formula (D-2) or the following formula (D-3). In the following formula (D-1) to formula (D-4), the symbol "*" is a bond with (L1) m in the formula (1) or a bond with (L2) n in the formula (1).

[0119] [Chemical formula]

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

[0121] [Chemical formula]

[0122] In the formula (D-3), formula (D-4), and formula (X-1) to formula (X-6), the definition of R D2 is, independently of one another, 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 substitutedoxysulfonyl 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.

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

[0124] In formulas (D-2) and (D-4), Ar 1 and Ar 2 are each independently an aromatic carbon ring which may have a substituent and in which a plurality of ring structures may be further fused, or an aromatic heterocyclic ring which may have a substituent and in which a plurality of ring structures may be further fused. Ar 1 and Ar 2 One of them may not be present.

[0125] Ar 1 and Ar 2 The aromatic heterocyclic rings that can form Ar and Ar include, in addition to monocyclic and condensed rings in which the heterocyclic ring itself exhibits aromaticity, rings in which an aromatic ring is condensed to the heterocyclic ring even if the heterocyclic ring itself that constitutes the ring does not exhibit aromaticity.

[0126] Ar 1 and Ar 2 The aromatic heterocyclic rings that can form Ar and Ar may each be a monocyclic ring or a condensed ring. When the aromatic heterocyclic ring is a condensed ring, the condensed ring may be a condensed ring in which all of the rings constituting the condensed ring have aromaticity, or a condensed ring in which only a part has aromaticity. When these rings have a plurality of substituents, these substituents may be the same or different.

[0127] Ar 1 and Ar 2 Specific examples of the aromatic carbon ring that can form Ar and Ar include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring. Preferably, they are 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 the aromatic heterocyclic ring that can constitute include oxadiazole ring, thiadiazole ring, thiazole ring, oxazole ring, thiophene ring, pyrrole ring, phosphole ring, furan ring, pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyridazine ring, quinoline ring, isoquinoline ring, carbazole ring, and dibenzophosphole ring, as well as phenoxazine ring, phenothiazine ring, dibenzoborole ring, dibenzosilole ring, and benzopyran ring. These rings may have substituents.

[0129] (Examples of D) Examples of the formula (D-1) include groups represented by the following formula (d-1-1) to formula (d-1-7). Examples of the formula (D-2) include groups represented by the following formula (d-2-1) to formula (d-2-10). Examples of the formula (D-3) include groups represented by the following formula (d-3-1) to formula (d-3-2). Examples of the formula (D-4) include groups represented by the following formula (d-4-1) to formula (d-4-9). In the formula (d-1-1) to formula (d-1-7), the definition of R D2 is, respectively independently, the same as the definition of R D2 described above. In the following formula (d-2-1) to formula (d-2-10), formula (d-3-1) to formula (d-3-2), and formula (d-4-1) to formula (d-4-9), the definition of R D2 is, respectively independently, the same as the definition of R D2 described above. In the following formula (d-2-1) to formula (d-2-10) and formula (d-4-1) to formula (d-4-9), U is, respectively independently, CR D2 2, S, SiR D2 2, Se, NR D2 , or O. U is preferably S. In the following formula (d-1-1) to formula (d-1-7), formula (d-2-1) to formula (d-2-10), formula (d-3-1) to formula (d-3-2), and formula (d-4-1) to formula (d-4-9), the symbol "*" indicates the bond with (L1) in the formula (1) m or the bond with (L2) n in the formula (1).

[0130] From the viewpoint that the compound is likely to absorb 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]

Chemical formula

[0132]

Chemical formula

[0133]

Chemical formula

[0134]

Chemical formula

[0135] (Specific examples of D) Specific examples of D include groups represented by the following formulas. In each formula, the symbol "*" represents the bond with (L1) in formula (1) m or the bond with (L2) n in formula (1).

[0136]

Chemical formula

[0137]

Chemical formula

[0138] <(L1) m ; The linker connecting A1 and D> (L1) in formula (1) m In the case where m is 2 or more, the plurality of L1s present in formula (1) are each independently defined in terms of their chemical structure. That is, the description of L1 given below is for each independent L1.

[0139] [Aromatic group] In formula (1), L1 is a divalent aromatic group. The aromatic group in L1 has a monocyclic or condensed-ring main skeleton. The aromatic group in L1 may be either an aromatic heterocyclic group or an aromatic carbocyclic group, and from the viewpoint of being likely to absorb light of a long wavelength, an aromatic heterocyclic group is preferred. 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 monocyclic or condensed-ring main skeleton constituting the aromatic group in L1 may or may not have sp3 carbon or sp3 silicon. When the monocyclic or condensed-ring main skeleton 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 the sp3 silicon in L1. Note that not having a monovalent side chain bonded to the sp3 carbon or the sp3 silicon in L1 means that at the sp3 carbon or the sp3 silicon in L1, two bonds form the monocyclic or condensed-ring main skeleton constituting the aromatic group in L1, and the remaining two bonds are each bonded to a hydrogen atom. That is, not having a monovalent side chain bonded to the sp3 carbon or the sp3 silicon in L1 means that only hydrogen atoms protrude with respect to the monocyclic or condensed-ring main skeleton (i.e., the π plane) constituting the aromatic group in L1.

[0141] On the other hand, the monocyclic or condensed-ring main skeleton constituting the aromatic group in L1 has sp2 carbon, and L1 has a monovalent side chain R bonded to the sp2 carbon L1has at least one. L1 is a monovalent side chain R bonded to the sp2 carbon L1 preferably has one or two, and more preferably has one. As described above, since L1 has no side chain protruding with respect to the main skeleton (i.e., the π plane) of the monocyclic or condensed ring constituting the aromatic group in L1, L1 does not inhibit the J aggregation of the compound in the formed thin film.

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

[0143] The element capable of non-covalent interaction with an element in an adjacent unit that the aromatic group in L1 has 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-covalent interaction 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] In addition, similarly to the unit adjacent to L1, it 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-covalent interaction with the aromatic group in L1, which is 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 being able to have non-covalent interaction, 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 included in the main skeleton of the monocyclic or condensed ring constituting the aromatic group in L1, may be included in the side chain bonded to the main skeleton of the monocyclic or condensed ring constituting the aromatic group in L1, or may be included in the side chain R L1 and may be included therein. The non-covalent interaction may be formed by the main skeleton of the monocyclic or condensed ring constituting the aromatic group in L1 and the side chain bonded to the main skeleton of the unit adjacent to L1. The side chain R bonded to the main skeleton of the monocyclic or condensed ring constituting the aromatic group in L1 L1 and the main skeleton of the unit adjacent to L1, or may be formed by side chains bonded to the main skeleton of the monocyclic or condensed ring constituting the aromatic group in L1.

[0148] As described above, when the aromatic group in L1 has an element capable of non-covalent interaction with an element in an adjacent unit, a non-covalent crosslink is formed between the element in L1 and the unit (A1, L1, or D) present adjacent to L1. That is, in the formed thin film, the planarity of the main skeleton (i.e., the π plane) of the monocyclic or condensed ring constituting the aromatic group in L1 is likely to be maintained.

[0149] [Side chain R L1 The side chain R in L1 L1 is each independently 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 Represents a nitro group.

[0150] From the viewpoint that the compound is likely to absorb light of a long wavelength, the side chain R in L1 L1 is 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 still more preferably an alkyloxy group which may have a substituent.

[0151] [Chemical structure of L1] From the viewpoint that the compound is likely to absorb light of a long wavelength, in the formula (1), L1 is preferably any group represented by the following formula (L1-1) to formula (L1-7), more preferably any group represented by the following formula (L1-1) to formula (L1-4), and still more preferably the group represented by the following formula (L1-1). That is, from the viewpoint that the compound is likely to absorb light of a long wavelength, L1 preferably has a thiophene structure, a thienothiophene structure, a thiazole structure, or a benzothiadiazole structure.

[0152] [Chemical formula]

[0153] In formulas (L1-1) to (L1-7), R L11 is, independently of each other, in addition to the definition of said R D2 preferably 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. As described above, when R 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 a unit adjacent to L1 having R L11 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, a non-covalent crosslink is formed between R L11 and the unit adjacent to L1 having R L11 . That is, in the formed thin film, the planarity of the main skeleton (i.e., the π plane) of the monocyclic or condensed 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 formulas.

[0155] [Chemical formula]

[0156] (m) In formula (1), m is an integer of any one of 1 to 4. From the viewpoints of the compound being likely to absorb light of a long wavelength and ease of synthesis, m is preferably an integer of any one of 2 to 4, more preferably 2 or 3, and still more preferably 2.

[0157] ((L1) m specific examples) (L1) m Specific examples of include the above-described specific examples of L1 (i.e., (L1) mIn addition to the specific examples where m is 1, groups represented by the following formulas can be mentioned.

[0158] [Chemical formula]

[0159] [Chemical formula]

[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. (L1) m Preferably has at least one thiophene structure having an alkyloxy group, and more preferably is an oligomer of a thiophene structure 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 the 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 described above, when "-(L1) m -" has a length of a certain level or more, the distance between the side chain R D1 in D and A1 becomes long, and (L1) m does not inhibit the J-aggregation of the compound by A1 and A2. When the distance is less than 9 Å, D and A1 are close to each other, resulting in a crowded structure in the compound of the present disclosure and making it difficult for J aggregation to occur. In the compound of the present disclosure, 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, from the viewpoint of making the distance 9 Å or more, when m = 1, L1 preferably has a dithienothiophene structure having an alkyloxy group. When m is any integer from 2 to 4, L1 preferably has 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 has a thiophene structure having an alkyloxy group.

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

[0164] The distance (d C1-C2 ) is subjected to ground state structure optimization by the density functional method at the B3LYP level using the quantum chemistry calculation program Gaussian 03, and 6-31g* is used as the basis function. For the obtained ground state optimized structure, d C1-C2 is calculated using GaussVeiw 6. In calculating d C1-C2 , for the alkyl group contained in each compound, as an example, the propyl group (-CH2-CH2-CH3) is taken as a representative for calculation. The calculated values are almost the same for the compound before changing the alkyl group to a propyl group and the compound after changing the alkyl group to a propyl group.

[0165] <(L2) n ; linker connecting A2 and D> (L2) in formula (1) nIn the case where n is an integer of 2 or more, the plurality of L2s present in formula (1) are each independently defined in terms of their chemical structure. That is, the descriptions of L2 below are descriptions of each independent L2.

[0166] [Aromatic group] In formula (1), L2 is a divalent aromatic group. The structure of the aromatic group in L2 has a monocyclic or condensed ring main skeleton. The aromatic group in L2 may be either an aromatic heterocyclic group or an aromatic carbocyclic group, and from the viewpoint of being likely to absorb light of a long wavelength, an aromatic heterocyclic group is preferred. 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 that the compound is likely to absorb light of a long wavelength, in the formula (1), each L2 is preferably independently any group represented by the following formula (L2-1) to formula (L2-12), more preferably any group represented by the following formula (L2-1) to formula (L2-9), and even more preferably any group represented by the following formula (L2-1) to formula (L2-7). That is, from the viewpoint that the compound is likely to absorb light of a long wavelength, L2 preferably has a thiophene structure, a thienothiophene structure, a thiazole structure, or a benzothiadiazole structure. From the viewpoint of the ease of J-aggregation of the compounds of the present disclosure, the chemical structure of L2 is not more restricted than the chemical structure of L1.

[0168] [Chemical formula]

[0169] In formula (L2-1) to formula (L2-12), the plurality of Rs L2 are each independently 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.

[0170] (Specific examples of L2) Specific examples of L2 include, in addition to the specific examples of L1 described above, groups represented by the following formulas.

[0171]

Chemical formula

[0172] (n) In formula (1), n is an integer of any one of 0 to 4. That n is 0 means that, namely, (L2) n does not exist, and it means that D and A2 in formula (1) are directly bonded. From the viewpoints of the compound being likely to absorb light of a long wavelength and ease of synthesis, n is preferably an integer of 1 or more, may be an integer of 2 or more, more preferably is an integer of any one of 1 to 4, still more preferably is an integer of any one of 1 to 3, particularly preferably is 1 or 2, and most preferably is 1.

[0173] ((L2) n Specific examples) (L2) n Specific examples of (L2) include, in addition to the specific examples of L2 described above (that is, the specific examples when n is 1 in (L2) n ) and the specific examples of (L1) m described above, a group represented by the following formula.

[0174]

Chemical formula

[0175] In formula (1), when taking D in formula (1) as the center point, the chemical structure of (L1) m and the chemical structure of (L2) n may be point-symmetrical or asymmetrical. From the viewpoint that the compound is likely to absorb light of a long wavelength, in formula (1), it is preferable that m is 2 and n is 1 or 2.

[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 indicates a bond with (L1) m in formula (1) or a bond with (L2) n in formula (1).

[0177] [Chemical formula]

[0178] In formula (A-1), Ar represents a carbocyclic ring which may have a substituent or a heterocyclic ring which may have a substituent, and the carbocyclic ring and the heterocyclic ring are each independently a monocyclic ring or a condensed ring. When the carbocyclic ring or the heterocyclic ring 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, 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.

[0180] The heterocyclic ring may be an aromatic heterocyclic ring. Specific examples of the aromatic heterocyclic ring 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, and a phenoxazine ring, a phenothiazine ring, a dibenzoborole ring, a dibenzosilole ring, and a benzopyran ring. These rings may have a substituent.

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

[0182] [Chemical formula]

[0183] In formulas (a-1) to (a-8), a plurality of Rs A1 are each independently a hydrogen atom, a halogen atom, or a cyano group. From the perspective that the compound easily absorbs light of a long wavelength, R A1 is preferably each independently a hydrogen atom, a chlorine atom, a fluorine atom, or a cyano group, and more preferably a cyano group. From the perspective that the compound easily absorbs light of a long wavelength, A1 and A2 are preferably each independently any group represented by formula (a-1) or 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 formulas. In each formula, the symbol "*" represents a bond with (L1) in formula (1) m or a bond with (L2) n .

[0185] [Chemical formula]

[0186] [Specific examples of the 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, in formula (1), 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 9.1 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 are each independently a group represented by formula (A-1), m is an integer of any one of 2 to 4, and n is an integer of any one of 1 to 4, The main skeleton of the monocyclic or condensed ring constituting the aromatic group in L1 has sp2 carbon, and L1 has one or two monovalent side chains R L1 bonded to the sp2 carbon, The aromatic group in L1 preferably has an element capable of non-covalent interaction with elements in adjacent units.

[0187] In the compound of the present disclosure, 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 9.2 Å or more, D is any group represented by formula (d-1-1) to formula (d-1-7) or formula (d-2-1) to formula (d-2-10), L1 is each independently any group represented by formula (L1-1) to formula (L1-7), L2 is each independently any group represented by formula (L2-1) to formula (L2-12), A1 and A2 are each independently any group represented by formula (a-1) to formula (a-8), m is 2 or 3, and n is 1 or 2, The main skeleton of the monocyclic or condensed ring constituting the aromatic group in L1 has sp2 carbon, and L1 has one monovalent side chain R L1 bonded to the sp2 carbon, More preferably, the aromatic group in L1 has an element capable of non-covalent interaction with elements in adjacent units.

[0188] Preferable specific examples of the compound of the present disclosure include compounds represented by the following formulas.

[0189]

Chemical formula

[0190]

Chem.

[0191]

Chem.

[0192]

Chem.

[0193]

Chem.

[0194]

Chem.

[0195] <Energy difference (Eg) between the energy level of the lowest excited singlet state and the energy level of the ground state of the compound> For the compound of the present disclosure, the energy difference (Eg) between the energy level of the lowest excited singlet state and the energy level of the ground state calculated by computational science methods is preferably 1.55 eV or less. Examples of computational science methods include methods calculated using quantum chemistry calculation programs.

[0196] Using the quantum chemistry calculation program Gaussian 03, the ground state structure optimization was carried out by density functional theory at the B3LYP level. For the optimized structure, the value obtained by calculation using 6-31g* as the basis function was taken as the value of the ground state energy level. Subsequently, the energy level of the lowest excited singlet state was 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 excited singlet state and the energy level of the ground state was defined as the energy band gap (Eg).

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

[0198] It is more preferable that the energy band gap of the compound is 1.50 eV or less, even more preferably 1.40 eV or less, and particularly preferably 1.30 eV or less. The lower limit value 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, for the compound of the present disclosure, the calculated value by density functional theory of the wavelength λ corresponding to the energy band gap Eg is preferably 800 nm or more.

[0200] In one embodiment of the present disclosure, for the compound of the present disclosure, the calculated value by density functional theory of the wavelength λ corresponding to the energy band gap Eg is more preferably 826 nm or more, even more preferably 885 nm or more, and particularly preferably 953 nm or more from the viewpoint that the compound is likely to absorb light of long wavelengths. The wavelength λ corresponding to the energy band gap EgThe calculated value by the density functional theory has no particular limitation on its upper limit value. For example, it is preferably 1650 nm or less, more preferably 1400 nm or less, and even more preferably 1200 nm or less. In one embodiment of the present disclosure, the wavelength λ corresponding to the energy band gap of the compound Eg The calculated value by the density functional theory is preferably 826 nm to 1650 nm.

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

[0202] <The optical absorption edge wavelength (λth) of the thin film> For the compound of the present disclosure, it is preferable that the optical absorption edge wavelength (λth) of the thin film formed from the compound is 1400 nm or more. The photoelectric conversion element containing the compound of the present disclosure is more likely to perform photoelectric conversion in light of a longer wavelength than before. From the viewpoint of utilizing light of a longer wavelength, it is preferable that the optical absorption edge wavelength (λth) is a long wavelength. The optical absorption edge wavelength is preferably 1400 nm or more, more preferably 1450 nm or more, even more preferably 1500 nm or more, and still more preferably 1550 nm or more. The upper limit value of the optical absorption edge wavelength is not particularly limited, and for example, it may be 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 optical absorption edge wavelength is preferably 1400 nm to 2000 nm.

[0203] The optical absorption edge wavelength is represented as the wavelength value at the long wavelength side end of the optical absorption wavelength. In the present disclosure, the numerical value of the optical absorption edge wavelength is specifically represented by the value obtained by the following method.

[0204] The method for preparing the measurement sample is as follows. The compound is added to orthodichlorobenzene so that the concentration becomes 1.0% by mass. Heating and stirring are carried out for 4 hours under the condition of 65 °C in a nitrogen atmosphere to prepare a solution. The filtrate of the said solution is used as a coating solution. The coating solution is placed on a glass substrate whose surface has been cleaned with UV-ozone, and a film is formed by spin coating. The coating film obtained by spin coating is placed on a hot plate. It is dried under the conditions of 70 °C and 5 minutes in the air to obtain a thin film for UV-Vis spectrum measurement.

[0205] For the measurement of the light absorption wavelength, a spectrophotometer operating in the wavelength regions of ultraviolet light, visible light, and near-infrared light (for example, the ultraviolet-visible-near-infrared spectrophotometer "Cary 5E" manufactured by Varian) is used.

[0206] The absorption spectrum of the 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 film thickness of the thin film so that the absorbance of the largest absorption peak is about 0.4 to 2.

[0207] The light absorption edge wavelength can be obtained from the intersection of the first reference line and the second reference line shown below.

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

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

[0210] Of the two intersections where a straight line parallel to the wavelength axis showing 44% of the absorbance of the above absorption peak point intersects the absorption waveform, the intersection closer to the longer wavelength than the above absorption peak point is taken as the second point. The straight line connecting the first point and the second point is taken as the first reference line.

[0211] - Second reference line - In the entire absorption waveform, the absorbance at the absorption peak point (maximum value) closest to the longest wavelength is set to 100%.

[0212] Of the two intersections where a straight line parallel to the wavelength axis showing 20% of the absorbance at the absorption peak point intersects the absorption waveform, the wavelength of the intersection closer to the longer wavelength than the absorption peak point is used as the reference point, and a point on the absorption waveform that is 100 nm longer in wavelength than the wavelength of the reference point is defined as the third point. Also, a point on the absorption waveform that is 150 nm longer in wavelength than the wavelength of the reference point is defined as the fourth point. The straight line connecting the third point and the fourth point is defined as the second reference line.

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

[0214] <The maximum optical absorption wavelength (λmax) of the solution> Preferably, for the compound of the present disclosure, the maximum optical absorption wavelength (λmax) of the solution formed from the compound is 900 nm or more. The photoelectric conversion element containing the compound of the present disclosure is more likely to perform photoelectric conversion in light of a longer wavelength than before. From the viewpoint of utilizing light of a longer wavelength, the maximum optical absorption wavelength (λmax) is preferably a longer wavelength. More preferably, the maximum optical absorption wavelength is 950 nm or more, still more preferably 980 nm or more, and even more preferably 1000 nm or more. The upper limit value of the optical absorption edge wavelength is not particularly limited, and for example, it may be 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 optical absorption edge wavelength is preferably 900 nm to 1800 nm.

[0215] The maximum optical absorption wavelength of the solution is represented as the wavelength value of the absorption peak wavelength. In the present disclosure, specifically, the maximum optical absorption wavelength of the solution is represented by the value obtained by the following method.

[0216] The method for preparing the measurement sample is as follows. The compound is added to orthodichlorobenzene to a concentration of 0.025% by mass to prepare a stock solution. The stock solution is diluted 20-fold with orthodichlorobenzene to obtain a solution for UV-Vis spectrum measurement (concentration: 0.00125% by mass).

[0217] For the measurement of the light absorption wavelength, a spectrophotometer that operates in the wavelength regions of ultraviolet light, visible light, and near-infrared light (for example, the ultraviolet-visible-near-infrared spectrophotometer "Cary 5E" manufactured by Varian) is used.

[0218] The absorption spectrum of the 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 includes a p-type semiconductor material and an n-type semiconductor material. As the n-type semiconductor material, it is preferable to include the compound of the present disclosure.

[0221] The composition of the present disclosure may contain components other than the p-type semiconductor material and the n-type semiconductor material. Further, the composition of the present disclosure may contain only the compound of the present disclosure as the n-type semiconductor material, or may contain other compounds other than the compound of the present disclosure. Other compounds that can be included as the n-type semiconductor material may be low molecular weight compounds or high molecular weight compounds.

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

[0223] Examples of the high molecular weight compounds that may be included as the n-type semiconductor material include polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives having an aromatic amine structure in the side chain or main chain, polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, and polyfluorene and its derivatives.

[0224] Also, other compounds may be fullerene derivatives.

[0225] Here, the fullerene derivative refers to a compound in which at least a part of fullerene (C 60 fullerene, C 70 fullerene, C 76 fullerene, C 78 fullerene, and C 84 fullerene) is modified. In other words, it refers to a compound having one or more groups added to the fullerene skeleton. Hereinafter, the fullerene derivative of C 60 fullerene is sometimes referred to as a "C 60 fullerene derivative", and the fullerene derivative of C 70 fullerene is sometimes referred to as a "C 70 fullerene derivative".

[0226] The fullerene derivatives that may be included as the n-type semiconductor material are not particularly limited as long as the object of the present disclosure is not impaired.

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

[0228] [Chemical formula]

[0229] The above C 60 In the formula of the fullerene derivative, R is a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, an alkyloxy group that may have a substituent, a cycloalkyloxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylthio group that may have a substituent, a cycloalkylthio group that may have a substituent, an arylthio group that may have a substituent, a monovalent heterocyclic group that may have a substituent, a substituted amino group that may have a substituent, an acyl group that may have a substituent, an imine residue that may have a substituent, an amide group that may have a substituent, an acid imide group that may have a substituent, a substituted carbonyl group that may have a substituent, a substituted oxycarbonyl group that may have a substituent, a substituted sulfonyl group that may have a substituent, a substitutedoxysulfonyl group that may have a substituent, an alkenyl group that may have a substituent, a cycloalkenyl group that 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 a plurality of Rs, the plurality of Rs may be the same as or different from each other.

[0230] C 70 Examples of the fullerene derivative include the following compounds.

[0231]

Chemical formula

[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 means the weight average molecular weight calculated using gel permeation chromatography (GPC) with a standard sample of polystyrene.

[0234] From the viewpoint of particularly improving the solubility in a solvent, the weight average molecular weight in terms of polystyrene of the p-type semiconductor material is preferably 3000 or more and 500000 or less.

[0235] The p-type semiconductor material is preferably a π-conjugated polymer compound (also referred to as a D-A type conjugated polymer compound) containing a donor structural unit (also referred to as a D structural unit) and an acceptor structural unit (also referred to as an A structural unit). Whether a particular unit 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, the donor structural unit is a structural unit with an excess of π electrons, and the acceptor structural unit is a structural unit lacking π electrons.

[0237] In the present disclosure, the 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, and further include structural units in which a donor structural unit and an acceptor structural unit are bonded via an arbitrarily suitable spacer (group or structural unit).

[0238] Examples of the p-type semiconductor material that is a polymer compound include polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives containing an aromatic amine structure in the side chain or main chain, polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene and its derivatives, and polyfluorene and its derivatives.

[0239] The p-type semiconductor material is preferably a polymer compound containing at least one selected from the group consisting of the structural unit represented by the following formula (3) and the 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]

Chemical formula

[0241] - Formula (3) - In formula (3), Ar 3 and Ar 4 each independently represent 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]

Chemical formula

[0243] In formula (Z-1) to formula (Z-7), the definition of R is each independently C60 It is the same as the definition of R in the formula of the fullerene derivative. In each of formulas (Z-1) to (Z-7), when there are two Rs, the two Rs may be the same as or different from each other.

[0244] Ar 3 and Ar 4 The aromatic heterocyclic rings that can form Ar and Ar include, in addition to monocyclic and condensed rings in which the heterocyclic ring itself exhibits aromaticity, rings in which an aromatic ring is condensed to the heterocyclic ring even if the heterocyclic ring itself that constitutes the ring does not exhibit aromaticity.

[0245] Ar 3 and Ar 4 The aromatic heterocyclic rings that can form Ar and Ar may each be a monocyclic ring or a condensed ring. When the aromatic heterocyclic ring is a condensed ring, the condensed ring may be a condensed ring in which all of the rings constituting the condensed ring have aromaticity, or a condensed ring in which only a part has aromaticity. When these rings have a plurality of substituents, these substituents may be the same or different.

[0246] Ar 3 and Ar 4 Specific examples of the aromatic carbon rings that can form Ar and Ar include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring. Preferably, they are a benzene ring and a naphthalene ring, more preferably a benzene ring and a naphthalene ring, and still more preferably a benzene ring. These rings may have substituents.

[0247] Specific examples of the aromatic heterocyclic ring include the ring structures of the compounds already described as aromatic heterocyclic compounds, such as oxadiazole ring, thiadiazole ring, thiazole ring, oxazole ring, thiophene ring, pyrrole ring, phosphole ring, furan ring, pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyridazine ring, quinoline ring, isoquinoline ring, carbazole ring, and dibenzophosphole ring, and also phenoxazine ring, phenothiazine ring, dibenzoborole ring, dibenzosilole ring, and benzopyran ring. These rings may have substituents.

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

[0249]

Chemical formula

[0250] In formulae (3-1), (3-2) and (3-3), the definitions of Ar 3 , Ar 4 and R are the same as the definitions of Ar 3 , Ar 4 in formula (3) and the definition of R in the formula of the C 60 fullerene derivative.

[0251] Specific examples of the preferred structural unit represented by formula (3) include structural units represented by the following formulae.

[0252]

Chemical formula

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

[0254] Examples of more specific preferred structural units represented by formula (3) include structural units represented by the following formulas.

[0255]

Chemical formula

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

[0257] Ar 5 The divalent aromatic heterocyclic group represented by 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 may have a substituent. Examples of the substituent that the divalent aromatic heterocyclic group represented by Ar 5 may have include a halogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkyloxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylthio group that may have a substituent, an arylthio group that may have a substituent, a monovalent heterocyclic group that may have a substituent, a substituted amino group that may have a substituent, an acyl group that may have a substituent, an imine residue that may have a substituent, an amide group that may have a substituent, an acid imide group that may have a substituent, a substituted oxycarbonyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, a cyano group, and a nitro group.

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

[0260]

Chemical formula

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

[0262] X in Formulas (4-1) to (4-10) 3 and X 4 are both preferably sulfur atoms from the viewpoint of availability of the starting compound.

[0263] Note that the structural units represented by Formulas (4-1) to (4-10) usually function as acceptor structural units as described above. However, the present invention is not limited thereto, and in particular, the structural units represented by Formulas (4-4), (4-5), and (4-7) can also function as donor structural units.

[0264] The p-type semiconductor material preferably contains a structural unit containing a thiophene skeleton and is a π-conjugated polymer compound containing a π-conjugated system.

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

[0266]

Chemical formula

[0267]

Chemical formula

[0268] [Chemistry]

[0269] [Chemistry]

[0270] The polymer compound that is a p-type semiconductor material preferably is a π-conjugated polymer compound containing a structural unit represented by Formula (3) as a donor structural unit and a structural unit represented by Formula (4) as an acceptor structural unit.

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

[0272] The polymer compound that is a p-type semiconductor material may contain two or more structural units represented by Formula (3), and may contain two or more structural 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 structural unit represented by the following Formula (5).

[0274] [Chemistry]

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

[0276] Ar 6The arylene group represented by means the atomic group remaining after removing two hydrogen atoms from an aromatic hydrocarbon which may have a substituent. The aromatic hydrocarbon includes compounds having a condensed ring, and compounds in which two or more selected from the group consisting of an independent benzene ring and a condensed ring are directly bonded or bonded 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 is usually preferably 6 to 60, more preferably 6 to 20, not including the number of carbon atoms of the substituent. 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 include a phenylene group (for example, the following Formula 1 to Formula 3), a naphthalene-diyl group (for example, the following Formula 4 to Formula 13), an anthracene-diyl group (for example, the following Formula 14 to Formula 19), a biphenyl-diyl group (for example, the following Formula 20 to Formula 25), a terphenyl-diyl group (for example, the following Formula 26 to Formula 28), a condensed ring compound group (for example, the following Formula 29 to Formula 35), a fluorene-diyl group (for example, the following Formula 36 to Formula 38), and a benzofluorene-diyl group (for example, the following Formula 39 to Formula 46).

[0280]

Chemical formula

[0281]

Chemical formula

[0282]

Chemical formula

[0283]

Chem.

[0284]

Chem.

[0285]

Chem.

[0286]

Chem.

[0287]

Chem.

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

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

[0290]

Chem.

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

[0292] The structural unit constituting the polymer compound which is a p-type semiconductor material may be a structural unit in which two or more kinds of structural units selected from the above structural units are combined and linked.

[0293] When the polymer compound as the p-type semiconductor material contains the structural unit represented by the formula (3) and / or the structural unit represented by the formula (4), the total amount of the structural unit represented by the formula (3) and the structural unit represented by the formula (4) is usually preferably 20 mol% to 100 mol%, more preferably 40 mol% to 100 mol%, and still more preferably 50 mol% to 100 mol% based on 100 mol% of the amount of all the structural units contained in the polymer compound, from the viewpoint of improving the charge transport property as the p-type semiconductor material.

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

[0295]

Chemical formula

[0296]

Chemical formula

[0297]

Chemical formula

[0298]

Chemical formula

[0299]

Chemical formula

[0300]

Chemical formula

[0301]

Chemical formula

[0302] [Chem.]

[0303] In the above formula, the definition of R is C 60 It is the same as the definition of R in the formula of the fullerene derivative. A plurality of Rs may be the same as or different from each other.

[0304] When the above-exemplified polymer compound is used as the p-type semiconductor material, it is possible to suppress a decrease in EQE with respect to heat treatment in a manufacturing process of a photoelectric conversion element or a process of incorporating the photoelectric conversion element into a device to which the photoelectric conversion element is applied, or to further improve the EQE, and it is possible to improve 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 contains a p-type semiconductor material and an n-type semiconductor material, and more preferably contains the compound of the present disclosure as the n-type semiconductor material. 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 type active layer.

[0306] According to the ink of the present disclosure, by containing a p-type semiconductor material and the compound of the present disclosure, it is possible to suppress a decrease in EQE with respect to heat treatment in a manufacturing process of a photoelectric conversion element or a process of incorporating the photoelectric conversion element into a device to which the photoelectric conversion element is applied, or to further improve the EQE, and it is possible to improve the heat resistance.

[0307] As the solvent, for example, a mixed solvent obtained by combining a first solvent and a second solvent described later can be used. Specifically, when the ink contains two or more solvents, it preferably contains a main solvent (first solvent) as a main component and another additive solvent (second solvent) added for improving solubility or the like. The solvent may be only the first solvent.

[0308] Hereinafter, the first solvent, the second solvent, and combinations thereof that can be suitably used in the ink for forming the active layer will be described.

[0309] <First Solvent> As the first solvent, a solvent in which the p-type semiconductor material is soluble is preferable. The first solvent is preferably an aromatic hydrocarbon.

[0310] Examples of the aromatic hydrocarbon 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 type of aromatic hydrocarbon or two or more types of aromatic hydrocarbons. The first solvent is preferably composed of one type of aromatic hydrocarbon.

[0312] The first solvent is preferably at least one 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 indane, 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 indane.

[0313] <Second solvent> The second solvent is preferably selected from the viewpoint of making the manufacturing process easier to carry out and 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 acetophenone, propiophenone, butyl benzoate or methyl benzoate, for example, from the viewpoint of further reducing the dark current.

[0315] <Combination of the first solvent and the 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, o-dichlorobenzene and methyl benzoate, more preferably combinations of tetralin and butyl benzoate, and o-dichlorobenzene and 1,2-dimethoxybenzene.

[0316] <Mass ratio of the first solvent and the second solvent> The mass ratio of the first solvent, which is the main solvent, to the second solvent, which is the additive solvent (first solvent: second solvent), is preferably in the range of 50:50 to 99:1 from the viewpoint of further improving the solubility of the p-type semiconductor material and the n-type semiconductor material.

[0317] <Any other solvent> The solvent may contain any other solvent other than the first solvent and the second solvent. When the total mass of all the solvents contained in the ink is 100% by mass, the content of any other solvent is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less. As any other solvent, a solvent having a boiling point higher than that of 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 any components such as a surfactant, an ultraviolet absorber, an antioxidant, a sensitizer for enhancing the function of generating charges by the absorbed light, and a light stabilizer for increasing the stability against ultraviolet rays, as long as 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 any suitable concentrations within a range that does not impair the object of the present disclosure, taking into account the solubility in the solvent and the like.

[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 still more preferably 1 / 1.5.

[0321] The total content of the "p-type semiconductor material" and 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 still more preferably 0.25% by mass or more. Also, the total content of the "p-type semiconductor material" and the "n-type semiconductor material" in the ink is usually preferably 20% by mass or less, more preferably 10% by mass or less, and still 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. Also, 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. Also, 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, a method of preparing a mixed solvent by mixing a first solvent or a first solvent and a second solvent, and adding a p-type semiconductor material and an n-type semiconductor material to the obtained mixed solvent, a method of adding a p-type semiconductor material to a first solvent and 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, etc. can be used for preparation.

[0325] The first solvent and the second solvent and the p-type semiconductor material and the n-type semiconductor material may be heated and mixed to a temperature below 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 obtained mixture may be filtered using a filter, and the obtained filtrate may be used. As the filter, for example, a filter formed of a fluororesin such as polytetrafluoroethylene (PTFE) can be used.

[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 containing a p-type semiconductor material and an n-type semiconductor material. As the n-type semiconductor material, it is preferable to include the compound of the present disclosure. Preferred embodiments 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 configuration, a decrease in the external quantum efficiency with respect to heat treatment in 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 can be suppressed, and the heat resistance can be effectively improved.

[0329] Here, a configuration example 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] As shown in FIG. 1, the 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] As another configuration example of the photoelectric conversion element, it 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 configuration example, a sealing member is further provided in contact with the anode.

[0332] Hereinafter, the components that can be included in the photoelectric conversion element of the present disclosure will be specifically described.

[0333] <Substrate> A photoelectric conversion element is usually formed on a substrate (support substrate). Further, it may be sealed by a substrate (sealing substrate). Usually, one of a pair of electrodes consisting of an anode and a cathode is formed on the substrate. The material of the substrate is not particularly limited as long as it does not chemically change when forming a layer containing an organic compound in particular.

[0334] Examples of the material of the substrate include glass, plastic, polymer film, and silicon. When an opaque substrate is used, the electrode on the side opposite to the electrode provided on the opaque substrate side (in other words, the electrode far from the opaque substrate) is preferably a transparent or translucent electrode.

[0335] <Electrode> A photoelectric conversion element includes an anode and a cathode which are a pair of electrodes. Among the anode and the cathode, at least one of the electrodes is preferably a transparent or translucent electrode for allowing light to enter.

[0336] Examples of the material of the transparent or translucent electrode include a conductive metal oxide film and a translucent metal thin film. Specifically, indium oxide, zinc oxide, tin oxide, and composites thereof such as indium tin oxide (ITO), indium zinc oxide (IZO), and NESA, conductive materials such as gold, platinum, silver, and copper can be mentioned. As the material of the transparent or translucent electrode, ITO, IZO, and tin oxide are preferable. Further, as the electrode, a transparent conductive film using an organic compound such as polyaniline and its derivatives, polythiophene and its derivatives as the material may be used. The transparent or translucent electrode may be an anode or a cathode.

[0337] If one of the pair of electrodes is transparent or translucent, the other electrode may be an electrode with low light transmittance. Examples of materials for the electrode with low light transmittance include metals and conductive polymers. Specific examples of materials for the electrode with low light transmittance include metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, etc., alloys of two or more of these, or alloys of one or more of these metals and 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, polythiophene and its derivatives. Examples of 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 of the present disclosure is assumed to have a bulk heterojunction structure, includes a p-type semiconductor material and an n-type semiconductor material, and the active layer includes the compound of the present disclosure as the n-type semiconductor material.

[0339] The thickness of the active layer is not particularly limited. The thickness of the active layer can be set to any suitable thickness in consideration of the balance between suppression of dark current and extraction of generated photocurrent. From the viewpoint of further reducing dark current in particular, the thickness of the active layer is preferably 100 nm or more, more preferably 150 nm or more, and still more preferably 200 nm or more. Also, the thickness of the active layer is preferably 10 μm or less, more preferably 5 μm or less, and still more preferably 1 μm or less.

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

[0341] <Intermediate layer> As shown in FIG. 1, in order to improve characteristics such as photoelectric conversion efficiency, 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).

[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 of PEDOT (poly(3,4-ethylenedioxythiophene)) and PSS (poly(4-styrenesulfonate)) (PEDOT:PSS).

[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 a function of transporting holes from the active layer to the electrode.

[0344] The hole transport layer provided in contact with the anode is sometimes particularly referred to as a hole injection layer. The hole transport layer (hole injection layer) provided in contact with the anode has a 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 transporting material. Examples of hole transporting materials include polythiophene and its derivatives, aromatic amine compounds, polymer compounds containing a structural unit having an aromatic amine residue, CuSCN, CuI, NiO, tungsten oxide (WO3), and molybdenum oxide (MoO3). Examples of hole transporting material products include P-10 and P-21 from Avantama.

[0346] The intermediate layer can be formed by any conventionally known suitable formation method. The intermediate layer can be formed by a vacuum evaporation 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 structure 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 laminated 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 particularly referred to as an electron injection layer. The electron transport layer (electron injection layer) provided in contact with the cathode has a 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. Examples of the electron transporting material include polyalkyleneimine and its derivatives, polymer compounds containing a fluorene structure, metals such as calcium, and metal oxides.

[0351] Examples of polyalkyleneimine and its derivatives include alkyleneimines having 2 to 8 carbon atoms such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, and octyleneimine, particularly polymers obtained by polymerizing one or more alkyleneimines having 2 to 4 carbon atoms by a conventional method, and polymers chemically modified by reacting them with various compounds. As polyalkyleneimine and its derivatives, polyethyleneimine (PEI) and ethoxylated polyethyleneimine (PEIE) are preferable.

[0352] Examples of the polymer compound 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 the metal oxide include zinc oxide, gallium-doped zinc oxide, aluminum-doped zinc oxide, titanium oxide, and niobium oxide. As the metal oxide, a metal oxide containing zinc is preferable, and zinc oxide is particularly preferable. Examples of the metal oxide products include Avantama's N-10, N-11, N-12, N-13, N-20X, N-21X, Infinity PV's ZnO, ZnO(2.8%), ZnO(5.6%), and Doped ZnO.

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

[0355] <Sealing member> The photoelectric conversion element of the present disclosure further includes a sealing member, and it is preferable to form a sealed body sealed by such a sealing member. Any suitable conventionally known member can be used as the sealing member. Examples of the sealing member include a combination of a glass substrate (sealing substrate) as a 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 the layers constituting the sealing layer include a gas barrier layer and a gas barrier film.

[0357] The sealing layer is preferably formed of a material having a property of blocking moisture (water vapor barrier property) or a property of blocking oxygen (oxygen barrier property). Examples of suitable materials as the material of the sealing layer include organic materials such as polytetrafluoroethylene, polychlorotrifluoroethylene (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 usually composed of a material that can withstand the heat treatment performed when the photoelectric conversion element is incorporated into a device, for example, in the following application examples, to which the photoelectric conversion element is applied.

[0359] <Applications of the photoelectric conversion element> Examples of the applications of the photoelectric conversion element of the present disclosure include a photodetector and a solar cell. More specifically, the photoelectric conversion element of the present disclosure can generate a photocurrent by irradiating light from a transparent or translucent electrode side in a state where a voltage (reverse bias voltage) is applied between the electrodes, and can operate as a photodetector (photosensor). Also, by integrating a plurality of photodetectors, it can be used as an image sensor. Thus, the photoelectric conversion element of the present disclosure can be particularly suitably used as a photodetector.

[0360] In addition, the photoelectric conversion element of the present disclosure can generate a photoelectromotive force between the electrodes by being irradiated with light, and can operate as a solar cell. By integrating a plurality of photoelectric conversion elements, a solar cell module can also be formed.

[0361] The photoelectric conversion element of the present disclosure can be suitably applied as a photodetector to detection units provided in various electronic devices such as workstations, personal computers, portable information terminals, entrance / exit management systems, digital cameras, and medical devices.

[0362] The photoelectric conversion element of the present disclosure can be suitably applied to detection units of solid-state imaging devices such as X-ray imaging devices and CMOS image sensors (such as image sensors such as X-ray sensors), fingerprint detection units, face detection units, vein detection units, and iris detection units, which are provided in the above-exemplified electronic devices, and are used to detect predetermined features of a part of a living body in a biometric authentication device (such as a near-infrared sensor), and detection units of optical biosensors such as pulse oximeters.

[0363] Since the compound of the present disclosure is included in the photoelectric conversion element of the present disclosure, it is driven at a longer wavelength than before.

[0364] <Method for manufacturing a photoelectric conversion element> The manufacturing method of 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 formation methods suitable for the materials selected for forming the components.

[0365] Hereinafter, a manufacturing method of a photoelectric conversion element having a configuration in which a substrate (support substrate), an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode are in contact with each other in this order will be described.

[0366] (Step of preparing a substrate) In this step, for example, a support substrate provided with an anode is prepared. Also, a substrate provided with a conductive thin film formed of the electrode material already described can be obtained from the market, and if necessary, the conductive thin film can be patterned to form an anode, thereby preparing a support substrate provided with an anode.

[0367] In the manufacturing method of the photoelectric conversion element of the present disclosure, the method for forming the anode when forming the anode on the support substrate is not particularly limited. The anode can be formed on a configuration (e.g., support substrate, active layer, hole transport layer) on which the anode is to be formed by any conventionally known suitable method such as a vacuum evaporation method, a sputtering method, an ion plating method, a plating method, or a coating method using the materials already described.

[0368] (Step of forming a hole transport layer) The manufacturing method of the 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 making the formation process of the hole transport layer simpler, it is preferable to form the hole transport layer by any conventionally known suitable coating method. The hole transport layer can be formed, for example, by a coating method using a coating solution containing the material and solvent of the hole transport layer already described or a vacuum evaporation method.

[0370] (Step of forming an active layer) In the method for manufacturing a photoelectric conversion element of the present disclosure, an active layer is formed on a hole transport layer. The active layer, which is a main component, can be formed by any suitable conventionally known forming process. The active layer is preferably manufactured by a coating method using ink (coating liquid). Preferred embodiments of the ink are as described above.

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

[0372] Step (i) As a method for applying ink to an object to be coated, any suitable coating method can be used. Preferred coating methods include a slit coating method, a knife coating method, a spin coating method, a microgravure coating method, a gravure coating method, a bar coating method, an inkjet printing method, a nozzle coating method, or a capillary coating method. More preferred are the slit coating method, the spin coating method, the capillary coating method, or the bar coating method. Even more preferred are the slit coating method or the spin coating method.

[0373] The ink for forming the active layer is applied to an object to be coated selected according to the photoelectric conversion element and its manufacturing method. The ink for forming the active layer can be applied to a functional layer of the photoelectric conversion element in the manufacturing process of the photoelectric conversion element, where the active layer can be present. Therefore, the object to be coated with the ink for forming the active layer varies depending on the layer configuration and the order of layer formation of the photoelectric conversion element to be manufactured. For example, when the photoelectric conversion element has a layer configuration in which a substrate, an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode are laminated, and the layers described on the left side are formed first, the object to be coated with the ink for forming the active layer is the hole transport layer. Also, for example, when the photoelectric conversion element has a layer configuration in which a substrate, a cathode, an electron transport layer, an active layer, a hole transport layer, and an anode are laminated, and the layers described on the left side are formed first, the object to be coated with the ink for forming the active layer is the electron transport layer.

[0374] Step (ii) As a method for removing the solvent from the ink coating film, that is, a method for removing the solvent from the coating film and solidifying it, any suitable method can be used. Examples of the method for removing the solvent include a method of directly heating using a hot plate in an inert gas atmosphere such as nitrogen gas, a hot air drying method, an infrared heating drying method, a flash lamp annealing drying method, a drying method such as a vacuum drying method, and the like.

[0375] The thickness of the active layer can be set to any suitable 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 step (i) and step (ii), provided that the objects and effects of the present disclosure are not impaired.

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

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

[0379] The method for forming the electron transport layer is not particularly limited. From the viewpoint of making the formation step of the electron transport layer simpler, it is preferable to form the electron transport layer by any suitable conventionally known vacuum evaporation method.

[0380] (Step of forming the cathode) The method for forming the cathode is not particularly limited. The cathode can be formed on the electron transport layer by any suitable conventionally known method such as a coating method, a vacuum evaporation method, a sputtering method, an ion plating method, a plating method, etc. using the materials of the electrodes exemplified above. Through the above steps, the photoelectric conversion element of the present disclosure is manufactured.

[0381] (Step of forming the encapsulant) In forming the sealing body, a conventionally known optional suitable sealing material (adhesive) and a substrate (sealing substrate) are used. Specifically, after applying a sealing material such as a UV curable resin on a support substrate so as to surround the periphery of the manufactured photoelectric conversion element, and then bonding them together without gaps with the sealing material, a photoelectric conversion element is sealed in the gap between the support substrate and the sealing substrate by using a method suitable for the selected sealing material such as irradiation with UV light, whereby a sealing body of the photoelectric conversion element can be obtained.

[0382] <Photoelectric detection element> The photoelectric conversion element of the present disclosure, particularly the photoelectric detection element (optical sensor), as described above, can be incorporated into an image sensor or a biometric authentication device (fingerprint authentication device, vein authentication device) and function.

Examples

[0383] Examples are shown below to explain the present disclosure in more detail. 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)> As the polymer compound P-19, PCE-10, manufactured by 1-material and sold under the trade name, was obtained from the market and used.

[0386] (Polymer compound P-19)

[0387]

Chemical formula

[0388] <n-type semiconductor material> As the n-type semiconductor material, the following compound was used. The synthesis method will be described later.

[0389] (Compound N-1)

[0390]

Chemical formula

[0391] (Compound N-2)

[0392]

Chem.

[0393] (Compound N-3)

[0394]

Chem.

[0395] (Compound N-4)

[0396]

Chem.

[0397] (Compound N-5)

[0398]

Chem.

[0399] (Compound N-6)

[0400]

Chem.

[0401] (Compound N-7)

[0402]

Chem.

[0403] (Compound N-8)

[0404]

Chem.

[0405] (Compound N-9)

[0406]

Chem.

[0407] (Compound N-10)

[0408]

Chem.

[0409] (Compound N-11)

[0410]

Chem.

[0411] (Compound N-12)

[0412]

Chem.

[0413] (Compound N-13)

[0414]

Chem.

[0415] (Compound N-14)

[0416]

Chem.

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

[0418]

Chem.

[0419] Into a 300 mL four-necked flask, 3-Methoxythiophene (manufactured by Tokyo Chemical Industry, 5.00 g, 43.8 mmol), 2-Hexyl-1-decanol (31.9 g, 131 mmol), p-TsOH·H2O (0.833 g, 4.38 mmol), and toluene (100 g) were charged. After nitrogen substitution, the temperature was raised to 110 °C. After stirring for 23 hours, it was cooled to room temperature. It was diluted with toluene, washed twice by liquid separation with water, dried over magnesium sulfate, filtered, and then concentrated to dryness with a rotary evaporator. The obtained crude product was purified by 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 obtained 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]

Chemical Structure

[0422] A 200 mL four-necked flask was charged with Compound 2 (4.0 g, 12.3 mmol) and THF (45 mL), purged with nitrogen, and then cooled to -73 °C. LDA (1 M in THF / Hexane, 13.6 mL, 13.6 mmol) was charged, and the internal temperature was maintained at -65 °C for 1 hour. A dropping funnel was charged with 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.2 mL, 18.5 mmol) and THF (22.5 mL), and the mixture was slowly added dropwise 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 2 hours. Quenching was carried out by pouring 20% aqueous ammonium chloride solution (26 mL). After removing the aqueous layer from the resulting mass by liquid separation, it was dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator to obtain 5.91 g of Compound 3 as a crude product. The obtained Compound 3 was analyzed by NMR spectrum. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 7.26 (1H), 6.56 (1H), 3.82 (2H), 1.74-1.72 (1H), 1.57-1.19 (m, 36H), 00.88 (6H)

[0423] Compound 4 was synthesized using Compound 3.

[0424]

Chemical Structure

[0425] Into a 500 mL four-necked flask, the crude product of 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), and THF (149 mL) were charged, and nitrogen bubbling was carried out for 30 minutes. Pd2(dba)3 (0.600 g, 0.655 mmol), P(tBu3)HBF4 (0.399 g, 1.38 mmol), and 3 mol / L aqueous K3PO4 solution (60.6 g) were charged in this order, and then the temperature was raised to 65 °C. After stirring for 2 hours, it was cooled to room temperature. After dilution with toluene and liquid-liquid washing with water twice, it was dried over magnesium sulfate, filtered, and then concentrated to dryness with a rotary evaporator. The obtained crude product was purified by silica gel column (developing solvent: heptane / ethyl acetate = 20 / 1 (volume ratio)) to obtain 3.72 g of Compound 4 as a yellowish-brown liquid. The NMR spectrum of the obtained 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]

Chemical Structure

[0428] A 100 mL four-necked flask was charged with Compound 4 (1.60 g, 2.84 mmol) and chloroform (56.0 g), purged with nitrogen, and then cooled to 0 °C. NBS (0.501 g, 2.81 mmol) was charged and stirred at 0 °C. After stirring for 2 hours, water (40.0 g) was charged. After warming to room temperature, the aqueous layer was removed from the resulting mass by liquid separation, dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. The resulting crude product was purified by silica gel column (developing solvent: heptane / ethyl acetate = 20 / 1 (volume ratio)) to obtain 1.84 g of Compound 5 as a yellowish-brown liquid. The NMR spectrum of the obtained Compound 5 was analyzed. The results are as follows. 1 1H-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]

Chemical formula

[0431] A 50 mL four-necked flask was charged with 4-Bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b’]dithiophene (manufactured by Tokyo Chemical Industry Co., Ltd., 1.00 g, 2.48 mmol) and THF (11.2 mL). After purging with nitrogen, it was cooled to -73 °C. nBuLi (1.56 mol / L in Hexane, 1.75 mL, 2.73 mmol) was charged, and the internal temperature was maintained at -65 °C for 1 hour. A dropping funnel was charged with 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.85 mL, 3.72 mmol) and THF (5.6 mL), and it was slowly added dropwise to the reaction mass at an internal temperature of -65 °C. After completion of the dropwise 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. Quenching was carried out by pouring 20% aqueous ammonium chloride solution (5.3 mL). After removing the aqueous layer from the obtained mass by liquid separation, it was dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator to obtain 1.49 g of the crude product of Compound 7.

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

[0433] [Chemical formula]

[0434] A 100 mL four-necked flask was charged with the crude product of 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. Pd2(dba)3 (0.113 g, 0.123 mmol), P(tBu3)HBF4 (0.0749 g, 0.258 mmol), and a 3 mol / L aqueous solution of K3PO4 (11.4 g) were charged in this order, and then the temperature was raised to 60 °C. After stirring for 2 hours, it was cooled to room temperature. It was diluted with toluene, washed twice by liquid separation with water, dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. The obtained crude product was purified by 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 obtained 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]

Chemical Structure

[0437] Into a 50 mL four-necked 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), Pd(OAc)2 (0.0364 g, 0.162 mmol), [(tBu)2MePH]BF4 (0.0644 g, 0.259 mmol), pivalic acid (0.133 g, 1.30 mmol), K2CO3 (0.538 g, 3.89 mmol), and DMF (12.5 g) were charged, and nitrogen bubbling was carried out 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, washed twice with water by liquid separation, dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. The obtained crude product was purified by silica gel column (developing solvent: heptane / ethyl acetate = 8 / 1 (volume ratio)) to obtain 0.620 g of compound 9 as a dark 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 N-1 was synthesized using compound 9.

[0439]

Chemical Structure

[0440] Into a 50 mL four-necked 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·H2O (0.285 g, 1.50 mmol), EtOH (5.5 g), toluene (11.0 g), and MgSO4 (0.300 g) were charged, and the flask was placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, the flask was removed from the oil bath and allowed to cool to room temperature. After removing MgSO4 by filtration, the precipitate was washed while dissolving it in chloroform. After concentration with an evaporator, the crude product was obtained by repulping and washing with methanol. The obtained crude product was purified by 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. 1 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]

Chemical Structure

[0443] Into a 50 mL four-necked flask, 4-Bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b’]dithiophene (manufactured by Tokyo Chemical Industry Co., Ltd., 1.00 g, 2.48 mmol), bis(pinacolato)diboron (1.58 g, 6.21 mmol), [Ir(OMe)(cod)]2 (19.8 mg, 0.0298 mmol), and tBu-bpy (16.0 mg, 0.0596 mmol) were charged. After purging with nitrogen, 15.0 g of cyclohexane was charged, and the flask was placed in an oil bath heated to 60 °C and kept warm. After stirring for 2 hours, the flask was removed from the oil bath and allowed to cool to room temperature. The quenching was carried out by pouring the cooled mass into water. After removing the aqueous layer from the obtained mass by liquid separation, it was dried over magnesium sulfate, filtered while passing through silica gel, and then concentrated to dryness using a rotary evaporator to obtain 2.30 g of the crude product of Compound 12.

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

[0445] [Chemical formula]

[0446] Into a 50 mL four-necked flask, the crude product of Compound 12 (1.13 g), Compound 5 (1.80 g, 2.81 mmol), and THF (18.2 g) were charged, and nitrogen bubbling was carried out for 30 minutes. Pd2(dba)3 (0.0560 g, 0.0612 mmol), P(tBu3)HBF4 (0.0372 g, 0.128 mmol), and a 3 mol / L aqueous solution of K3PO4 (5.66 g) were charged in this order, and then the temperature was raised to 60 °C. After stirring for 2 hours, it was cooled to room temperature. After diluting with toluene and washing twice by liquid separation with water, it was dried over magnesium sulfate, filtered, and then concentrated to dryness using a rotary evaporator. The obtained crude product was purified by silica gel column (developing solvent: heptane / ethyl acetate = 8 / 1 (volume ratio)) to obtain 1.19 g of Compound 13 as a dark red viscous liquid. The NMR spectrum of the obtained Compound 13 was analyzed. The results are as follows. 1H-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 N-2 was synthesized using Compound 13.

[0448]

Chemical Structure

[0449] Into a 100 mL four-necked flask, Compound 13 (1.15 g, 0.754 mmol), Compound 10 (0.553 g, 2.26 mmol), p-TsOH·H2O (0.431 g, 2.26 mmol), EtOH (10.5 g), toluene (23.0 g), and MgSO4 (0.575 g) were charged, and the flask was placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, it was taken out of the oil bath and allowed to cool to room temperature. After removing MgSO4 by filtration, the precipitate was washed while dissolving it in chloroform. After concentration with an evaporator, the crude product was obtained by repulping and washing with methanol. The obtained crude product was purified by a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 0.890 g (yield 60%) of Compound N-2 as a black solid. For the obtained Compound N-2, the NMR spectrum was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 8.94 - 8.93 (m, 2H), 8.69 (2H), 8.10 (2H), 7.50 - 7.35 (m, 6H), 4.19 - 4.15 (m, 8H), 1.94 - 0.64 (m, 126H)

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

[0451]

Chemical Structure

[0452] Into a 300 mL four-necked flask, 3-Methoxythiophene (manufactured by Tokyo Chemical Industry, 4.50 g, 39.4 mmol), 2-Ethyl-1-hexanol (15.4 g, 118 mmol), p-TsOH·H2O (0.750 g, 3.94 mmol), and toluene (90 g) were charged. After purging with nitrogen, the temperature was raised to 110 °C. After stirring for 7 hours, it was cooled to room temperature. It was diluted with toluene, washed twice by liquid separation with water, dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. The obtained crude product was purified by 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 obtained 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]

Chemical formula

[0455] A 100 mL four-necked flask was charged with Compound 13 (2.0 g, 9.42 mmol) and THF (22.5 mL). After purging with nitrogen, it was cooled to -73 °C. LDA (1 M in THF / Hexane, 11.3 mL, 11.3 mmol) was charged, and the internal temperature was maintained at -65 °C for 1 hour. A dropping funnel was charged with 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.2 mL, 14.1 mmol) and THF (11.2 mL), and it was slowly added dropwise 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 2 hours. Quenching was carried out by pouring 20% aqueous ammonium chloride solution (20 mL). After removing the aqueous layer from the resulting mass by liquid separation, it was dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator to obtain 3.13 g of Compound 14 as a crude product. The obtained Compound 14 was analyzed by NMR spectrum. 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]

Chemical Structure

[0458] Into a 100 mL four-necked flask, charged were the crude product of 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), and THF (31.4 mL). Nitrogen bubbling was carried out for 30 minutes. Pd2(dba)3 (0.420 g, 0.458 mmol), P(tBu3)HBF4 (0.279 g, 0.962 mmol), and an aqueous solution of 3 mol / L K3PO4 (17.0 g) were charged in sequence, and then the temperature was raised to 65 °C. After stirring for 2 hours, it was cooled to room temperature. Diluted with toluene, washed twice with water by liquid separation, dried over magnesium sulfate, filtered, and then concentrated to dryness with a rotary evaporator. The obtained crude product was purified by a silica gel column (developing solvent: heptane / ethyl acetate = 15 / 1 (volume ratio)) to obtain 2.81 g of Compound 15 as a yellowish-brown liquid. The NMR spectrum of the obtained Compound 15 was analyzed. The results are as follows. 1 1H-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]

Chemical Structure

[0461] A 100 mL four-necked flask was charged with Compound 15 (1.15 g, 2.55 mmol) and chloroform (40.3 g), purged with nitrogen, and then cooled to 0 °C. NBS (0.450 g, 2.53 mmol) was charged, and the mixture was stirred at 0 °C. After stirring for 2 hours, water (28.8 g) was charged, the temperature was raised to room temperature, and after removing the aqueous layer by liquid separation from the resulting mass, it was dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. The obtained crude product was purified by 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 obtained 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]

Chemical formula

[0464] Compound 17 was synthesized with reference to the method described in International Publication No. 2014 / 112656. A 50 mL four-necked flask was charged with Compound 17 (0.720 g, 0.915 mmol), Compound 16 (1.12 g, 2.11 mmol), and THF (16.4 g), and nitrogen bubbling was carried out for 30 minutes. Pd2(dba)3 (0.0419 g, 0.0458 mmol), P(tBu3)HBF4 (0.0279 g, 0.0961 mmol), and an aqueous solution of 3 mol / L K3PO4 (4.24 g) were charged in this order, and then the temperature was raised to 60 °C. After stirring for 2 hours, it was cooled to room temperature. It was diluted with toluene, washed twice by liquid separation with water, dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. The obtained crude product was purified by a silica gel column (developing solvent: heptane / ethyl acetate = 8 / 1 (volume ratio)) to obtain 1.25 g of Compound 18 as a blue-violet viscous liquid. The NMR spectrum of the obtained Compound 18 was analyzed. The results are as follows. 1 1H-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 N-3 was synthesized using Compound 18.

[0466]

Chemical Structure

[0467] Into a 100 mL four-necked flask, compound 18 (1.20 g, 0.840 mmol), compound 10 (0.616 g, 2.52 mmol), p-TsOH·H2O (0.480 g, 2.52 mmol), EtOH (10.9 g), toluene (24.0 g), and MgSO4 (0.600 g) were charged, and it was placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, it was taken out of the oil bath and allowed to cool to room temperature. After removing MgSO4 by filtration, the precipitate was washed while dissolving it with chloroform. After concentration with an evaporator, the crude product was obtained by repulping and washing with methanol. The obtained crude product was purified by a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 1.23 g (yield 78%) of compound N-3 as a black solid. For the obtained compound N-3, the NMR spectrum was analyzed. The results are as follows. 1 1H-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]

Chemical Structure

[0470] Into a 100 mL four-necked flask, 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. After purging with nitrogen, the internal temperature was raised to 80 °C and stirred for 3 hours. After cooling to room temperature, it was quenched with a 5% aqueous K3PO4 solution. It was separated and washed twice with water, the organic layer was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the whole volume was concentrated on a rotary evaporator. The obtained crude product was purified by 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 obtained compound 19 was analyzed. The results are as follows. 1 H-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]

Chemical formula

[0473] A 100 mL four-necked flask was charged with 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). After purging with nitrogen, the internal temperature was raised to 80 °C and stirred for 2 hours. Another 100 mL four-necked flask was charged with 8.48 g of water, and the cooled reaction mass was added dropwise. The aqueous layer was removed by liquid separation, and the organic layer was dried over magnesium sulfate and then filtered while passing through silica gel. The resulting filtrate was concentrated to dryness using a rotary evaporator to obtain 1.98 g of Compound 20 (yield 84%). The obtained Compound 20 was analyzed by NMR spectrum. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 7.42(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]

Chemical Structure

[0476] A 50 mL four-necked flask was charged with 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), and nitrogen bubbling was carried out for 30 minutes. Pd2(dba)3 (0.027 g, 0.030 mmol), P(tBu3)HBF4 (0.018 g, 0.063 mmol), and a 3 mol / L aqueous K3PO4 solution (1.9 mL) were charged in this order, and then the temperature was raised to 60 °C. After stirring for 2 hours, it was cooled to room temperature. The reaction mass was diluted with toluene, washed twice with water by liquid separation, dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. The obtained crude product was purified by recycled GPC to obtain 0.82 g of Compound 22 (yield 50%). The NMR spectrum of the obtained Compound 22 was analyzed. The results are as follows. 1 1H-NMR (300 MHz, CHLOROFORM-D) δ 9.81(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 23 was synthesized using Compound 22.

[0478]

Chemical Structure

[0479] A 50 mL four-necked flask was purged with nitrogen, charged with Compound 22 (0.39 g, 0.289 mmol), THF (18.5 mL), water (4.5 mL), and trifluoroacetic acid (0.45 mL), and 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 by liquid separation with water. The organic layer was dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator to obtain a crude product. The obtained crude product was purified by 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 obtained Compound 23 was analyzed. The results are as follows. 1 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]

Chemical formula

[0482] Into a 50 mL four-necked flask, compound 23 (0.32 g, 0.247 mmol), compound 10 (0.181 g, 0.742 mmol), p-TsOH·H2O (0.141 g, 0.742 mmol), EtOH (3.6 ml), toluene (7.3 ml), and MgSO4 (0.141 g) were charged, and it was placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, it was taken out of the oil bath and allowed to cool to room temperature. After removing MgSO4 by filtration, the precipitate was washed while dissolving it with chloroform. After concentration with an evaporator, the crude product was obtained by repulping and washing with methanol. The obtained crude product was purified by recycled GPC to obtain 0.342 g (yield 79%) of compound N-4 as a black solid. For the obtained compound N-4, the NMR spectrum was analyzed. The results are as follows. 1 1H-NMR (300 MHz, CHLOROFORM-D) δ 8.99(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]

Chemical Structure

[0485] A 1-L four-necked flask was charged with Compound 2 (15.35 g, 47.3 mmol) and THF (460.5 g), purged with nitrogen, and then cooled to 0 °C. NBS (8.33 g, 46.8 mmol) was charged and stirred at 0 °C. After stirring for 2 hours, an aqueous solution of 3% sodium sulfite (249 g) was charged. After warming to room temperature, the aqueous layer was removed from the resulting mass by liquid separation, dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. The obtained crude product was purified by 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]

Chemical formula

[0488] A 3-L four-necked flask was charged with Compound 24 (92.28 g, 228.7 mmol) and THF (1038 mL), 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 complete, the internal temperature was maintained at -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. After the addition was complete, the temperature was raised to room temperature and stirred for 2 hours. Quenching was carried out by pouring a 20% aqueous ammonium chloride solution (489 mL). After that, the aqueous layer was removed from the resulting mass by liquid separation, dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. The obtained crude product was purified by 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. 1H-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]

Chem.

[0491] To a 50 mL four-necked flask were charged Compound 8 (0.964 g, 1.00 mmol), Compound 25 (0.518 g, 1.20 mmol), Pd(OAc)2 (0.0561 g, 0.250 mmol), [(tBu)2MePH]BF4 (0.0992 g, 0.400 mmol), pivalic acid (0.102 g, 1.00 mmol), K2CO3 (0.415 g, 3.00 mmol), and DMF (9.5 g). Nitrogen bubbling was carried out 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, washed twice with water by liquid separation, dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. The obtained crude product was purified by silica gel column (developing solvent: heptane / ethyl acetate = 8 / 1 (volume ratio)) to obtain 0.280 g of Compound 26 as a dark red-violet 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 N-5 was synthesized using Compound 26.

[0493]

Chem.

[0494] Into a 50 mL four-necked 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·H2O (0.117 g, 0.613 mmol), EtOH (2.5 g), toluene (5.5 g), and MgSO4 (0.140 g) were charged, and the flask was placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, the flask was removed from the oil bath and allowed to cool to room temperature. After removing MgSO4 by filtration, the precipitate was washed while dissolving it in chloroform. After concentration with an evaporator, the crude product was obtained by repulping and washing with methanol. The obtained crude product was purified by 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 obtained compound N-5 was analyzed by NMR spectrum. 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]

Chemical Structure

[0497] Into a 50 mL four-necked flask, compound 8 (2.89 g), 5-Bromo-4-(2-ethylhexyl)thiophene-2-carbaldehyde (1.34 g), Pd(OAc)2 (0.126 g), [(tBu)2MePH]BF4 (0.223 g), pivalic acid (0.306 g), K2CO3 (1.24 g), and DMF (20 mL) were charged, and nitrogen bubbling was carried out for 30 minutes. After nitrogen substitution, 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 by liquid separation, dried over magnesium sulfate, filtered, and then concentrated to dryness by a rotary evaporator. The obtained crude product was purified by a silica gel column (developing solvent: heptane / ethyl acetate = 9 / 1 (volume ratio)) to obtain 3.32 g of compound 27.

[0498] Compound N-6 was synthesized using compound 27.

[0499] [Chemical formula]

[0500] Into a 100 mL four-necked flask, compound 27 (1.30 g, 1.10 mmol), compound 10 (0.767 g, 3.14 mmol) synthesized according to the method described in International Publication No. 2020 / 109823, p-TsOH·H2O (0.597 g, 1.50 mmol), EtOH (12 g), toluene (26 g), and MgSO4 (0.65 g) were charged, and it was placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, it was taken out of the oil bath and allowed to cool to room temperature. After removing MgSO4 by filtration, the precipitate was washed while dissolving it with chloroform. After concentration by an evaporator, the crude product was obtained by repulping with methanol. The obtained crude product was purified by 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. 1H-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] [Chemical formula]

[0503] The crude product of 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 charged into a 50 mL three-necked flask, and nitrogen bubbling was carried out for 30 minutes. Pd2(dba)3 (0.054 g, 0.06 mmol), P(tBu3)HBF4 (0.034 g, 0.12 mmol), and a 3 mol / L aqueous solution of K3PO4 (2.19 g) were charged in this order, and then the temperature was raised to 60 °C. After stirring for 2 hours, it was cooled to room temperature. It was diluted with toluene, washed twice by liquid separation with water, dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. The obtained crude product was purified by 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 red-violet viscous liquid. The NMR spectrum of the obtained Compound 28 was analyzed. The results are as follows. 1H-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 N-11 was synthesized using Compound 28.

[0505]

Chemical Structure

[0506] A 50 mL four-necked flask was charged with Compound 28 (0.521 g, 0.59 mmol), Compound 10 (0.434 g, 1.78 mmol), p-TsOH·H2O (0.338 g, 1.78 mmol), EtOH (4.7 g), toluene (10.4 g), and MgSO4 (0.26 g), and then placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, it was removed from the oil bath and allowed to cool to room temperature. After removing MgSO4 by filtration, the precipitate was washed while dissolving it with chloroform. After concentration using an evaporator, the crude product was obtained by repulping with methanol. The obtained crude product was purified by silica gel column (developing solvent: chloroform = 100 wt%), and then repulped with acetone to obtain 0.432 g (yield 55%) of Compound N-11 as a blue-green to 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]

Chem.

[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), and THF (9.0 g) were charged into a 100 mL three-necked flask, and nitrogen bubbling was carried out for 30 minutes. Pd2(dba)3 (0.058 g, 0.06 mmol), P(tBu3)HBF4 (0.037 g, 0.13 mmol), and an aqueous solution of 3 mol / L K3PO4 (2.36 g) were charged in this order, and then the temperature was raised to 60 °C. After stirring for 2 hours, it was cooled to room temperature (25 °C). It was diluted with toluene, washed twice with water by liquid separation, dehydrated with magnesium sulfate, the magnesium sulfate was removed by filtration, and then the whole amount was concentrated with a rotary evaporator. The obtained crude product was purified by 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-violet solid. For the obtained Compound 29, the NMR spectrum was analyzed. The results are as follows. 1 1H-NMR (300 MHz, 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 N-12 was synthesized using Compound 29.

Chem.

[0511] Into a 30 mL three-necked flask, compound 29 (0.266 g, 0.264 mmol), compound 10 (0.194 g, 0.793 mmol), p-TsOH·H2O (0.151 g, 0.0793 mmol), EtOH (2.4 g), toluene (5.3 g), and MgSO4 (0.13 g) were charged, and it was placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, it was taken out of the oil bath and allowed to cool to room temperature. After removing MgSO4 by filtration, the precipitate was washed while dissolving it with chloroform. After concentration with an evaporator, the crude product was obtained by repulping and washing with methanol. The obtained crude product was purified by a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 0.265 g (yield 72%) of compound N-12 as a blue-greenish black solid. The NMR spectrum of the obtained compound N-12 was analyzed. The results are as follows. 1 1H-NMR (300 MHz, 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] [Chemical formula]

[0514] In a 50 mL four-necked flask, magnesium (shavings) (0.353 g, 14.5 mmol), diethyl ether (10.0 mL), and a small amount of iodine were charged. After purging with nitrogen, the mixture was stirred at room temperature. 2-Bromo-3-(2-ethylhexyl)thiophene (2.00 g, 7.27 mmol) and diethyl ether (10.0 mL) were charged into a dropping funnel and added dropwise little by little with the internal temperature kept below 30 °C. After completion of the dropwise addition, the bath temperature was raised to 43 °C and the mixture was heated under reflux for 2 hours. After maintaining the temperature for 2 hours, it was cooled to room temperature to obtain a Grignard reagent. In a 100 mL four-necked flask, 2,5-Dibromothiophene (1.76 g, 7.27 mmol), PdCl2dppf (0.200 g, 0.273 mmol), and diethyl ether (20.0 mL) were charged. After purging with nitrogen, the mixture was stirred at an internal temperature of 0 °C. The Grignard reagent was added dropwise little by little at an internal temperature of 0 °C and stirred at an internal temperature of 0 °C for 2 hours. Quenching was carried out by pouring water (40 mL). After removing the aqueous layer from the obtained mass by liquid separation, it was dried over magnesium sulfate, filtered, and then concentrated to dryness using a rotary evaporator. The obtained crude product was purified by silica gel column (developing solvent: heptane = 100 wt%) to obtain 1.48 g of Compound 31 as a yellow liquid. For the obtained Compound 31, the NMR spectrum was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 7.19 (1H), 7.00 (1H), 6.89 (1H), 6.84 (1H), 2.64 (2H), 1.62-1.51 (m, 1H), 1.33-1.16 (m, 8H), 0.90-0.80 (m, 6H)

[0515] Compound 32 was synthesized using Compound 17.

[0516]

Chemical formula

[0517] 100 mL of a three-necked flask was charged with Compound 17 (1.40 g, 1.78 mmol), Compound 31 (1.46 g, 4.09 mmol), and THF (52.7 g), and nitrogen bubbling was carried out for 30 minutes. Pd2(dba)3 (0.0813 g, 0.089 mmol), P(tBu3)HBF4 (0.103 g, 0.355 mmol), and 3 mol / L aqueous K3PO4 solution (8.22 g) were charged in this order, and then the temperature was raised to 65 °C. After stirring for 2 hours, it was cooled to room temperature (25 °C). It was diluted with toluene, washed twice by liquid separation with water, dehydrated with magnesium sulfate, the magnesium sulfate was removed by filtration, and then the whole amount was concentrated with a rotary evaporator. The obtained crude product was purified by a silica gel column (developing solvent: heptane = 100 wt%) to obtain 1.81 g (yield 94%) of Compound 32 as a red liquid. The obtained Compound 32 was analyzed by NMR spectrum. The results are as follows. 1 H-NMR (300 MHz, 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]

Chemical Structure

[0520] A 200 mL four-necked flask was charged with Compound 32 (1.79 g, 1.65 mmol) and dichloromethane (109 g). After purging with nitrogen, (Chloromethylene)dimethyliminium Chloride (0.845 g, 6.60 mmol) was charged, and the flask was placed in an oil bath heated to 49 °C and kept warm. After stirring for 24 hours, the flask was removed from the oil bath and allowed to cool to room temperature. After liquid-liquid washing twice with water, it was dehydrated with magnesium sulfate, the magnesium sulfate was removed by filtration, and the whole volume was concentrated using a rotary evaporator. The obtained crude product was purified by silica gel column (developing solvent: heptane / ethyl acetate = 100 / 0 to 20 / 1 (volume ratio)) to obtain 1.72 g (yield 92%) of Compound 33 as a dark red liquid. The NMR spectrum of the obtained Compound 33 was analyzed. The results are as follows. 1 H-NMR (300 MHz, 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]

Chemical Structure

[0523] Into a 100 mL four-necked flask, compound 33 (0.627 g, 0.550 mmol), compound 10 (0.322 g, 1.32 mmol), p-TsOH·H2O (0.209 g, 1.10 mmol), EtOH (21.7 g), and toluene (23.8 g) were charged, and it was placed in an oil bath heated to 89 °C and kept warm. After stirring for 3 hours, it was taken out of the oil bath and allowed to cool to room temperature, then dropped into methanol (115 g), and the precipitate was collected by filtration to obtain a crude product. To the obtained crude product, chloroform (50 g) was added, the internal temperature was raised to 60 °C, and it was heated and stirred for 10 minutes. After cooling to room temperature, heptane (50 g) was added, and the precipitate was collected by filtration to obtain 0.230 g (yield 30%) of compound N-13 as a black solid. For the obtained compound N-13, the NMR spectrum was analyzed. The results are as follows. 1 1H-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]

Chemical Structure

[0526] 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) were charged into a 50 mL four-necked flask, and nitrogen bubbling was carried out for 30 minutes. Pd2(dba)3 (0.0415 g, 0.045 mmol), P(tBu3)HBF4 (0.0276 g, 0.095 mmol), and an aqueous solution of 3 mol / L K3PO4 (4.19 g) were charged in sequence, and then the temperature was raised to 60 °C. After stirring for 2 hours, it was cooled to room temperature. It was diluted with toluene, washed twice with water by liquid separation, dried over magnesium sulfate, filtered, and then concentrated to dryness with a rotary evaporator. The obtained crude product was purified by 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 obtained Compound 35 was analyzed. The results are as follows. 1 1H-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 N-14 was synthesized using Compound 35.

[0528]

Chemical Structure

[0529] Into a 50 mL four-necked flask, compound 35 (0.500 g, 0.294 mmol), compound 10 (0.215 g, 0.882 mmol), p-TsOH·H2O (0.168 g, 0.882 mmol), EtOH (4.6 g), toluene (10.0 g), and MgSO4 (0.250 g) were charged, and the flask was placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, the flask was removed from the oil bath and allowed to cool to room temperature. After removing MgSO4 by filtration, the precipitate was washed while dissolving it with chloroform. After concentration using an evaporator, the crude product was obtained by repulping and washing with methanol. The obtained crude product was purified by 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. 1 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]

Chemical Structure

[0532] A 100 mL four-necked flask was purged with nitrogen, charged with 60% sodium hydride (3.68 g, 92.06 mmol) and THF (23.3 mL), and 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) was added dropwise at 70 °C and stirred for 2 hours. The reaction solution was cooled to room temperature, quenched with a saturated aqueous ammonium chloride solution, and the solids were removed by filtration through Celite while washing with heptane. The filtrate was washed three times with water by liquid separation and then concentrated using a rotary evaporator to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (heptane / ethyl acetate = 5 / 1) to obtain 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 38 was synthesized using compound 37.

[0534]

Chemical Structure

[0535] A 500 ml four-necked flask was purged with nitrogen, charged with Compound 37 (4.70 g, 14.43 mmol) and THF (105.7 ml), and 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 the mixture was stirred for 1.5 hours. Then, N-formylpiperidine (16.01 ml, 14.43 mmol) was added dropwise, and the temperature was raised to room temperature. The reaction mixture was stirred at room temperature for 2 hours, and the reaction vessel was placed in an ice bath and quenched with a 20% aqueous ammonium chloride solution. Heptane was added to remove the aqueous layer, and the organic layer was washed once with water. The organic layer was dried over magnesium sulfate, and after removing the magnesium sulfate by filtration, it was concentrated on a rotary evaporator to obtain 4.42 g of a crude product. The obtained crude product was used in the next reaction without purification. For Compound 38, the NMR spectrum 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]

Chemical Structure

[0538] A 100 mL four-necked flask was purged with nitrogen, charged with Compound 38 (5.10 g) and chloroform (53.7 mL), and cooled to 2 °C in an ice bath. Then, N-bromosuccinimide (2.96 g, 16.63 mmol) was 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, magnesium sulfate was removed by filtration, and the residue was concentrated on a rotary evaporator to obtain a crude product. The obtained 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. 1 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]

Chemical Structure

[0541] A 100 mL four-necked flask was purged with nitrogen, charged with Compound 20 (1.00 g, 0.752 mmol), Compound 39 (0.390 g, 0.902 mmol), and THF (22.6 mL), and nitrogen bubbling was carried out for 30 minutes. Pd2(dba)3 (0.0344 g, 0.0376 mmol), P(tBu3)HBF4 (0.0229 g, 0.0789 mmol), and a 3 mol / L aqueous solution of K3PO4 (2.51 mL) were charged in this order, and then the temperature was raised to 60 °C. After stirring for 2 hours, it was cooled to room temperature. The reaction mass was diluted with heptane, washed twice with water by liquid separation, dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. The obtained crude product was purified by recycled GPC (chloroform) to obtain 0.421 g of Compound 40 (yield 40%). The NMR spectrum of the obtained Compound 40 was analyzed. The results are as follows. 1 1H-NMR (300 MHz, CHLOROFORM-D) δ 9.77(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]

Chemical Structure

[0544] A 50 mL four-necked flask was purged with nitrogen, charged with Compound 40 (0.323 g, 0.230 mmol), THF (15.1 mL), water (3.78 mL), and trifluoroacetic acid (0.353 mL), 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 by liquid separation. The organic layer was dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator to obtain a crude product. The obtained crude product was purified by recycled GPC (chloroform) to obtain 0.386 g of Compound 41 (yield 97%). The NMR spectrum of the obtained 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 N-7 was synthesized using Compound 41.

[0546]

Chemical Structure

[0547] To a 50 mL three-necked flask, compound 41 (0.363 g, 0.276 mmol), compound 10 (0.202 g, 0.828 mmol), p-TsOH·H2O (0.157 g, 0.828 mmol), EtOH (4.1 ml), toluene (8.4 ml), and MgSO4 (0.182 g) were charged, and the flask was placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, the flask was removed from the oil bath and allowed to cool to room temperature. After removing MgSO4 by filtration, the precipitate was washed while dissolving it in chloroform. After concentration with an evaporator, the crude product was obtained by repulping and washing with methanol. The obtained crude product was purified by recycled GPC to obtain 0.210 g (yield 43%) of compound N-7 as a black solid. For the obtained compound N-7, the NMR spectrum was analyzed. The results are as follows. 1 1H-NMR (300 MHz, CHLOROFORM-D) δ 8.99(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. For the obtained compound 48, the NMR spectrum was analyzed. The results are as follows. 1 1H-NMR (300 MHz, DMSO-d6) δ 8.36(1H), 8.18(1H), 6.05(1H)

[0549]

Chemical formula

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

[0551]

Chemical formula

[0552] Into a 100 mL four-necked flask, 27 (0.300 g, 0.25 mmol), 48 (0.399 g, 1.26 mmol), p-TsOH·H2O (0.336 g, 1.77 mmol), EtOH (19.5 g), and toluene (8.1 g) were charged, and the flask was placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, the flask was removed from the oil bath and allowed to cool to room temperature. The precipitated solid was collected by filtration and washed with methanol, ethanol, and heptane to obtain a crude product. The obtained crude product was purified by recycled 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. 1 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]

Chemical Structure

[0555] A 200 ml four-necked 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. The mixture was stirred at 100 °C for 2.5 hours. After cooling to room temperature, it was washed twice by liquid separation with water. The organic layer was dried over magnesium sulfate, filtered, and then concentrated to dryness using a rotary evaporator to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (developing solvent: heptane) to obtain 4.05 g of compound 49. The NMR spectrum of the obtained compound 49 was analyzed. The results are as follows. 1 1H-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]

Chemical formula

[0558] A 200 ml four-necked flask was purged with nitrogen, and compound 49 (1.99 g, 8.76 mmol) and chloroform (21.1 ml) were added. The mixture 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, it was quenched with a 3% aqueous Na2SO3 solution, warmed to room temperature, and the aqueous layer was removed. After further washing once by liquid separation with water, the organic layer was dried over magnesium sulfate, filtered, and then concentrated to dryness using a rotary evaporator to obtain a crude product. The obtained crude product was dissolved in heptane and filtered through silica gel spread 10 mm thick on a Kiriyama funnel, and then 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. 1H-NMR (300 MHz, CHLOROFORM-D) δ 7.25 (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]

Chemical Structure

[0561] A 100 mL four-necked 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 nitrogen bubbling for 30 minutes, Pd2(dba)3 (0.096 g, 0.11 mmol), [(tBu)3PH]BF4 (0.061 g, 0.21 mmol), and an aqueous 3M K3PO4 solution (7.00 mL) were added, and the temperature was raised to 60 °C. After maintaining the temperature for 1 hour, the reaction solution was cooled to room temperature, diluted with 25 mL of heptane, and washed twice by liquid separation with 12.5 mL of water. After drying over magnesium sulfate and removing the magnesium sulfate by filtration, the solution was concentrated using a rotary evaporator to obtain a crude product. The obtained crude product was purified by 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. 1 H-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]

Chemical Structure

[0564] A 300 ml four-necked flask was purged with nitrogen, and compound 51 (5.93 g, 5.66 mmol) and THF (66.8 ml) were added. The internal temperature was cooled to -78 °C in a dry ice / acetone bath. A 1.6 M nBuLi hexane solution (4.17 ml, 6.51 mmol) was added dropwise and stirred for 1 hour. A solution of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.58 g, 8.50 mmol) in THF (33.4 ml) was prepared and added dropwise over 20 minutes. After the addition, the mixture was stirred at -78 °C for 1 hour, warmed to room temperature, and left overnight. The reaction vessel was cooled in an ice bath and quenched with 20% aqueous ammonium chloride solution (12.1 ml). The reaction solution was diluted with heptane, the aqueous layer was removed, and the liquid-liquid washing with water was repeated twice. The organic layer was dried over magnesium sulfate, filtered, and concentrated by an evaporator to obtain 5.89 g of the crude product of compound 52.

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

[0566]

Chemical Structure

[0567] Into a 100 mL four-necked flask, compound 50 (0.524 g, 1.70 mmol), the crude product of compound 52 (3.83 g), and tetrahydrofuran (51.3 mL) were added. After purging with nitrogen, Pd2(dba)3 (0.0781 g, 0.085 mmol, manufactured by Strem Chemicals), [(tBu)3PH]BF4 (0.0495 g, 0.171 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), and 3 M aqueous K3PO4 solution (5.7 mL) were charged, and the temperature was raised to 60 °C. After stirring for 1 hour while maintaining the temperature, the reaction solution was cooled to room temperature, diluted with heptane, and washed twice by liquid separation with water. After drying over magnesium sulfate and removing the magnesium sulfate by filtration, the solution was concentrated using a rotary evaporator to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (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 1H-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]

Chemical Structure

[0570] Into a 50 mL four-necked flask, compound 53 (1.04 g, 0.823 mmol) and CHCl3 (10.0 ml) were added, and the mixture was purged with nitrogen. (Chloromethylene)dimethyliminium Chloride (manufactured by Tokyo Chemical Industry Co., Ltd., 0.969 g, 7.57 mmol) was added, and the temperature was raised to 60 °C and kept warm with stirring. After stirring for 5 hours, the flask was taken out of the oil bath and allowed to cool to room temperature. Quenching was carried out by sequentially pouring water (4.9 ml) and 5 wt% NaHCO3 aq. (9.9 ml) into the cooled mass while stirring, and the aqueous layer was removed from the resulting mass by liquid separation. The separated mass was washed with water, dried over magnesium sulfate, filtered, and then concentrated to dryness using a rotary evaporator to obtain a crude product of compound 54. The obtained crude product was purified by silica gel column (developing solvent: heptane / ethyl acetate = 10 / 1 (v / v)) to obtain 1.09 g of compound 54 as a red-violet oil. The NMR spectrum of the obtained compound 54 was analyzed. The results are as follows. 1 H-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]

Chemical Structure

[0573] In a 100 mL four-necked flask, add compound 54 (0.400 g, 0.301 mmol), compound 48 (0.237 g, 0.752 mmol), p-TsOH·H2O (0.200 g, 1.05 mmol), EtOH (26.0 g), and toluene (10.8 g). Place it in an oil bath heated to 65 °C and keep it warm. After stirring for 2 hours, remove it from the oil bath and let it cool to room temperature. Collect the precipitated solid by filtration, wash it with methanol, ethanol, and heptane to obtain the crude product. The obtained crude product was purified by recycled GPC (developing solvent: chloroform = 100 wt%) to obtain 0.359 g of compound N-9 as a black solid. For the obtained compound N-9, the NMR spectrum 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]

Chemical Structure

[0576] A 100 mL four-necked flask was charged with compound 54 (0.300 g, 0.23 mmol), compound 10 (0.165 g, 0.68 mmol), p-TsOH·H2O (0.129 g, 0.68 mmol), EtOH (3.4 ml), toluene (6.9 ml), and MgSO4 (0.150 g). After purging with nitrogen, the mixture was heated to 65 °C and stirred while maintaining the temperature. After stirring for 3 hours, the mixture was removed from the oil bath and allowed to cool to room temperature. After removing MgSO4 by filtration, the precipitate was washed with chloroform while dissolving it. The solution obtained by the evaporator was concentrated, and then washed with methanol by Kiriyama filtration to obtain a crude product. The obtained crude product was purified by recycled 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 the optical absorption edge wavelength of the thin film> Compound N-1, compound N-2, compound N-3, compound N-4, compound N-5, compound N-6, compound N-7, compound N-9, compound N-10, compound N-11, compound N-12, compound N-13, and compound N-14 were each added to orthodichlorobenzene so that the concentration became 1.0% by mass. In addition, compound -8 was added to 1,2,4-trimethylbenzene so that the concentration became 1.0% by mass. Heating and stirring were carried out 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 was 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. It was dried under the conditions of 70 °C and 5 minutes in air to obtain a thin film for UV-Vis spectrum measurement. Using this thin film, the optical absorption edge wavelength (λth) was measured. The details of the measurement method are as described above.

[0578] Compound N-1: 1567 nm Compound N-2: 1804 nm Compound N-3: 1620 nm Compound N-4: 1480 nm Compound N-5: 1546 nm Compound N-6: 1437 nm Compound N-7: 1630 nm Compound N-8: 1502 nm 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 with a wavelength of 1400 nm or more, which is particularly long in the SWIR region.

[0580] <Measurement of the maximum optical absorption wavelength of the 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 so that the concentration became 0.00125% by mass to obtain a solution for UV-Vis spectrum measurement. In addition, Compound N-8 was added to 1,2,4-trimethylbenzene so that the concentration became 0.00125% by mass to obtain a solution for UV-Vis spectrum measurement. Using this solution, the maximum optical absorption wavelength (λmax) was measured. The 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 the optical absorption edge wavelength of the thin film and the maximum optical absorption wavelength of the solution> 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, the difference between the optical absorption edge wavelength of the thin film and the maximum optical absorption wavelength of the solution was calculated.

[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, in Compounds N-1 to N-10, the difference between the light absorption end wavelength of the thin film and the maximum light absorption wavelength of the solution was large. That is, Compounds N-1 to N-10 existed in a single-molecule state in solution, but when in the form of a thin film, the compounds associated with each other and became more likely to absorb light with a longer wavelength.

[0585] <Distance (d from Group D to Group A1 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 ) from the carbon atom (C1) that forms a single bond with Group L1 of Group D to the carbon atom (C2) that forms a single bond with Group A1 and Group L1 was calculated.

[0586] d C1-C2 was calculated by performing structure optimization in the ground state using the density functional method at the B3LYP level with the quantum chemistry calculation program Gaussian 03 and using 6-31g* as the basis function. For the obtained optimized structure in the ground state, d C1-C2 was calculated using GaussView 6. In addition, when calculating d C1-C2 , for the alkyl groups contained in each compound, the propyl group (-CH2-CH2-CH3) was taken as an example for calculation as a representative. The calculated values were almost the same for the compound before changing the alkyl group to a propyl group and the compound after changing the alkyl group to a propyl group.

[0587]

Table 1

[0588]

Table 2

[0589]

Table 3

[0590]

Table 4

[0591]

Table 5

[0592] <Preparation of Ink> (Preparation of Ink (I-1)) The following components were mixed and stirred at room temperature for 12 hours. The obtained mixture was filtered using a filter to obtain Ink (I-1). · p-type semiconductor material: Polymer compound P-19... 0.8 mass% · n-type semiconductor material: Compound N-1... 0.56 mass% · n-type semiconductor material: C60PCBM... 0.24 mass% · Solvent: Chloroform / 1-chloronaphthalene = 98 wt% / 2 wt%... The remaining amount to make 100 mass% of the whole ink

[0593] C60PCBM ([6,6]-Phenyl C61 butyric acid methyl ester) was obtained from the market 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 the preparation of Ink (I-1), except that Compound N-1 was changed to Compound N-11.

[0595] <Manufacture of Photovoltaic Conversion Element and Its Encapsulant> A glass substrate on which a thin film (anode) of ITO with a thickness of 45 nm was formed by sputtering was prepared, and this glass substrate was subjected to ozone UV treatment as a surface treatment.

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

[0597] Next, Ink (I-1) was coated on the electron transport layer by spin coating to form a coating film. Then, the coating film was heat-treated and dried for 5 minutes using a hot plate heated to 70 °C under air (pre-bake process). Subsequently, the coating film was heat-treated on a hot plate at 100 °C for 10 minutes under a nitrogen atmosphere (post-bake process) to form an active layer. The thickness of the formed active layer was about 350 nm.

[0598] Next, a molybdenum oxide (MoO3) layer was formed on the formed active layer to a thickness of about 30 nm to serve as a hole transport layer.

[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 as a sealing material was applied to the outer periphery of a glass substrate as a sealing substrate. After bonding the glass substrate as a sealing substrate to the center of a glass substrate as a support substrate, the photoelectric conversion element was sealed in the gap between the support substrate and the sealing substrate by irradiating UV light to obtain a sealed body of the photoelectric conversion element. The planar shape when viewed from the thickness direction of the photoelectric conversion element sealed in the gap between the support substrate and the sealing substrate was a square of 2 mm × 2 mm. The obtained sealed body was designated as Sample 1.

[0601] [Evaluation of Photoelectric Conversion Element] While applying a reverse bias voltage of 3 V to the obtained photoelectric conversion element, using a spectroscopic sensitivity measuring device (manufactured by Spectro Instruments Co., Ltd., product name: CEP-25SC type), monochromatic light of 1500 nm (photon number: 1×10 14) was irradiated onto the photoelectric conversion element, the generated current value was measured, and a photodiode drive test was carried out by a known method. In this test, when the photoelectric conversion effect was confirmed, it was judged as Y, and when there was no photoelectric conversion, it was judged as N.

[0602]

Table 6

[0603] As described above, it was found that according to the photoelectric conversion element using the compound of the present disclosure as the n-type semiconductor material, it is possible to perform photoelectric conversion up to a longer wavelength compared to the photoelectric conversion element using the conventional n-type semiconductor material.

Explanation of symbols

[0604] 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. Represented by the following formula (1): A compound in which, in formula (1), 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. 【Chemistry 1】 (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 Ｄ１ At least one of 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 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 condensed ring constituting the aromatic group in L1 has an sp2 carbon, and L1 is a monovalent side chain R Ｌ１ At least one of 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 are each independently Halogen atoms, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an optionally substituted aryl group, an alkyloxy group which may have a substituent; a cycloalkyloxy group which may be substituted; an optionally substituted aryloxy group, an optionally substituted alkylthio group, a cycloalkylthio group which may be substituted; an optionally substituted arylthio group; a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted carbonyl group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; a substituted sulfonyl group which may have a substituent; a substituted oxysulfonyl group which may have a substituent; an alkenyl group which may have a substituent; a cycloalkenyl group which may have a substituent, an optionally substituted alkynyl group, a cycloalkynyl group which may be substituted, a cyano group, or represents a nitro group, L2 is a divalent aromatic group, m is an integer from 1 to 4, n is an integer from 0 to 4, A1 and A2 each independently represent a group represented by the following formula (A-1). 【Chemistry 2】 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. In the formula (1), The compound according to claim 1, wherein D is any of groups represented by the following formulas (D-1) to (D-4): 【Chemistry 3】 In formulas (D-1) to (D-4), X is any of the groups represented by the following formulas (X-1) to (X-6). 【Chemistry 4】 In formula (D-3), formula (D-4), and formula (X-1) to formula (X-6), R Ｄ２ The definitions of are, independently, Hydrogen atom, Halogen atoms, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an optionally substituted aryl group, an alkyloxy group which may have a substituent; a cycloalkyloxy group which may be substituted; an optionally substituted aryloxy group, an optionally substituted alkylthio group, a cycloalkylthio group which may be substituted; an optionally substituted arylthio group; a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted carbonyl group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; a substituted sulfonyl group which may have a substituent; a substituted oxysulfonyl group which may have a substituent; an alkenyl group which may have a substituent; a cycloalkenyl group which may have a substituent, an optionally substituted alkynyl group, a cycloalkynyl group which may be substituted, a cyano group, or Represents 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 the formula (1), L1 is each independently any of groups represented by the following formulas (L1-1) to (L1-7): 【Chemistry 5】 (In formulas (L1-1) to (L1-7), R Ｌ１１ are each independently Hydrogen atom, Halogen atoms, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an optionally substituted aryl group, an alkyloxy group which may have a substituent; a cycloalkyloxy group which may be substituted; an optionally substituted aryloxy group, an optionally substituted alkylthio group, a cycloalkylthio group which may be substituted; an optionally substituted arylthio group; a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted carbonyl group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; a substituted sulfonyl group which may have a substituent; a substituted oxysulfonyl group which may have a substituent; an alkenyl group which may have a substituent; a cycloalkenyl group which may have a substituent, an optionally substituted alkynyl group, a cycloalkynyl group which may be substituted, a cyano group, or represents 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 the formula (1), L2 is each independently any of groups represented by the following formulas (L2-1) to (L2-9): 【Chemistry 6】 (In formula (L2-1) to formula (L2-9), a plurality of R Ｌ２ are each independently Hydrogen atom, Halogen atoms, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an optionally substituted aryl group, an alkyloxy group which may have a substituent; a cycloalkyloxy group which may be substituted; an optionally substituted aryloxy group, an optionally substituted alkylthio group, a cycloalkylthio group which may be substituted; an optionally substituted arylthio group; a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted carbonyl group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; a substituted sulfonyl group which may have a substituent; a substituted oxysulfonyl group which may have a substituent; an alkenyl group which may have a substituent; a cycloalkenyl group which may have a substituent, an optionally substituted alkynyl group, a cycloalkynyl group which may be substituted, a cyano group, or represents a nitro group.

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

6. In the formula (1), A1 and A2 are each independently any of groups represented by the following formulas (a-1) to (a-8): 【Chemistry 7】 (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): 【Chemistry 8】 (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): 【Chemistry 9】 In formulas (Z-1) to (Z-7), Each R is independently Hydrogen atom, Halogen atoms, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an optionally substituted aryl group, an alkyloxy group which may have a substituent; a cycloalkyloxy group which may be substituted; an optionally substituted aryloxy group, an optionally substituted alkylthio group, a cycloalkylthio group which may be substituted; an optionally substituted arylthio group; a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted carbonyl group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; a substituted sulfonyl group which may have a substituent; a substituted oxysulfonyl group which may have a substituent; an alkenyl group which may have a substituent; a cycloalkenyl group which may have a substituent, an optionally substituted alkynyl group, a cycloalkynyl group which may be substituted, a cyano group, or represents 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. In formula (4), Ar ５ represents a divalent aromatic heterocyclic group.

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

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

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.

Images