Compound, composition, film, photoelectric conversion element and CMOS image sensor

Abstract

Provided are: a compound which enables both the elongation of absorption wavelengths and the achievement of high solubility in an A-D-A type non-fullerene acceptor material; and a composition, a film, a photoelectric conversion element, and a CMOS image sensor each obtained using the compound. This compound is represented by general formula (1).　(1): A-D-A In general formula (1), the A moieties are each independently a specific electron-withdrawing group, and D is an electron-donating group comprising four or more rings connected along the main-chain direction of the molecule and includes a structure represented by general formula (2). In general formula (2), Q1 represents an oxygen atom, a sulfur atom, etc., and the R1 moieties each independently represent a hydrogen atom, an alkyl group, etc. and at least two of the R1 moieties are not hydrogen atoms.

Description

Compound, composition, film, photoelectric conversion element, and CMOS image sensor

[0001] The present invention relates to a compound, composition, film, photoelectric conversion element, and CMOS image sensor suitable as a semiconductor material for use in a photoelectric conversion element. This application claims priority based on Japanese Patent Application No. 2023-221213 filed on December 27, 2023, and Japanese Patent Application No. 2024-152134 filed on September 4, 2024, the contents of which are incorporated herein by reference.

[0002] CMOS image sensors equipped with photoelectric conversion elements are used as imaging elements in digital cameras and smartphones, for example. CMOS image sensors are divided into inorganic and organic types, with inorganic CMOS image sensors using silicon photodiodes being the most commonly used. On the other hand, organic CMOS image sensors utilize the high light absorption capacity of organic thin films to achieve high resolution and a wide dynamic range while also incorporating a global shutter that minimizes image distortion. Thus, organic CMOS image sensors are believed to be able to solve the problem of achieving both a high dynamic range and a global shutter, which is difficult with inorganic CMOS image sensors. Therefore, materials suitable for organic CMOS image sensors are in demand.

[0003] Furthermore, in photoelectric conversion elements (hereinafter also referred to as "inorganic photoelectric conversion elements") provided in inorganic CMOS image sensors, inexpensive silicon semiconductors are generally used for photoresponse up to an absorption wavelength of 1000 nm, but extremely expensive indium gallium arsenide (InGaAs) semiconductors are used for absorption wavelengths of 1000 nm or more. Therefore, there is a demand for semiconductor materials that are inexpensive and can be used in the long wavelength region, and organic semiconductor materials (hereinafter also referred to as "organic semiconductor materials") are attracting attention as candidates for such materials.

[0004] In photoelectric conversion elements (hereinafter also referred to as "organic photoelectric conversion elements") provided in organic CMOS image sensors, the photoelectric conversion capacity and absorption wavelength range can be controlled by molecular design of the p-type and n-type semiconductor materials used in the organic thin film (photoelectric conversion layer) that constitutes the photoelectric conversion element. In recent years, high photoconversion capacity has been reported in elements using non-fullerene acceptors as n-type semiconductor materials. In photoelectric conversion elements using non-fullerene acceptors, the role of controlling the absorption wavelength range is primarily played by the n-type semiconductor material. Known n-type semiconductor materials (light-absorbing and electron-transporting materials) include compounds having an electron acceptor (A) moiety and an electron donor (D) moiety, known as A-D-A type compounds (hereinafter also referred to as "A-D-A type non-fullerene acceptor materials"). The absorption wavelength of A-D-A type compounds can be designed by narrowing the HOMO-LUMO gap through selection of the electron-withdrawing property of the A moiety and the electron-donating property of the D moiety.

[0005] The AD-A type compounds include cyclopentadithiophene as the central donor (D) moiety and a thiophene ring (D １ ), (D ２ ) with part D sandwiched between them, A-D １ -DD ２ -A type compounds are known. For example, Non-Patent Document 1 discloses a compound represented by the following formula (a), which is an A-D'-D-D'-A type compound, a compound represented by the following formula (b), which is an A-D'-D-D"-A type compound, and a compound represented by the following formula (c), which is an A-D"-D-D"-A type compound. Here, D' represents a thiophene ring substituted with an alkoxy group, and D" represents a thiophene ring substituted with an alkyl group. Non-Patent Document 1 states that the compound represented by the following formula (a) is the most capable of achieving a longer absorption wavelength. The compound represented by the following formula (a) is a compound in which the alkyl group bonded to the thiophene ring in the D" portion of the compound represented by the following formula (b) or (c) is replaced with an alkoxy group, which is a strong electron-donating group, to form the D' portion.

[0006]

[0007] Jaewon Lee and 12 others, "ACS Energy Lett.", 2019, Vol. 4, pp. 1401-1409

[0008] In order to extend the absorption wavelength of an A-D-A non-fullerene acceptor material, it is necessary to strengthen the electron-donating and electron-withdrawing properties and expand the π-conjugated system. However, expanding the π-conjugated system strengthens intermolecular interactions, reducing the solubility of the material, leading to issues with the purification process during material production and ink stability during coating and film formation. In particular, when the thiophene ring is substituted with a substituent such as a linear alkyl group or a linear alkoxy group, the solubility tends to decrease as the chain length of the substituent increases due to a zipper effect. In the compound described in Non-Patent Document 1, the thiophene ring is substituted with an alkyl group or an alkoxy group branched at the 2-position to suppress the decrease in solubility, but this is not necessarily sufficient to further extend the absorption wavelength, and a method for achieving better solubility is needed.

[0009] An object of the present invention is to provide an A-D-A type non-fullerene acceptor material that can achieve both a longer absorption wavelength and high solubility, and to provide a composition, a film, a photoelectric conversion element, and a CMOS image sensor that use this compound.

[0010] In view of the above-mentioned problems, the present inventors have investigated A-D-A type non-fullerene acceptor materials for compounds that can achieve both a longer absorption wavelength and high solubility. Specifically, they investigated the π-conjugated units in the D moiety and their substituents. As a result, they found that by branching the alkoxy group at the 1-position of an alkoxy-substituted thiophene ring, which is a strong electron-donating unit, it is possible to achieve both a longer absorption wavelength and high solubility, thereby completing the present invention.

[0011] That is, the present invention has the following aspects: [1] A compound represented by the following general formula (1): A-D-A (1) In general formula (1), each A is independently a group represented by any one of the following general formulas (3a), (3c) to (3y), and D is an electron-donating group having four or more rings linked in the main chain direction of the molecule, and including a structure represented by the following general formula (2).

[0012]

[0013] In general formulas (3a), (3c) to (3y), Z １ ~Z ７ are each independently an oxygen atom, a sulfur atom, or a dicyanomethylene group, and R ３ are each independently a hydrogen atom or an alkyl group, and R ４ are each independently a methyl group or a trifluoromethyl group, and X １ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a cyano group; Ar is an aryl group; and V is each independently C-X ２ or a nitrogen atom, and Q ２ are each independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or CR ５ =CR ５ and Q ３ is a sulfur atom, a carbon atom substituted with an alkyl group or an aryl group, a nitrogen atom substituted with an alkyl group or an aryl group, a silicon atom substituted with an alkyl group or an aryl group, or a germanium atom substituted with an alkyl group or an aryl group; ２ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a cyano group, and R ５ are each independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group (provided that in general formula (3o), Z ４ and Z ５ one of which is an oxygen atom and the other is a dicyanomethylene group, and V is C-X ２ and X １ and X ２ are all hydrogen atoms.

[0014]

[0015] In general formula (2), Q １ is an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or CR ２ =CR ２ and R １ are each independently a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and R １ At least two of the R groups are alkyl groups, aryl groups, or heteroaryl groups. However, when at least two of the R groups are alkyl groups, at least one of the alkyl groups has two or more carbon atoms. １ may form a ring structure. ２ Each of Q is independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group. １ The ring structure containing the following may further form a ring structure with an adjacent structure.

[0016] [2] The compound of [1] above, wherein D in the general formula (1) contains two structures represented by the general formula (2). [3] The compound of [1] above, wherein the structure represented by the general formula (2) is a structure represented by the following general formula (2'):

[0017]

[0018] In general formula (2'), Q １ is an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or CR ２ =CR ２ and R １ are each independently an alkyl group, an aryl group, or a heteroaryl group, provided that R １ When all of R are alkyl groups, at least one of the alkyl groups has two or more carbon atoms. １ may form a ring structure. ２ are each independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group.

[0019] [4] Q in the general formula (2') １ is a sulfur atom, and R １ [5] The compound of the above [3], wherein Q in the above general formula (2) is an alkyl group. １ is an oxygen atom or a sulfur atom, and R １are each independently a hydrogen atom or an alkyl group, and R １ [6] The compound according to any one of [1] to [4] above, wherein at least two of Z in the general formulae (3a), (3c) to (3y) are alkyl groups. １ is a dicyanomethylene group, and Z ２ is an oxygen atom, and Z ３ is a sulfur atom or a dicyanomethylene group, and Z ４ and Z ５ one of which is an oxygen atom and the other is a dicyanomethylene group, and Z ６ and Z ７ [7] The compound according to any one of [1] to [6] above, wherein D in the general formula (1) is a group represented by any one of the following general formulas (4) to (6):

[0020]

[0021] In the general formulas (4) to (6), W is C—(R ６ ) ２ , Si—(R ６ ) ２ , Ge-(R ６ ) ２ , N-R ６ , O-CR ６ , or CR ６ -O and R ６ are each independently an alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group, E, J, K, and L are each independently an aryl group, a cyclopentadienyl group, or a heteroaryl group having 1 to 5 rings and containing an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, a germanium atom, or a selenium atom, G is a heteroaryl ring containing a nitrogen atom, s is a number from 0 to 1, and t is a number from 0 to 3. However, at least one of J and E in general formula (4) contains a structure represented by general formula (2), at least one of J, K, and L in general formula (5) contains a structure represented by general formula (2), and at least one of J and K in general formula (6) contains a structure represented by general formula (2).

[0022] [8] In the general formulas (4) to (6), -(E)ｔ [9] The compound of any one of [1] to [8] above, wherein - is an optionally substituted thiophene, furan, selenophene, thienothiophene, bithiophene, or terthiophene, or an optionally substituted aryl or heteroaryl group having 3 to 5 fused rings selected from benzene, thiophene, furan, selenophene, cyclopentadiene, silole, and pyrrole, J and K each independently represent an optionally substituted phenyl group, furan, thiophene, selenophene, or thienothiophene, L is an optionally substituted phenyl group, naphthyl group, thiophene, thienothiophene, or a heteroaryl group having 1 to 3 fused rings selected from benzene, thiophene, furan, selenophene, cyclopentadiene, silole, and pyrrole, and G is thiadiazole, selenadiazole, triazole, benzoquinoxaline, or diphenylpyrazine.

[0023]

[0024] In the general formula (7), each A is independently a group represented by any one of the general formulas (3a), (3c) to (3y), and Y １ ~Y ４ are each independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group; M is a carbon atom substituted with an alkyl group or an aryl group, a nitrogen atom substituted with an alkyl group or an aryl group, a silicon atom substituted with an alkyl group or an aryl group, or a germanium atom substituted with an alkyl group or an aryl group; Q １ are each independently an oxygen atom, a sulfur atom, a selenium atom, or N—R ３ or CR ６ =CR ６ and Ar ２ are each independently an aryl group or a heteroaryl group, or Ar ２ and two Ar ２ The total number of rings is 0 to 3, and a and b each represent 1 or 2.

[10] The compound according to any one of [1] to [9] above, which is represented by the following general formula (4a):

[0025]

[0026] In the general formula (4a), each A is independently a group represented by any one of the general formulas (3a), (3c) to (3y), and Y １ ~Y ４ are each independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group; Y １ ~Y ４ at least one of the groups is an alkoxy group branched at the 1-position, and M is a carbon atom substituted with an alkyl group or an aryl group, a nitrogen atom substituted with an alkyl group or an aryl group, a silicon atom substituted with an alkyl group or an aryl group, or a germanium atom substituted with an alkyl group or an aryl group.

[0027]

[11] The compound of

[10] above, wherein M in the general formula (4a) is a carbon atom substituted with an alkyl group or an aryl group, a nitrogen atom substituted with an alkyl group or an aryl group, or a silicon atom substituted with an alkyl group or an aryl group.

[12] Y in the general formula (4a) １ is an alkoxy group branched at the 1-position, and Y ２ and Y ４ one of which is a hydrogen atom and the other is an alkyl group, an alkoxy group, or an ester group; Y ３

[13] The compound of the above

[10] or

[11] , wherein Y in the general formula (4a) is a hydrogen atom. １ and Y ２ are each independently an alkoxy group branched at the 1-position, and Y ３ and Y ４

[14] The compound of any one of the above

[10] to

[12] , wherein each A in the general formula (4a) is independently a group represented by any one of the general formulas (3m), (3n), (3o), (3s), (3v), (3w), (3x), and (3y), and Y １ and Y ２ are identical and are alkoxy groups branched at the 1-position, and Y ３ and Y ４

[15] The compound of any one of the above

[10] to

[13] , wherein Z in the general formulae (3m), (3n), (3o), (3s), (3v), (3w), (3x) and (3y) is a hydrogen atom, and M is a carbon atom substituted with an alkyl group or an aryl group, or a nitrogen atom substituted with an alkyl group or an aryl group. ４ and Z ５ one of which is an oxygen atom and the other is a dicyanomethylene group, and X １ is a fluorine atom, a chlorine atom or a cyano group, and V is C-X ２ or a nitrogen atom, and X ２ is a hydrogen atom.

[16] A composition containing any of the compounds of [1] to

[15] .

[17] A film containing any of the compounds of [1] to

[15] .

[18] A photoelectric conversion element comprising the film of

[17] .

[19] A CMOS image sensor comprising the photoelectric conversion element of

[18] .

[0028] According to the present invention, it is possible to provide an A-D-A type non-fullerene acceptor material that can achieve both a longer absorption wavelength and high solubility, as well as a composition, a film, a photoelectric conversion element, and a CMOS image sensor that use this compound.

[0029] 1 is a cross-sectional view schematically illustrating an example of an embodiment of a photoelectric conversion element of the present invention.

[0030] The present invention will be described in further detail below by showing preferred embodiments of the invention. However, the following description is merely an example of an embodiment of the present invention, and the present invention is not limited to the following description as long as it does not deviate from the gist of the invention. In this specification, the symbol "to" indicating a range of values ​​means that the values ​​before and after it are included as the lower and upper limits. In addition, in the present invention, the wavy line in the general formula indicates the bonding position to the adjacent group.

[0031] [Compound] The compound of the present invention is a compound represented by the following general formula (1) (hereinafter also referred to as "compound (1)"; the same applies hereinafter): A-D-A ... (1) In general formula (1), each A is independently a group represented by any one of the following general formulas (3a), (3c) to (3y), and D is an electron-donating group having four or more rings linked in the main chain direction of the molecule, and includes a structure represented by the following general formula (2).

[0032]

[0033] In general formulas (3a), (3c) to (3y), Z １ ~Z ７ are each independently an oxygen atom, a sulfur atom, or a dicyanomethylene group, and R ３ are each independently a hydrogen atom or an alkyl group, and R ４ are each independently a methyl group or a trifluoromethyl group, and X １ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a cyano group; Ar is an aryl group; and V is each independently C-X ２ or a nitrogen atom, and Q ２ are each independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or CR ５ =CR ５ and Q ３ is a sulfur atom, a carbon atom substituted with an alkyl group or an aryl group, a nitrogen atom substituted with an alkyl group or an aryl group, a silicon atom substituted with an alkyl group or an aryl group, or a germanium atom substituted with an alkyl group or an aryl group; ２ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a cyano group, and R ５ are each independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group (provided that in general formula (3o), Z ４ and Z ５ one of which is an oxygen atom and the other is a dicyanomethylene group, and V is C-X ２ and X １ and X ２ are all hydrogen atoms.

[0034]

[0035] In general formula (2), Q １ is an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or CR ２ =CR ２ and R １ are each independently a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and R １ At least two of the R groups are alkyl groups, aryl groups, or heteroaryl groups. However, when at least two of the R groups are alkyl groups, at least one of the alkyl groups has two or more carbon atoms. １ may form a ring structure. ２ are each independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group. １ The ring structure containing the following may further form a ring structure with an adjacent structure.

[0036] In the compound of the present invention, the D portion of the ADA type non-fullerene acceptor material contains the structure represented by the general formula (2), and therefore, both the longer absorption wavelength and high solubility can be achieved.

[0037] The reason why the compound of the present invention can achieve both a longer absorption wavelength and high solubility is not clear, but is presumed to be as follows. The compound of the present invention includes a thiophene ring substituted with an alkoxy group branched at the 1-position (hereinafter also referred to as a "1-branched alkoxy group-substituted thiophene ring") in the D portion of an ADA non-fullerene acceptor material. The alkoxy group in the 1-branched alkoxy group-substituted thiophene ring branches at a position one atom closer to the π-conjugated skeleton than the alkoxy group branched at the 2-position of the prior art. Therefore, a bulky branch can be arranged at a position closer to the π-conjugated skeleton than in conventional ADA non-fullerene acceptor materials, making it possible to maintain an appropriate intermolecular distance. As a result, it is presumed that the compound of the present invention can exhibit higher solubility than conventional ADA non-fullerene acceptor materials. This effect is particularly evident when at least one of the carbon chains in the 1-branched alkoxy group has a chain structure of two or more carbon atoms. In this case, the crystallinity of the material is not increased, defects are less likely to occur during thin film formation in devices, and device characteristics can be improved. Moreover, the 1-position branched alkoxy group-substituted thiophene ring is a strong electron-donating group. Therefore, it is believed that the compound of the present invention can achieve both a longer absorption wavelength and high solubility.

[0038] In the general formula (1), each A is independently a group represented by any one of the general formulas (3a), (3c) to (3y). The A's may be the same or different, but are preferably the same.

[0039] In the general formulas (3a), (3c) to (3y), Z １ ~Z ７ are each independently an oxygen atom, a sulfur atom, or a dicyanomethylene group. １ ~Z ７ is an oxygen atom, a sulfur atom, or a dicyanomethylene group, it is believed that Z in the general formula (3c), (3l), or (3t) can be an electron-withdrawing group in the acceptor portion. １ is preferably a dicyanomethylene group. ２is preferably an oxygen atom, and Z ３ is preferably a sulfur atom or a dicyanomethylene group. ４ and Z ５ It is preferable that one of Z is an oxygen atom and the other is a dicyanomethylene group. ５ is preferably an oxygen atom or a dicyanomethylene group. ６ and Z ７ is preferably an oxygen atom.

[0040] In the general formulas (3a), (3c) to (3y), R ３ Each R is independently a hydrogen atom or an alkyl group. ４ Each R is independently a methyl group or a trifluoromethyl group. ３ The number of carbon atoms in the alkyl group of R is preferably small in terms of the conductivity of the material. ３ The number of carbon atoms in the alkyl group of R is preferably 30 or less, more preferably 20 or less, even more preferably 15 or less, and particularly preferably 10 or less. ３ The number of carbon atoms in the alkyl group of R is preferably 1 or more, and more preferably 2 or more. The above upper and lower limits can be combined arbitrarily. For example, it may be 1 to 30, 1 to 20, 1 to 15, 1 to 10, or 2 to 10. ３ The alkyl group of R may be chain-like or cyclic. When the alkyl group is chain-like, it may be linear or branched. ３ may be the same or different, but are preferably the same. ４ may be the same or different, but are preferably the same.

[0041] In the general formulas (3a), (3c) to (3y), X １are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a cyano group. In the case of the general formulae (3m), (3n), (3o), (3s), (3v), (3w), (3x), and (3y), X １ are each preferably a fluorine atom, a chlorine atom or a cyano group. １ may be the same or different, but are preferably the same.

[0042] Ar is an aryl group. The number of carbon atoms in the aryl group is preferably small in terms of the conductivity of the material. Therefore, the number of carbon atoms in the aryl group is preferably 18 or less, more preferably 12 or less, even more preferably 10 or less, and particularly preferably 6. The lower limit of the number of carbon atoms in the aryl group is 6. The aryl group may or may not have a substituent. That is, the aryl group is an unsubstituted or substituted aryl group. Examples of the substituent include an alkyl group, an alkoxy group, an ester group, a hydroxy group, an amino group, a cyano group, a fluorine atom, and a chlorine atom. Ar in the general formulas (3e) and (3r) is preferably a phenyl group.

[0043] In the general formulas (3a), (3c) to (3y), each V independently represents C-X ２ or a nitrogen atom. ２ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a cyano group. That is, V is a carbon atom, a carbon atom in which a hydrogen atom bonded to the carbon atom is substituted with a fluorine atom, a chlorine atom, a bromine atom, or a cyano group, or a nitrogen atom. ２ may be the same or different, but are preferably the same. ２ is preferably a hydrogen atom. ２ is a hydrogen atom ２ is also referred to as an "unsubstituted carbon atom". ２ is a fluorine atom, a chlorine atom, a bromine atom or a cyano group; ２ is also referred to as a "substituted carbon atom." V in the general formulae (3o) and (3x) is C-X ２or a nitrogen atom, and X ２ is preferably a hydrogen atom, that is, V is preferably an unsubstituted carbon atom or nitrogen atom, more preferably an unsubstituted carbon atom. ２ In the general formulae (3o), (3p), (3q), (3s), (3u), (3x) and (3y), X is preferably a nitrogen atom, and V is preferably a nitrogen atom. １ and X ２ At least one of the groups is preferably a fluorine atom, a chlorine atom, a bromine atom or a cyano group.

[0044] In the general formulas (3a), (3c) to (3y), Q ２ are each independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or CR ５ =CR ５ It is. ５ R are each independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group. ５ The number of carbon atoms in the alkyl group of R is preferably small in terms of the conductivity of the material. ５ The number of carbon atoms in the alkyl group of R is preferably 30 or less, more preferably 20 or less, even more preferably 15 or less, and particularly preferably 10 or less. ５ The number of carbon atoms in the alkyl group of R is preferably 2 or more, more preferably 4 or more, and even more preferably 6 or more. ５ The alkyl group may be chain-like or cyclic. When the alkyl group is chain-like, it may be linear or branched.

[0045] R ５ The number of carbon atoms in the alkoxy group of R is preferably small in terms of the conductivity of the material. ５ The number of carbon atoms in the alkoxy group of R is preferably 30 or less, more preferably 20 or less, even more preferably 15 or less, and particularly preferably 10 or less. ５The number of carbon atoms in the alkoxy group is preferably 2 or more, more preferably 4 or more, and even more preferably 6 or more. The above upper and lower limits can be combined arbitrarily. For example, it may be 2 to 30, 2 to 20, 2 to 15, 4 to 15, 6 to 15, or 6 to 10. An alkoxy group has a structure in which an alkyl group is bonded to an oxygen atom, and the alkyl group bonded to the oxygen atom may be either linear or cyclic. When the alkyl group bonded to the oxygen atom is linear, it may be either linear or branched. Q in the general formulae (3c), (3l), and (3t) ２ is preferably a sulfur atom.

[0046] R ５ The ester group may be a monovalent group having an ester bond. Specific examples include groups represented by the following general formula (i): —COO—R ７ ...(i) In general formula (i), R ７ is an alkyl group or an aryl group. ７ The alkyl group of R ５ Examples of the alkyl group include those exemplified above in the description of R ７ The alkyl group may be chain-like or cyclic. When the alkyl group is chain-like, it may be linear or branched.

[0047] In the general formulas (3a), (3c) to (3y), Q ３ is a sulfur atom, a carbon atom substituted with an alkyl group or an aryl group, a nitrogen atom substituted with an alkyl group or an aryl group, a silicon atom substituted with an alkyl group or an aryl group, or a germanium atom substituted with an alkyl group or an aryl group. A carbon atom substituted with an alkyl group or an aryl group is represented by the following general formula (ii). A nitrogen atom substituted with an alkyl group or an aryl group is represented by the following general formula (iii). A silicon atom substituted with an alkyl group or an aryl group is represented by the following general formula (iv). A germanium atom substituted with an alkyl group or an aryl group is represented by the following general formula (v).

[0048]

[0049] In general formulas (ii) to (v), R ８ ~R １４ are each independently an alkyl group or an aryl group. ８ ~R １４ The alkyl group of R ５ Examples of the alkyl group include those exemplified above in the description of R ８ ~R １４ Examples of the aryl group of R include the aryl groups exemplified above in the description of Ar. ８ ~R １４ The aryl group in R may or may not have a substituent. ８ ~R １４ The aryl group may be an unsubstituted or substituted aryl group, and examples of the substituent include an alkyl group, an alkoxy group, an ester group, a hydroxy group, and an amino group.

[0050] In terms of ease of synthesis of compound (1), Q ３ In terms of synthesis cost, it is preferable that the two alkyl groups or aryl groups carried by the carbon atom, silicon atom, and germanium atom in the general formula (3t) are the same. ３ is preferably a sulfur atom, a carbon atom substituted with an alkyl group or an aryl group, a nitrogen atom substituted with an alkyl group or an aryl group, or a silicon atom substituted with an alkyl group or an aryl group, more preferably a sulfur atom or a carbon atom substituted with an alkyl group or an aryl group, and even more preferably a sulfur atom. ３ is preferably a carbon atom substituted with an alkyl group or an aryl group, a nitrogen atom substituted with an alkyl group or an aryl group, a silicon atom substituted with an alkyl group or an aryl group, or a germanium atom substituted with an alkyl group or an aryl group.

[0051] A is more preferably a group represented by any one of the general formulae (3m), (3n), (3o), (3s), (3v), (3w), (3x), and (3y). In particular, Z in the general formulae (3m), (3n), (3o), (3s), (3v), (3w), (3x), and (3y) is ４ and Z ５ one of which is an oxygen atom and the other is a dicyanomethylene group, and X １ is a fluorine atom, a chlorine atom or a cyano group, and V is C-X ２ or a nitrogen atom, and X ２ is preferably a hydrogen atom. Among them, A is more preferably a group represented by the general formula (3o), (3s), (3x) or (3y), and Z ４ and Z ５ one of which is an oxygen atom and the other is a dicyanomethylene group, and X １ are each independently a fluorine atom, a chlorine atom or a cyano group, and V is C-X ２ or a nitrogen atom, and X ２ In the case of the general formula (3o) or (3x), Z is more preferably a hydrogen atom. ４ and Z ５ one of which is an oxygen atom and the other is a dicyanomethylene group, and X １ is a chlorine atom or a cyano group, and V is C-X ２ and X ２ is more preferably a hydrogen atom, and X １ It is particularly preferred that Z is a cyano group and V is C—H. ４ and Z ５ one of which is an oxygen atom and the other is a dicyanomethylene group, and X １ More preferably, X is a chlorine atom or a cyano group, and V is a nitrogen atom. １ is particularly preferably a cyano group.

[0052] In the general formula (1), D is an electron-donating group having four or more rings linked in the main chain direction of the molecule, and includes a structure represented by the general formula (2). D is preferably an electron-donating group having four or more rings linked in the main chain direction of the molecule. When the number of rings linked in the main chain direction of the molecule is four or more, the π-conjugated system is sufficiently extended, and the absorption wavelength can be sufficiently extended. Furthermore, when the number of rings linked in the main chain direction of the molecule is three or less, the intermolecular interactions are relatively weak, so the solubility of the material does not decrease, and it is believed that the problem of achieving both long absorption wavelengths and high solubility does not arise. Here, when counting the number of rings linked in the main chain direction of the molecule, fused rings conjugated in the side chain direction are counted as one.

[0053] D preferably contains two structures represented by the general formula (2). By containing two structures represented by the general formula (2), the solubility is further improved. １ is an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or CR ２ =CR ２ and R １ are each independently a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and R １ At least two of the R groups are alkyl groups, aryl groups, or heteroaryl groups. However, when at least two of the R groups are alkyl groups, at least one of the alkyl groups has two or more carbon atoms. １ may form a ring structure. ２ R are each independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group. １ and R ２ The alkyl groups of R ５ Examples of the alkyl group include those exemplified above in the description of R ２ The alkoxy group of the R ５ Examples of the alkoxy groups include those exemplified above in the description of R ２ The ester group of R ５ Examples thereof include the ester groups exemplified above in the description of (1), that is, the groups represented by the general formula (i).

[0054] Q１ The ring structure containing Q may further form a ring structure with an adjacent structure. １ is preferably an oxygen atom or a sulfur atom. １ may be the same or different. １ may be bonded to each other to form a ring. １ are each independently a hydrogen atom or an alkyl group, and three R １ At least two of the three R １ It is more preferable that one of R is a hydrogen atom and the remaining two are alkyl groups. ２ may be the same or different, but are preferably the same.

[0055] The structure represented by the general formula (2) is preferably a structure represented by the following general formula (2').

[0056]

[0057] In general formula (2'), Q １ is an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or CR ２ =CR ２ and R １ are each independently an alkyl group, an aryl group, or a heteroaryl group, provided that R １ When all of R are alkyl groups, at least one of the alkyl groups has two or more carbon atoms. １ may form a ring structure. ２ are each independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group.

[0058] Q in general formula (2') １ As R in the general formula (2'), a sulfur atom is preferred. １ may be the same or different. １ may be bonded to each other to form a ring. １ In general formula (2′), R is preferably an alkyl group. ２may be the same or different, but are preferably the same.

[0059] D is preferably a group represented by any one of the following general formulas (4) to (6).

[0060]

[0061] In the general formulas (4) to (6), W is C—(R ６ ) ２ , Si—(R ６ ) ２ , Ge-(R ６ ) ２ , N-R ６ or CR ６ -O and R ６ are each independently an alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group; E, J, K, and L are each independently an aryl group, a cyclopentadienyl group, or a heteroaryl group having 1 to 5 rings and containing an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, a germanium atom, or a selenium atom; G is a heteroaryl ring containing a nitrogen atom; s is a number from 0 to 1; and t is a number from 0 to 3. However, at least one of J and E in general formula (4) contains a structure represented by the general formula (2), preferably at least one of J contains a structure represented by the general formula (2), more preferably both of J contain a structure represented by the general formula (2); at least one of J, K, and L in general formula (5) contains a structure represented by the general formula (2), preferably at least one of J and K contains a structure represented by the general formula (2), more preferably at least one of J contains a structure represented by the general formula (2), particularly preferably both of J contain a structure represented by the general formula (2); at least one of J and K in general formula (6) contains a structure represented by the general formula (2), preferably either two Js or two Ks contain a structure represented by the general formula (2).

[0062] In the general formulas (4) to (6), W is C—(R ６ ) ２ , Si—(R ６ ) ２ , Ge-(R６ ) ２ , N-R ６ or CR ６ -O and R ６ R is independently an alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group. ６ The alkyl group of R ５ Examples of the alkyl group include those exemplified above in the description of R ６ Examples of the aryl group of R include the aryl groups exemplified above in the description of Ar. ６ Examples of the heteroaryl group of R include groups formed by removing one hydrogen atom from any ring atom of a heteroarene such as thiophene, and heteroaryl groups containing an oxygen atom, sulfur atom, or selenium atom are preferred. ６ The number of carbon atoms in the heteroaryl group of R is preferably 17 or less, more preferably 11 or less, even more preferably 9 or less, and particularly preferably 4. ６ The lower limit of the number of carbon atoms in the heteroaryl group is 4. ６ The aryl group and heteroaryl group may or may not have a substituent, but preferably have a substituent. ６ The aryl group of R is an unsubstituted or substituted aryl group; ６ The heteroaryl group in the formula (1) is an unsubstituted or substituted heteroaryl group. Examples of the substituent include an alkyl group, an alkoxy group, an ester group, a hydroxy group, and an amino group. Among these, an alkyl group and an alkoxy group are preferred.

[0063] In the general formulas (4) to (6), E is a heteroaryl group having one to five rings and containing an aryl group, a cyclopentadienyl group, or an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, a germanium atom, or a selenium atom. ｔ- is preferably an optionally substituted thiophene, furan, selenophene, thienothiophene, bithiophene, or terthiophene, or an optionally substituted aryl or heteroaryl group having 3 to 5 fused rings selected from benzene, thiophene, furan, selenophene, cyclopentadiene, silole, and pyrrole. Specific examples of the heteroaryl group having 3 fused rings selected from benzene, thiophene, furan, selenophene, cyclopentadiene, silole, and pyrrole include dibenzothiophene, dibenzofuran, dibenzosilole, carbazole, dithienocyclopentadiene, dithienosilole, dithienogermole, dithienothiophene, and dithienopyrrole. Among these, dithienocyclopentadiene, dithienosilole, dithienogermole, and dithienopyrrole are preferred, dithienocyclopentadiene and dithienosilole are more preferred, and dithienocyclopentadiene is even more preferred. The heteroaryl group having four fused rings selected from benzene, thiophene, furan, selenophene, cyclopentadiene, silole, and pyrrole is preferably a heteroaryl group having four fused rings selected from thiophene, cyclopentadiene, silole, and pyrrole, and more preferably a heteroaryl group having two or three thiophene rings in total, in which both ends of the four fused rings are thiophenes.

[0064] In the general formulas (4) to (6), J and K each independently represent an aryl group, a cyclopentadienyl group, or a heteroaryl group having one to five rings and containing an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, a germanium atom, or a selenium atom. J and K each independently represent an optionally substituted phenyl group, furan, thiophene, selenophene, or thienothiophene.

[0065] In the general formulas (4) to (6), L is an aryl group, a cyclopentadienyl group, or a heteroaryl group containing one to five rings and an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, a germanium atom, or a selenium atom. L is preferably an optionally substituted phenyl group, a naphthyl group, a thiophene, a thienothiophene, or a heteroaryl group containing one to three fused rings selected from benzene, thiophene, furan, selenophene, cyclopentadiene, silole, and pyrrole. Specific examples of the heteroaryl group containing three fused rings selected from benzene, thiophene, furan, selenophene, cyclopentadiene, silole, and pyrrole include dibenzothiophene, dibenzofuran, dibenzosilole, carbazole, dithienocyclopentadiene, dithienosilole, dithienogermole, dithienothiophene, and dithienopyrrole. Among these, dithienocyclopentadiene, dithienosilole, dithienothiophene, and dithienopyrrole are preferred, dithienocyclopentadiene, dithienosilole, and dithienopyrrole are more preferred, and dithienocyclopentadiene is even more preferred.

[0066] In the general formulae (4) to (6), G is a heteroaryl ring containing a nitrogen atom, and is preferably thiadiazole, selenadiazole, triazole, benzoquinoxaline, or diphenylpyrazine.

[0067] s is a number from 0 to 1. t is a number from 0 to 3.

[0068] As the compound (1), it is preferable that D in the general formula (1) is a group represented by the general formula (4) or (5), and as such a compound, a compound represented by the following general formula (7) (hereinafter also referred to as "compound (7)") is preferable.

[0069]

[0070] In the general formula (7), each A is independently a group represented by any one of the general formulas (3a), (3c) to (3y), and Y １ ~Y ４are each independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group; M is a carbon atom substituted with an alkyl group or an aryl group, a nitrogen atom substituted with an alkyl group or an aryl group, a silicon atom substituted with an alkyl group or an aryl group, or a germanium atom substituted with an alkyl group or an aryl group; Q １ are each independently an oxygen atom, a sulfur atom, a selenium atom, or N—R ３ or CR ６ =CR ６ and Ar ２ are each independently an aryl group or a heteroaryl group, or Ar ２ and two Ar ２ The total number of rings is 0 to 3, and a and b each represent 1 or 2.

[0071] A and its preferred embodiments in the general formula (7) are the same as A and its preferred embodiments in the general formula (1).

[0072] Y in the general formula (7) １ ~Y ４ Is Y １ and Y ３ one of which is a hydrogen atom and the other is an alkyl group, an alkoxy group, or an ester group; Y ２ and Y ４ Preferably, one of Y is a hydrogen atom and the other is an alkyl group, an alkoxy group, or an ester group. ３ and Y ４ is a hydrogen atom, and Y １ and Y ２ is more preferably an alkyl group, an alkoxy group or an ester group, and Y ３ and Y ４ is a hydrogen atom, and Y １ and Y ２ It is more preferred that is an alkoxy group.

[0073] M in the general formula (7) is preferably a carbon atom substituted with an alkyl group or an aryl group, a silicon atom substituted with an alkyl group or an aryl group, or a germanium atom substituted with an alkyl group or an aryl group, more preferably a carbon atom substituted with an alkyl group or an aryl group, or a silicon atom substituted with an alkyl group or an aryl group, and even more preferably a carbon atom substituted with an alkyl group or an aryl group.

[0074] In the general formula (7), Q １ is preferably an oxygen atom or a sulfur atom, more preferably a sulfur atom.

[0075] In the general formula (7), Ar ２ is a group selected from optionally substituted benzene, thiophene, furan, selenophene, cyclopentadiene, silole and pyrrole, or Ar ２ and two Ar ２ The total number of rings in Ar is preferably 0 to 3, and Ar is a group selected from optionally substituted thiophene, furan, and cyclopentadiene. ２ and two Ar ２ It is more preferable that the total number of rings in one of Ar ２ is a group having 1 to 3 rings selected from thiophene or cyclopentadiene which may be substituted, and the other Ar ２ It is more preferable that the compound does not have one Ar ２ is a group having 2 to 3 rings selected from thiophene or cyclopentadiene which may be substituted, and the other Ar ２ It is even more preferable that Ar does not have ２ is a group having two rings which is an optionally substituted thiophene, and the other Ar ２ In another aspect, it is particularly preferable that one Ar ２ is a tricyclic group selected from two optionally substituted thiophenes and one optionally substituted cyclopentadiene, and the other Ar ２ It is particularly preferred that the polymer does not have

[0076] It is preferable that a and b are both 1.

[0077] Furthermore, as compound (1), it is more preferable that D in the general formula (1) is a group represented by the general formula (4), and as such a compound, a compound represented by the following general formula (4a) (hereinafter also referred to as "compound (4a)") is preferable.

[0078]

[0079] In the general formula (4a), each A is independently a group represented by any one of the general formulas (3a), (3c) to (3y), and Y １ ~Y ４ are each independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group; Y １ ~Y ４ at least one of the groups is an alkoxy group branched at the 1-position, and M is a carbon atom substituted with an alkyl group or an aryl group, a nitrogen atom substituted with an alkyl group or an aryl group, a silicon atom substituted with an alkyl group or an aryl group, or a germanium atom substituted with an alkyl group or an aryl group.

[0080] A and its preferred embodiments in the general formula (4a) are the same as A and its preferred embodiments in the general formula (1).

[0081] Y in the general formula (4a) １ ~Y ４ are each independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group; Y １ ~Y ４ At least one of the groups is an alkoxy group branched at the 1-position. １ ~Y ４ The alkyl group of R ５ Examples of the alkyl group include those exemplified above in the description of Y. １ ~Y ４The alkyl group may be chain-like or cyclic. When the alkyl group is chain-like, it may be linear or branched. In terms of ease of synthesis, a linear or branched alkyl group in which the carbon atom bonded to the thiophene ring is a primary carbon atom is preferred. In terms of solubility of the material, a branched alkyl group in which the carbon atom bonded to the thiophene ring is a primary carbon atom, or a linear, branched, or cyclic alkyl group in which the carbon atom bonded to the thiophene ring is a secondary carbon atom is preferred. In terms of ease of synthesis and solubility, a branched alkyl group in which the carbon atom bonded to the thiophene ring is a primary carbon atom is even more preferred.

[0082] Y １ ~Y ４ The alkoxy group of the R ５ Examples of suitable alkyl groups include the alkoxy groups exemplified above in the description of (1). An alkoxy group has a structure in which an alkyl group is bonded to an oxygen atom, and the alkyl group bonded to the oxygen atom may be linear or cyclic. When the alkyl group bonded to the oxygen atom is linear, it may be linear or branched. In terms of ease of synthesis, a linear or branched alkyl group in which the carbon atom bonded to the oxygen atom is a primary carbon atom is preferred. In terms of the solubility of the material, a branched alkyl group in which the carbon atom bonded to the oxygen atom is a primary carbon atom, or a linear, branched, or cyclic alkyl group in which the carbon atom bonded to the oxygen atom is a secondary carbon atom is preferred, a linear, branched, or cyclic alkyl group in which the carbon atom bonded to the oxygen atom is a secondary carbon atom is more preferred, and a linear or branched alkyl group in which the carbon atom bonded to the oxygen atom is a secondary carbon atom is even more preferred.

[0083] Y １ ~Y ４ The ester group of R ５ Examples of the ester groups include those exemplified above in the description of R in the general formula (i), that is, the group represented by the general formula (i). ７The alkyl group may be linear or cyclic. When the alkyl group is linear, it may be linear or branched. In terms of ease of synthesis, a linear or branched alkyl group in which the carbon atom bonded to the oxygen atom is a primary carbon atom is preferred. In terms of solubility of the material, a branched alkyl group in which the carbon atom bonded to the oxygen atom is a primary carbon atom, or a linear, branched, or cyclic alkyl group in which the carbon atom bonded to the oxygen atom is a secondary carbon atom is preferred, a linear, branched, or cyclic alkyl group in which the carbon atom bonded to the oxygen atom is a secondary carbon atom is more preferred, and a linear or branched alkyl group in which the carbon atom bonded to the oxygen atom is a secondary carbon atom is even more preferred.

[0084] R ７ Examples of the aryl group of R include the aryl groups exemplified above in the description of Ar. ７ The aryl group of R may or may not have a substituent. ７ The aryl group may be an unsubstituted or substituted aryl group, and examples of the substituent include an alkyl group, an alkoxy group, an ester group, a hydroxy group, and an amino group.

[0085] Y １ ~Y ４ At least one of the alkoxy groups is branched at the 1-position (hereinafter also referred to as "1-branched alkoxy group"). The 1-branched alkoxy group is an alkoxy group having an O—C(R １ ) ２ Examples include: R １ is R in the general formula (2). １ is the same as:

[0086] Y １ ~Y ４ In particular, Y is preferably selected from the viewpoint of facilitating the formation of a lamellar structure in the film obtained by using the compound of the present invention. １ and Y ３ one of which is a hydrogen atom and the other is an alkyl group, an alkoxy group, or an ester group; Y ２ and Y ４It is preferable that one of Y is a hydrogen atom and the other is an alkyl group, an alkoxy group, or an ester group. Among these, Y is particularly preferable from the viewpoint of increasing the absorption wavelength. １ is preferably an alkoxy group. In particular, Y is preferably an alkoxy group because the orientation of the substituents is parallel and the lamellar structure is more easily formed. ２ and Y ３ is a hydrogen atom, and Y １ and Y ４ is more preferably an alkyl group, an alkoxy group or an ester group. １ ~Y ４ Among these, at least one is an alkoxy group branched at the 1-position, but when any or all of the remaining three substituents are alkoxy groups, this alkoxy group may be a 1-branched alkoxy group, or an alkoxy group other than the 1-branched alkoxy group (hereinafter also referred to as "another alkoxy group"). The other alkoxy group may be a linear alkoxy group, or may be branched at a position other than the 1-position. In another embodiment, in terms of shifting the absorption wavelength to a longer wavelength, １ and Y ２ are each independently an alkoxy group; ３ and Y ４ is preferably a hydrogen atom, and in particular, from the viewpoint of solubility, Y １ and Y ２ are each independently an alkoxy group branched at the 1-position, and from the viewpoint of ease of synthesis, Y １ and Y ２ It is more preferable that are the same.

[0087] In the general formula (4a), M is a carbon atom substituted with an alkyl group or an aryl group, a nitrogen atom substituted with an alkyl group or an aryl group, a silicon atom substituted with an alkyl group or an aryl group, or a germanium atom substituted with an alkyl group or an aryl group. It is believed that compound (4a) can improve its solubility when M is a carbon atom substituted with an alkyl group or an aryl group, a nitrogen atom substituted with an alkyl group or an aryl group, a silicon atom substituted with an alkyl group or an aryl group, or a germanium atom substituted with an alkyl group or an aryl group. The carbon atom substituted with an alkyl group or an aryl group is represented by the general formula (ii). The nitrogen atom substituted with an alkyl group or an aryl group is represented by the general formula (iii). The silicon atom substituted with an alkyl group or an aryl group is represented by the general formula (iv). The germanium atom substituted with an alkyl group or an aryl group is represented by the general formula (v).

[0088] From the viewpoint of the ease of synthesis of compound (4a), M is preferably the same as the two alkyl groups or aryl groups that carbon atom, silicon atom and germanium atom have.From the viewpoint of synthesis cost, M is preferably the carbon atom substituted with alkyl group or aryl group, the nitrogen atom substituted with alkyl group or aryl group or the silicon atom substituted with alkyl group or aryl group, among which, from the viewpoint of the longer wavelength of absorption wavelength, more preferably the carbon atom substituted with alkyl group or aryl group or the nitrogen atom substituted with alkyl group or aryl group, more preferably the carbon atom substituted with alkyl group or the nitrogen atom substituted with alkyl group, and particularly preferably the carbon atom substituted with alkyl group.

[0089] The compound (4a) is a compound represented by the general formula (4a), wherein each A is independently a group represented by any one of the general formulas (3m), (3n), (3o), (3s), (3v), (3w), (3x), and (3y); and Y １ and Y ２ are identical and are alkoxy groups branched at the 1-position, and Y ３ and Y ４is a hydrogen atom, and M is a carbon atom substituted with an alkyl group or an aryl group, or a nitrogen atom substituted with an alkyl group or an aryl group. ４ and Z ５ one of which is an oxygen atom and the other is a dicyanomethylene group, and X １ is a fluorine atom, a chlorine atom or a cyano group, and V is C-X ２ or a nitrogen atom, and X ２ Among them, A is preferably a group represented by the general formula (3o), (3s), (3x) or (3y), and Z ４ and Z ５ one of which is an oxygen atom and the other is a dicyanomethylene group, and X １ are each independently a fluorine atom, a chlorine atom or a cyano group, and V is C-X ２ or a nitrogen atom, and X ２ In the case of the general formula (3o) or (3x), Z is more preferably a hydrogen atom. ４ and Z ５ one of which is an oxygen atom and the other is a dicyanomethylene group, and X １ is a chlorine atom or a cyano group, and V is C-X ２ or a nitrogen atom, and X ２ is more preferably a hydrogen atom, and X １ It is particularly preferred that Z is a cyano group and V is C—H. ４ and Z ５ one of which is an oxygen atom and the other is a dicyanomethylene group, and X １ is a chlorine atom or a cyano group, and V is C-X ２ or a nitrogen atom, and X ２ is more preferably a hydrogen atom, and X １ It is particularly preferred that is a cyano group and V is a nitrogen atom.

[0090] Preferred embodiments of the general formula (4a) include the general formulae (4b) to (4d) and (4f) to (4h).

[0091]

[0092]

[0093] In general formulas (4b) to (4d), (4f) to (4h), １ R is a fluorine atom, a chlorine atom or a cyano group, preferably a chlorine atom or a cyano group, more preferably a cyano group. ８ and R ９ Y is an aryl group substituted with an alkyl group or an alkoxy group, or an alkyl group, preferably an alkyl group. １ and Y ２ is an alkyl group, an alkoxy group or an ester group, preferably an alkoxy group.

[0094] Specific examples of compound (1) include compounds represented by the following formulas, but compound (1) is not limited to these: In the following formulas, the crossed double bonds mean that the compound can exist as an E isomer, a Z isomer, or a mixture thereof.

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203] The method for producing compound (1) is not particularly limited, but as an example of the method for producing compound (1), the method for producing compound (A) of the following formula will be specifically described. X in compound (A) represents X in the general formula (3o) above.１ and Z in compound (A) corresponds to Z in the general formula (3o). ４ or Z ５ and R in compound (A) corresponds to １ is R in the general formula (2'). １ and M in compound (A) corresponds to M in general formula (4a).

[0204]

[0205] First, commercially available 3-methoxythiophene is reacted with a secondary alcohol in a reaction solvent to obtain a compound (B) of the following formula.

[0206]

[0207] Here, the secondary alcohol may be synthesized by a known method, or a commercially available product may be used. The ratio of the raw materials charged is preferably 0.9 to 1.5 equivalents of secondary alcohol relative to 3-methoxythiophene, and 0.1 to 0.5 equivalents of sodium hydrogen sulfate. The reaction solvent is not particularly limited as long as it does not react with the raw material compounds, and examples include aromatic hydrocarbon solvents such as toluene and xylene. The reaction temperature is preferably room temperature to reflux temperature. The reaction time is preferably 1 to 24 hours.

[0208] Next, compound (B) is reacted with lithium diisopropylamide (LDA) in a reaction solvent, and then further reacted with N,N-dimethylformamide to obtain compound (C) of the following formula.

[0209]

[0210] The ratio of the raw materials to be charged is preferably 0.9 to 1.5 equivalents of LDA relative to compound (B), and preferably 0.9 equivalents or more of N,N-dimethylformamide. N-formylpiperidine may be used instead of N,N-dimethylformamide. The reaction solvent is not particularly limited as long as it does not react with the raw material compounds, and examples include saturated aliphatic hydrocarbon solvents such as hexane; ether solvents such as tetrahydrofuran (THF), diethyl ether, cyclopentyl methyl ether, and methyl t-butyl ether; and aromatic hydrocarbon solvents such as toluene and xylene. The reaction temperature is preferably −78 to 50° C. The reaction time is preferably 10 minutes to 12 hours after the addition of LDA and 10 minutes to 12 hours after the addition of N,N-dimethylformamide.

[0211] Next, compound (C) is reacted with N-bromosuccinimide (NBS) in a reaction solvent to obtain compound (D) of the following formula.

[0212]

[0213] The ratio of NBS to compound (C) is preferably 0.9 to 1.2 equivalents, more preferably 0.9 to 1.05 equivalents. Bromine may be used instead of NBS. The reaction solvent is not particularly limited as long as it does not react with the starting compounds, and examples include saturated aliphatic hydrocarbon solvents such as hexane; ether solvents such as tetrahydrofuran (THF); aromatic hydrocarbon solvents such as toluene and xylene; halogenated solvents such as chloroform; and N,N-dimethylformamide. The reaction temperature is preferably −78 to 50° C. The reaction time is preferably 10 minutes to 24 hours after the addition of NBS.

[0214] In producing the compound (A), the compound (E) of the following formula may be used instead of the compound (D): Compound (E) can be obtained, for example, as follows.

[0215] That is, first, compound (B) is reacted with lithium diisopropylamide (LDA) in a reaction solvent, and then further reacted with 1,2-dibromo-1,1,2,2-tetrachloroethane to obtain compound (D') of the following formula.

[0216]

[0217] The ratio of the raw materials to be charged is preferably 0.9 to 1.5 equivalents of LDA relative to compound (B), and 0.9 or more equivalents of 1,2-dibromo-1,1,2,2-tetrachloroethane. The reaction solvent is not particularly limited as long as it does not react with the raw material compounds, and examples include saturated aliphatic hydrocarbon solvents such as hexane; ether solvents such as tetrahydrofuran (THF), diethyl ether, cyclopentyl methyl ether, and methyl t-butyl ether; and aromatic hydrocarbon solvents such as toluene and xylene. The reaction temperature is preferably −78 to 50° C. The reaction time is preferably 10 minutes to 12 hours after the addition of LDA and 10 minutes to 12 hours after the addition of 1,2-dibromo-1,1,2,2-tetrachloroethane.

[0218] Next, compound (D') is reacted with lithium diisopropylamide (LDA) in a reaction solvent, and then further reacted with N,N-dimethylformamide to obtain compound (E) of the following formula.

[0219]

[0220] The ratio of the raw materials to compound (D') is preferably 0.9 to 1.5 equivalents of LDA, and 0.9 or more equivalents of N,N-dimethylformamide. N-formylpiperidine may be used instead of N,N-dimethylformamide. The reaction solvent is not particularly limited as long as it does not react with the raw material compounds, and examples include saturated aliphatic hydrocarbon solvents such as hexane; ether solvents such as tetrahydrofuran (THF), diethyl ether, cyclopentyl methyl ether, and methyl t-butyl ether; and aromatic hydrocarbon solvents such as toluene and xylene. The reaction temperature is preferably −78 to 50° C. The reaction time is preferably 10 minutes to 12 hours after the addition of LDA and 10 minutes to 12 hours after the addition of N,N-dimethylformamide.

[0221] Next, in a reaction solvent, at least one of compound (D) and compound (E) is cross-coupled with compound (F) of the following formula to obtain compound (G) of the following formula. The method for producing compound (G) is not particularly limited, but for example, Adv. Energy Mater., 2018, Vol. 8, p. 1801212.; J. Mater. Chem. C, 2020, Vol. 8, p. 15175.; ACS Energy Lett., 2019, Vol. 4, p. 1401. Compound (G) can be produced by a method similar to the method described in. An example of a specific production condition is as follows.

[0222]

[0223] Here, compound (F) may be synthesized by a known method (e.g., Polym. Chem., 2013, Vol. 4, pp. 5351-5360; J. Phys. Chem. C, 2011, Vol. 15, pp. 2398-2405; Chem. Commun., 2012, Vol. 48, pp. 11130-11132), or a commercially available product may be used. Alternatively, a compound (F) (where "L" in compound (F) is an alkyltin group, boric acid, a borate ester group, zinc halide, magnesium halide, a silyl group, or the like) appropriate for the cross-coupling reaction may be used. The type of cross-coupling reaction, which is a reaction between at least one of compound (D) and compound (E) and compound (F), is not particularly limited, and the reaction can be carried out by Stille coupling, Suzuki coupling, Negishi coupling, Kumada coupling, Hiyama coupling, or the like. The cross-coupling reaction may be carried out in the presence of a catalyst such as a palladium catalyst, a nickel catalyst, or a copper catalyst. For example, when compound (D) or compound (E) is reacted with compound (F) by a Stille coupling reaction, the raw material charge ratio is preferably 1.9 to 3.0 equivalents of compound (D) or compound (E) relative to compound (F). Furthermore, it is preferable to use a palladium catalyst during the Stille coupling reaction, and the palladium content in the catalyst is preferably 0.1 to 50 mol%. The reaction solvent is not particularly limited as long as it does not react with the raw material compounds, and examples thereof include saturated aliphatic hydrocarbon solvents such as hexane; ether solvents such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran (THF), and 1,4-dioxane; aromatic hydrocarbon solvents such as toluene and xylene; N,N-dimethylformamide (DMF), dimethyl sulfoxide, and N-methyl-2-pyrrolidone. The reaction temperature is preferably from 20° C. to the reflux temperature of the reaction solvent. The reaction time is preferably from 1 to 24 hours.

[0224] Next, in a reaction solvent, compound (G) and compound (I) are reacted in the presence of an acid catalyst or a base catalyst to obtain compound (A). The method for producing compound (A) is not particularly limited, but for example, under acid catalyst conditions, compound (A) can be produced by a method similar to that described in JP 2022-511781 A; JP 2023-500815 A, etc. On the other hand, under base catalyst conditions, compound (A) can be produced by a method similar to that described in Adv. Energy Mater., 2018, Vol. 8, p. 1801212.; J. Mater. Chem. C, 2020, Vol. 8, p. 15175.; ACS Energy Lett., 2019, Vol. 4, p. 1401. An example of specific production conditions is as follows.

[0225]

[0226] Here, compound (I) can be synthesized by a known method (for example, JP 2022-511781 A, JP 2023-500815 A, Adv. Mater., 2017, Vol. 29, p. 1703080.; Angew. Chem. Int. Ed., 2017, Vol. 56, p. 3045.; J. Am. Chem. Soc., 2017, Vol. 139, p. 1336-1343., etc.). As the acid catalyst, p-toluenesulfonic acid hydrate (PTSA.H ２ O). Examples of the base catalyst include pyridine and piperidine. The ratio of the raw materials to be charged is preferably 1.9 to 10 equivalents of compound (I) relative to compound (G). The acid catalyst is preferably 2.1 to 11 equivalents. The base catalyst is preferably 1 to 10 mass% relative to the reaction solvent. The reaction solvent is not particularly limited as long as it does not react with the raw material compounds, and examples include alcoholic solvents such as methanol and ethanol; aromatic hydrocarbon solvents such as toluene and xylene; and halogenated solvents such as chloroform, and these may be used in combination. The reaction temperature is preferably room temperature to reflux temperature. The reaction time is preferably 10 minutes to 24 hours.

[0227] In this way, compound (A) can be produced. Here, X in compound (A) is X in the general formula (3o). １ and Z in the compound (A) is Z in the general formula (3o). ４ or Z ５ and R in compound (A) １ is R in the general formula (2'). １ and M in compound (A) is M in the general formula (4a).

[0228] The compound of the present invention can achieve both a longer absorption wavelength and high solubility, and is therefore suitable as an n-type semiconductor material (light-absorbing material and electron-transporting material) used in a photoelectric conversion element. The uses of the compound of the present invention are not limited to those described above. For example, the compound of the present invention also has excellent luminescence properties, and can therefore also be used in bioimaging, organic electroluminescence, and near-infrared luminescent dyes for wavelength conversion films and compositions.

[0229] [Composition] The composition of the present invention contains the above-described compound (1). The compound (1) may be used alone, or two or more types may be used in any proportion and combination. The content of compound (1) in the composition of the present invention is not particularly limited. However, when the composition of the present invention is used for forming a photoelectric conversion layer (active layer) of a photoelectric conversion element, a high content of compound (1) is preferable in terms of light absorption, while a low content is preferable in terms of carrier balance. Therefore, the content of compound (1) relative to the total amount (total mass) of all components other than the solvent in the composition of the present invention is preferably 10% by mass or more, more preferably 25% by mass or more, and even more preferably 40% by mass or more. Furthermore, the content of compound (1) relative to the total amount (total mass) of all components other than the solvent in the composition of the present invention is preferably 100% by mass or less, more preferably 90% by mass or less, even more preferably 75% by mass or less, and particularly preferably 60% by mass or less.

[0230] The composition of the present invention may further contain a solvent. A composition containing compound (1) and a solvent is suitable as an ink (active layer-forming composition) for forming a photoelectric conversion layer (active layer) of a photoelectric conversion element. The solvent is preferably a liquid that does not react with compound (1) and dissolves compound (1), such as aromatic hydrocarbon solvents such as toluene and xylene; halogenated solvents such as dichloromethane and chloroform; and the like. When the composition of the present invention contains a solvent, the solvent may be used alone, or two or more solvents may be used in any ratio and combination. When the composition of the present invention contains a solvent, the content of compound (1) in the composition of the present invention is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, relative to the total mass of the composition of the present invention. Furthermore, the content of compound (1) is preferably 5.0% by mass or less, more preferably 3.5% by mass or less, and even more preferably 2.0% by mass or less, relative to the total mass of the composition of the present invention.

[0231] When the composition of the present invention is used as a composition for forming an active layer, the composition preferably further contains a p-type semiconductor material in addition to compound (1). The p-type semiconductor material is not particularly limited as long as it is used in the photoelectric conversion layer of an organic photoelectric conversion element, and examples thereof include polymers described in literature (ACS Energy Lett., 2019, Vol. 4, p. 1401. and Adv. Optical Mater., 2022, Vol. 10, p. 2200747.). When the composition of the present invention contains a p-type semiconductor material, the p-type semiconductor material may be used alone, or two or more types may be used in any ratio and combination. The mass ratio of compound (1) to the p-type semiconductor material (compound (1) / p-type semiconductor material) is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 0.75 or more. The mass ratio of compound (1) to the p-type semiconductor material is preferably 3.0 or less, more preferably 2.0 or less, and even more preferably 1.5 or less.

[0232] The composition of the present invention may further contain components (optional components) other than compound (1), the p-type semiconductor material, and the solvent, as necessary, as long as the effects of the present invention are not impaired. Examples of optional components include 1,8-diiodooctane and 1-chloronaphthalene. When the composition of the present invention contains optional components, the optional components may be used alone, or two or more may be used in any combination and in any ratio. When the composition of the present invention contains optional components, a large amount of optional components is preferable in terms of easily manifesting the effects of the optional components. On the other hand, a large content of compound (1) is preferable in terms of easily maintaining suitable physical properties for a photoelectric conversion element. Therefore, when the composition of the present invention contains optional components, the content of the optional components is preferably 0.1% by mass or more, and more preferably 0.3% by mass or more, relative to the total amount (total mass) of all components other than the solvent in the composition of the present invention. Furthermore, the content of the optional components is preferably 2.0% by mass or less, and more preferably 1.0% by mass or less, relative to the total amount (total mass) of all components other than the solvent in the composition of the present invention.

[0233] The composition of the present invention can be obtained, for example, by dissolving compound (1) and, if necessary, one or more of a p-type semiconductor material and optional components in a solvent, and by removing the solvent from the obtained composition, a solvent-free composition of the present invention can be obtained.

[0234] The composition of the present invention is suitable as an ink (composition for forming an active layer) for forming a photoelectric conversion layer (active layer) of a photoelectric conversion element.

[0235] [Film] The film of the present invention is a film containing the above-mentioned compound (1), and is also referred to as an organic thin film. The film of the present invention can be obtained, for example, by removing the solvent from the above-mentioned solvent-containing composition of the present invention. Specifically, it can be obtained by applying the composition of the present invention to a substrate and then drying it. The content of compound (1) in the film is the same as the content of compound (1) relative to the total amount (total mass) of all components other than the solvent in the above-mentioned composition of the present invention. That is, relative to the total mass of the film, the content of compound (1) is preferably 10% by mass or more, more preferably 25% by mass or more, and even more preferably 40% by mass or more. Furthermore, relative to the total mass of the film, the content of compound (1) is preferably 100% by mass or less, more preferably 90% by mass or less, even more preferably 75% by mass or less, and particularly preferably 60% by mass or less.

[0236] The film thickness is preferably thick in terms of the amount of light absorption. On the other hand, in terms of the external quantum efficiency (EQE) when the film of the present invention is used as a photoelectric conversion layer (active layer) of a photoelectric conversion element, the film thickness is preferably thin. Therefore, the film thickness is preferably 10 nm or more, more preferably 100 nm or more. In addition, the film thickness is preferably 1000 nm or less, more preferably 500 nm or less. The film thickness can be adjusted by the amount of the composition applied to the substrate.

[0237] The method for applying the composition is not particularly limited, but examples thereof include brush coating, bar coating, spray coating, dip coating, spin coating, curtain coating, etc. The drying temperature after application is preferably 20 to 250° C. The drying time is preferably 10 minutes to 5 hours.

[0238] The film of the present invention is suitable as a photoelectric conversion layer (active layer) of a photoelectric conversion element.

[0239] [Photoelectric conversion element] The photoelectric conversion element of the present invention is an element comprising the above-described film of the present invention, and is also referred to as an organic photoelectric conversion element. Specifically, the photoelectric conversion element of the present invention comprises the film of the present invention as a photoelectric conversion layer (active layer). The structure of the photoelectric conversion element can be that of a known organic photoelectric conversion element. For example, reference can be made to the description in JP 2007-324587 A. The specific structure is not particularly limited, and examples thereof include an element having a stacked structure in which a photoelectric conversion layer (active layer) is sandwiched between a pair of electrodes.

[0240] An example of a photoelectric conversion element of the present invention will be described below with reference to Fig. 1. Note that, in each drawing used in the following description, characteristic portions may be enlarged for convenience in order to make the features easier to understand, and the dimensional ratios of each component may differ from the actual ones. Furthermore, the materials, dimensions, etc. exemplified in the following description are merely examples, and the present invention is not limited thereto. Appropriate changes can be made within the scope of the present invention.

[0241] 1 has a structure in which a transparent electrode 12, a hole transport layer 13, a photoelectric conversion layer 14, an electron transport layer 15, and a metal electrode 16 are laminated in this order on a transparent substrate 11. The positions of the hole transport layer 13 and the electron transport layer 15 may be interchanged. That is, the photoelectric conversion element may have a structure in which a transparent electrode, an electron transport layer, a photoelectric conversion layer (active layer), a hole transport layer, and a metal electrode are laminated in this order on a transparent substrate.

[0242] The transparent substrate 11 may be a substrate having an average transmittance of 80% or more for visible light of 450 nm or more. Examples of materials for forming the transparent substrate 11 include glass and plastics such as polyethylene terephthalate, polyethylene naphthalate, polycarbonate, and polyethylene sulfide.

[0243] The transparent electrode 12 may be an electrode having an average transmittance of 80% or more in visible light of 450 nm or more. The material for forming the transparent electrode 12 is not particularly limited as long as it can form the transparent electrode 12. For example, tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), tungsten-doped indium oxide (IWO), zinc aluminum oxide (AZO), indium oxide (In ２ O ３ ), zinc oxide (ZnO), titanium oxide (TiO ２ ) etc.

[0244] The metal electrode 16 is an electrode paired with the transparent electrode 12. The material constituting the metal electrode 16 is not particularly limited, but examples include metals such as gold, platinum, silver, aluminum, nickel, titanium, magnesium, calcium, barium, sodium, chromium, copper, and cobalt, or alloys thereof. The metal electrode 16 is preferably a transparent electrode or a reflective electrode. That is, the photoelectric conversion element preferably has a laminated structure in which a photoelectric conversion layer (active layer) is sandwiched between a pair of electrodes (transparent or metal), and more preferably has a laminated structure in which an electron transport layer, a photoelectric conversion layer (active layer), and a hole transport layer are sandwiched between a pair of electrodes (transparent or metal). In the case of a pair of transparent electrodes, the materials forming the electrodes may be the same or different. The film thickness of the metal electrode 16 is not particularly limited, but is preferably about 10 nm from the viewpoint of enhancing transparency. Furthermore, when transparency is not required, a thickness of 40 nm or more is preferable, and 100 nm or more is more preferable, taking into account durability and the like.

[0245] The method for forming the transparent electrode 12 and the metal electrode 16 is not particularly limited, but they can be formed by, for example, a dry process such as vacuum deposition or sputtering; or a wet process using conductive ink or the like.

[0246] When the hole transport layer 13 and the electron transport layer 15 are provided, there are no particular limitations on the constituent members and manufacturing methods thereof, and known techniques can be used. For example, members and manufacturing methods thereof described in known documents such as International Publication No. 2013 / 171517, International Publication No. 2013 / 180230, or Japanese Patent Application Laid-Open No. 2012-191194 can be used.

[0247] The photoelectric conversion layer 14 is a layer that absorbs light and separates charges. The photoelectric conversion layer 14 of the photoelectric conversion element of the present invention is a layer containing the compound (1) of the present invention described above. More specifically, it is the film of the present invention described above. The photoelectric conversion layer 14 can be formed, for example, by applying the composition of the present invention described above onto a layer that will be below the photoelectric conversion layer 14, such as the hole transport layer 13, and drying the applied composition.

[0248] The photoelectric conversion element 10 can be obtained, for example, by forming a transparent electrode 12, a hole transport layer 13, a photoelectric conversion layer 14, an electron transport layer 15, and a metal electrode 16 in this order on a transparent substrate 11.

[0249] In the photoelectric conversion element of the present invention, since the photoelectric conversion layer 14 contains the compound (1), the absorption wavelength can be shifted to a longer wavelength while suppressing dark current, and the sensor has high sensitivity on the longer wavelength side.

[0250] [CMOS Image Sensor] The CMOS image sensor of the present invention includes the photoelectric conversion element of the present invention described above. The structure of the CMOS image sensor can be that of a known CMOS image sensor. For example, the description of JP 2021-57422 A can be referenced, and is not particularly limited. More specifically, a CMOS image sensor having a structure in which metal wiring, the photoelectric conversion element of the present invention, a color filter, and a microlens are stacked in this order on a substrate such as a silicon substrate can be mentioned.

[0251] The present invention will be described in more detail below with reference to examples, but the following examples are not intended to limit the scope of the present invention.

[0252] [Synthesis of Compound (4-3o-31)] Compound (B-1) of the following formula was synthesized by a method similar to that described in a known literature (New J. Chem., 2020, Vol. 44, p. 8032). Using the obtained compound (B-1), compound (C-1) of the following formula was synthesized by a method similar to that described in a known literature (J. Mater. Chem. A, 2020, Vol. 8, p. 5163). １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CDCl ３ , ppm): δ 7.14 (dd, 1H), 6.74 (dd, 1H), 6.21 (dd, 1H), 4.00 (quin, 1H), 1.71-1.58 (m, 4H), 1.50-1.28 (m, 6H), 0.95 (t, 3H), 0.88 (t, 3H). １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CDCl ３ , ppm): δ9.81 (s, 1H), 7.40 (dd, 1H), 6.73 (m, 1H), 4.03 (quin, 1H), 1.72-1.57 (m, 4H), 1.45-1.29 (m, 6H), 0.96 (t, 3H), 0.87 (t, 3H).

[0253]

[0254] Next, 4.99 g (20.7 mmol) of compound (C-1) was dissolved in 40 mL of acetonitrile. To this was slowly added 3.73 g (20.9 mmol) of N-bromosuccinimide. After stirring at room temperature for 1 hour, water and hexane were added, and the organic layer was washed three times with water. After drying over anhydrous sodium sulfate, the mixture was purified by silica gel chromatography to obtain the compound (yield 98%). １ The resulting compound was confirmed to be compound (D-1) by H-NMR analysis. １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CDCl ３, ppm): δ9.70 (s, 1H), 7.33 (s, 1H), 4.10 (quin, 1H), 1.73-1.59 (m, 4H), 1.45-1.29 (m, 6H), 0.96 (t, 3H), 0.88 (t, 3H).

[0255]

[0256] Separately, compound (F-1) of the following formula was synthesized by the method described in a known literature (Macromolecules, 2007, Vol. 40, p. 1981.). Subsequently, with reference to the method described in JP-A-2022-030124, 1.46 g (2.0 mmol) of compound (F-1) and 1.35 g (4.2 mmol) of compound (D-1) were reacted. Thereafter, the solvent was removed under reduced pressure, and the resulting mixture was purified by silica gel column chromatography to obtain a compound (yield 85%). １ The resulting compound was confirmed to be compound (G-1) by H-NMR analysis. １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CDCl ３ , ppm): δ9.74 (s, 2H), δ7.44 (s, 2H), 7.34 (s, 2H), 4.31 (quin, 2H), 1.97-0.61 (m, 66H).

[0257]

[0258] Separately, compound (I-1) of the following formula was synthesized by the method described in JP 2023-500815 A. Compound (G-1) 0.294 g (0.33 mmol) and compound (I-1) 0.408 g (1.67 mmol) were placed in a reaction vessel, and 8.2 mL of toluene and 16.3 mL of ethanol were added and dissolved. Then, 0.477 g (2.51 mmol) of p-toluenesulfonic acid monohydrate was added and stirred at 65 ° C. for 2 hours. After cooling, the organic layer was extracted with ethyl acetate and water, and the extract was dried over sodium sulfate. The solid content was removed by filtration, and the solvent of the solution was distilled off to obtain a solid. The solid was dispersed in methanol and filtered to obtain 0.30 g of a solid compound (yield 67%). １ H-NMR analysis confirmed that the obtained compound was compound (4-3o-31).１ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CDCl ３ , ppm): δ8.74 (s, 2H), 8.69 (s, 2H), 7.92 (s, 2H), 7.61-7.62 (m, 2H), 7.50 (br.s., 2H), 4.41-4.44 (quin, 2H) ), 1.76-2.03 (m, 12H), 1.45-1.51 (br.s., 4H), 1.33-1.37 (m, 8H), 0.89-1.10 (m, 28H), 0.63-0.74 (m, 14H).

[0259]

[0260] [Synthesis of Compound (4-3o-50)] Compound (G-1) was synthesized in the same manner as in the synthesis of compound (4-3o-31). Separately, compound (I-2) of the following formula was synthesized by the same method as described in a publicly known document (Adv. Mater., 2017, Vol. 29, p. 1703080.). 0.22 g (0.25 mmol) of compound (G-1) and 0.16 g (0.59 mmol) of compound (I-2) were placed in a reaction vessel, 6.2 mL of chloroform was added, and the mixture was stirred to dissolve. 0.25 mL of pyridine was then added, and the mixture was stirred at 60°C for 3 hours. After allowing to cool, the solvent was distilled off, and the resulting crude product was purified by silica gel chromatography to obtain 0.29 g of a solid compound (yield 86%). １ H-NMR analysis confirmed that the obtained compound was compound (4-3o-50). １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CDCl ３ , ppm): δ8.74 (s, 2H), 8.70 (s, 2H), 7.92 (s, 2H), 7.61-7.62 (m, 2H), 7.50 (br.s., 2H), 4.41-4.44 (quin, 2H) ), 1.75-2.03 (m, 12H), 1.43-1.60 (br.s., 4H), 1.34-1.37 (m, 8H), 0.89-1.10 (m, 28H), 0.63-0.74 (m, 14H).

[0261]

[0262] [Synthesis of Compound (4-3o-57)] Compound (B-2) of the following formula was synthesized by a method similar to that described in a known literature (New J. Chem., 2020, Vol. 44, p. 8032). Compound (C-2) of the following formula was synthesized using the obtained compound (B-2) by a method similar to that described in a known literature (J. Mater. Chem. A, 2020, Vol. 8, p. 5163). １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CDCl ３ , ppm): δ 7.15 (dd, 1H), 6.73 (dd, 1H), 6.22 (dd, 1H), 4.22 (sext, 1H), 1.71-1.58 (m, 1H), 1.50-1.20 (m, 10H), 0.89 (t, 3H). １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CDCl ３ , ppm): δ9.81 (s, 1H), 7.39 (d, 1H), 6.73 (m, 1H), 4.22 (sext, 1H), 1.76-1.69 (m, 1H), 1.61-1.29 (m, 10H), 0.89 (t, 3H).

[0263]

[0264] Next, 2.92 g (12.9 mmol) of compound (C-2) was dissolved in 25 mL of acetonitrile. 2.41 g (13.5 mmol) of N-bromosuccinimide was slowly added thereto. After stirring at room temperature for 1 hour, water and hexane were added, and the organic layer was washed three times with water. After drying over anhydrous sodium sulfate, the mixture was purified by silica gel chromatography to obtain the compound (yield 99%). １ The resulting compound was confirmed to be compound (D-2) by H-NMR analysis. １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CDCl ３, ppm): δ9.71 (s, 1H), 7.34 (s, 1H), 4.27 (sext, 1H), 1.80-1.71 (m, 1H), 1.64-1.30 (m, 10H), 0.90 (t, 3H).

[0265]

[0266] Separately, compound (F-1) was synthesized in the same manner as in the synthesis of compound (4-3o-31). Subsequently, 4.29 g (5.93 mmol) of compound (F-1) was reacted with 3.71 g (12.2 mmol) of compound (D-2) with reference to the method described in JP 2022-030124 A. Thereafter, the solvent was removed under reduced pressure, and the resulting mixture was purified by silica gel column chromatography to obtain a compound (yield 93%). １ H-NMR analysis confirmed that the resulting compound was compound (G-2). １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CDCl ３ , ppm): δ9.75 (s, 2H), 7.43 (s, 2H), 7.29 (s, 2H), 4.45 (sext, 2H), 1.95-1 .85 (m, 6H), 1.77-1.68 (m, 2H), 1.61-0.92 (m, 42H), 0.71-0.60 (m, 12H).

[0267]

[0268] Separately, compound (I-1) was synthesized in the same manner as in the synthesis of compound (4-3o-31). 0.590 g (0.69 mmol) of compound (G-2) and 0.508 g (2.08 mmol) of compound (I-1) were placed in a reaction vessel, and 10.2 mL of toluene and 20.3 mL of ethanol were added to dissolve the mixture. Then, 0.593 g (3.12 mmol) of p-toluenesulfonic acid monohydrate was added and stirred at 65°C for 4 hours. After cooling, the organic layer was extracted with ethyl acetate and water, and the extract was dried over sodium sulfate. The solids were removed by filtration, and the solvent of the solution was distilled off to obtain a crude product. The crude product was purified by silica gel chromatography to obtain 0.89 g of a solid compound (yield 98%). １H-NMR analysis confirmed that the obtained compound was compound (4-3o-57). １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CDCl ３ , ppm): δ8.73 (s, 2H), 8.69 (s, 2H), 7.91 (s, 2H), 7.61-7.62 (m, 2H), 7.52 (br.s., 2H), 4.53-4.61 (quin, 2H), 1.90-2.03 (m, 6H) ), 1.75-1.83 (m, 2H), 1.52-1.61 (br.s., 2H), 1.46-1.50 (m, 8H), 1.38-1.40 (m, 8H), 0.93-1.02 (m, 22H), 0.64-0.76 (m, 14H).

[0269]

[0270] [Synthesis of Compound (4-3o-116)] Compound (D-1) was synthesized in the same manner as in the synthesis of compound (4-3o-31). Separately, compound (F-2) of the following formula was synthesized by the same method as described in a publicly known document (Nat. Mater., 2012, Vol. 11, p. 44.). Subsequently, with reference to the method described in JP 2022-030124 A, 0.74 g (1.00 mmol) of compound (F-2) and 0.66 g (2.07 mmol) of compound (D-1) were reacted. Thereafter, the solvent was removed under reduced pressure, and the resulting mixture was purified by silica gel column chromatography to obtain a compound (yield 86%). １ H-NMR analysis confirmed that the resulting compound was compound (G-3). １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CDCl ３ , ppm): δ9.75 (s, 2H), 7.41-7.42 (m, 4H), 4.45 (quin, 2H), 1.70-1.84 (m, 8H), 1.50-1.55 (m, 6H), 0.76-1.35 (m, 52H).

[0271]

[0272] Separately, compound (I-5) of the following formula was synthesized by the method described in a publicly known literature (Angew. Chem. Int. Ed., 2017, Vol. 56, p. 3045.). 0.22 g (0.24 mmol) of compound (G-3) and 0.13 g (0.58 mmol) of compound (I-5) were placed in a reaction vessel, and 6.1 mL of chloroform was added to dissolve the mixture. 0.25 mL of pyridine was then added, and the mixture was stirred at 60°C for 3 hours. After allowing the mixture to cool, the solvent was distilled off, and the resulting crude product was purified by silica gel chromatography to obtain 0.30 g of a solid compound (yield 94%). １ H-NMR analysis confirmed that the obtained compound was compound (4-3o-116). １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CDCl ３ , ppm): δ8.69 (s, 2H), 8.52 (dd, 2H), 7.74 (m, 2H), 7.64-7.68 (m, 2H), 7.52 (br.s., 2H), 4.37-4.43 (quin, 2H), 1.75-1.89 (m, 8H), 1.17-1.59 (m, 30H), 1.03-1.07 (m, 10H), 0.89-0.93 (m, 6H), 0.78-0.82 (m, 12H).

[0273]

[0274] [Synthesis of Compound (4-3o-115)] Compound (I-2) was synthesized in the same manner as in the synthesis of compound (4-3o-50). Separately, compound (G-3) was synthesized in the same manner as in the synthesis of compound (4-3o-116). 0.15 g (0.17 mmol) of compound (G-3) and 0.11 g (0.40 mmol) of compound (I-2) were placed in a reaction vessel, and 4.3 mL of chloroform was added to dissolve the mixture. 0.17 mL of pyridine was then added, and the mixture was stirred at 60°C for 3 hours. After allowing the mixture to cool, the solvent was distilled off, and the resulting crude product was purified by silica gel chromatography to obtain 0.18 g of a solid compound (yield 78%). １ H-NMR analysis confirmed that the obtained compound was compound (4-3o-115). １ The H-NMR measurement data is shown below.１ H-NMR (400 MHz, solvent: CDCl ３ , ppm): δ8.74 (s, 2H), 8.69 (s, 2H), 7.91 (s, 2H), 7.53-7.79 (m, 2H), 7.52 (br.s., 2H), 4.37-4.43 (quin, 2H), 1.74-1.91 (m, 8H), 1.13-1.59 (m, 30H), 1.04-1.08 (m, 10H), 0.89-0.93 (m, 6H), 0.79-0.82 (m, 12H).

[0275]

[0276] [Synthesis of Compound (4-3o-237)] 2.00 g (8.87 mmol) of compound (I-4-1) of the following formula was dissolved in 39 mL of THF and cooled in a dry ice acetone bath. 14.7 mL (1.51 M, 22.2 mmol) of n-butyllithium was slowly added dropwise thereto. After stirring for 1 hour, dry ice was added. The mixture was stirred for 0.5 hours under cooling in the dry ice acetone bath, and then stirred at room temperature for 4 hours. Hydrochloric acid was added, followed by addition of ethyl acetate to extract the organic layer. The extract was dried over sodium sulfate, and the solids were removed by filtration. The solvent was then evaporated to obtain 2.37 g of a solid compound (yield 99%). １ H-NMR analysis confirmed that the resulting compound was compound (I-4-2). １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CD ３ OD, ppm): δ8.13 (s, 1H).

[0277]

[0278] 2.37 g (8.80 mmol) of compound (I-4-2) was suspended in 15 mL of acetic anhydride and stirred at 140°C for 9 hours. After allowing to cool, ethyl acetate was added to extract the organic layer. The extract was dried over sodium sulfate, and the solid content was removed by filtration. The solvent of the solution was then distilled off to obtain 2.20 g of a solid compound (yield 99%). １ H-NMR analysis confirmed that the resulting compound was compound (I-4-3). １The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CDCl ３ , ppm): δ8.04 (s, 1H).

[0279]

[0280] 2.20 g (8.75 mmol) of compound (I-4-3), 1.26 g (9.71 mmol) of ethyl acetoacetate, 9.6 mL of triethylamine, and 15 mL of acetic anhydride were mixed and stirred at 65°C for 10 hours. After cooling, 9.6 mL of ice water and 9.6 mL of hydrochloric acid were added, and the mixture was refluxed for 1 hour. After cooling, water and hexane were added to extract the organic layer. The extract was dried over sodium sulfate, and the solids were removed by filtration. The solvent was then distilled off to obtain 1.69 g of a solid compound (yield 77%). １ H-NMR analysis confirmed that the resulting compound was compound (I-4-4). １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CDCl ３ , ppm): δ8.00 (s, 1H), 3.32-3.33 (m, 2H).

[0281]

[0282] 1.69 g (6.77 mmol) of compound (I-4-4), 0.90 g (13.6 mmol) of malononitrile, and 21.1 mL of absolute ethanol were mixed, and then 1.11 g (13.6 mmol) of sodium acetate was added and stirred at room temperature for 12 hours. Next, water and hydrochloric acid were added, and the organic layer was extracted with dichloromethane. The extract was dried over sodium sulfate, and the solids were removed by filtration. The solvent of the solution was then distilled off to obtain 0.56 g of a solid compound (yield 27%). １ H-NMR analysis confirmed that the resulting compound was compound (I-4). １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CDCl ３ , ppm): δ8.69 (s, 1H), 3.81 (s, 2H).

[0283]

[0284] Compound (G-1) was synthesized in the same manner as in the synthesis of compound (4-3o-31). 0.32 g (0.36 mmol) of compound (G-1) and 0.26 g (0.87 mmol) of compound (I-4) were placed in a reaction vessel, 9.1 mL of chloroform was added, and the mixture was stirred to dissolve. 0.37 mL of pyridine was then added, and the mixture was stirred at 60°C for 3 hours. After allowing the mixture to cool, the solvent was distilled off, and the resulting crude product was purified by silica gel chromatography to obtain 0.43 g of a solid compound (yield 83%). １ H-NMR analysis confirmed that the obtained compound was compound (4-3o-237). １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CDCl ３ , ppm): δ8.73 (s, 4H), 7.69-7.70 (m, 2H), 7.41 (br.s., 2H), 4.40-4.44 (quin, 2H), 1.77-2.06 (m, 12H), 1.42-1.58 (br.s., 4H), 1.34-1.38 (m, 8H), 0.89-1.10 (m, 28H), 0.62-0.75 (m, 14H).

[0285]

[0286] [Synthesis of Compound (4-3o-279)] Compound (G-1) was synthesized in the same manner as in the synthesis of Compound (4-3o-31). Separately, commercially available 4H-cyclopenta[2,1-b:3,4-b']dithiophene (0.220 g, 1.23 mmol), commercially available 4-bromo-N,N-dihexylaniline (1.01 g, 2.96 mmol), tris(dibenzylideneacetone)dipalladium(0) (Pd ２ (dba) ３ , 0.057 g, 0.06 mmol), triphenylphosphine (PPh ３To a mixture of 1,2-dimethyl-2,4-dichloro-1,4-dichloro-2 ... １ 1 H-NMR analysis confirmed that the obtained compound was the compound (F-3-1) of the following formula: １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CD ２ Cl ２ , ppm): δ7.10 (d, 2H), 6.95 (d, 2H), 6.92 (dd, 4H), 6.38 (dd, 4H), 3.10 (dd, 8H), 1.48-1.38 (m, 8H), 1.19 (m, 24H), 0.79 (m, 12H).

[0287]

[0288] Compound (F-3-1) (0.13 g, 0.19 mmol) was dissolved in tetrahydrofuran (THF, 7 mL) and cooled in a dry ice acetone bath. Lithium diisopropylamide (0.41 mL, 1.01 M, 0.42 mmol) was slowly added dropwise thereto. After stirring for 0.5 hours, a THF solution of trimethyltin chloride (0.16 mL, 0.42 mmol, 2.65 M) was added dropwise and stirred for 1 hour. After heating, water was added, and then ethyl acetate was added to extract the organic layer. The extract was dried over sodium sulfate, and the solids were removed by filtration. The solvent was then distilled off to obtain a solid compound (F-3) of the following formula. Compound (F-3) was used directly in the next reaction without purification.

[0289] Subsequently, compound (F-3) was reacted with compound (D-1) (0.12 g, 0.39 mmol) by referring to the method described in JP 2022-030124 A. Thereafter, the solvent was removed under reduced pressure, and the resulting mixture was purified by silica gel column chromatography to obtain a solid compound (yield 85%).１ H-NMR analysis confirmed that the resulting compound was compound (G-4). １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CD ２ Cl ２ , ppm): δ9.78 (s, 2H), 7.48 (s, 2H), 7.43 (s, 2H), 7.09 (d, 4H), 6.54 (d, 4H), 4.34 (t, 2H), 3.23 ( t, 8H), 1.90-1.72 (m, 8H), 1.59-1.44 (m, 10H), 1.38-1.24 (m, 34H), 1.05 (t, 6H), 0.92 (m, 18H).

[0290]

[0291] Separately, compound (I-5) was synthesized in the same manner as in the synthesis of compound (4-3o-116). 0.070 g (0.06 mmol) of compound (G-4) and 0.033 g (0.14 mmol) of compound (I-5) were placed in a reaction vessel, and 2.0 mL of chloroform was added to dissolve the mixture. 0.08 mL of pyridine was then added, and the mixture was stirred at 60°C for 3 hours. After allowing the mixture to cool, the solvent was distilled off, and the resulting crude product was purified using silica gel chromatography to obtain 0.086 g of a solid compound (yield 91%). １ H-NMR analysis confirmed that the obtained solid was compound (4-3o-279). １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CD ２ Cl ２ , ppm): δ8.70 (s, 2H), 8.53 (dd, 2H), δ 7.70-7.66 (m, 4H), 7.57 (s, 2H), 7.13 (d, 4H), 6.58 (d, 4H), 4.47 (t, 2H) , 3.26 (t, 8H), 1.93-1.77 (m, 8H), 1.63-1.47 (m, 10H), 1.40-1.25 (m, 34H), 1.08 (t, 6H), 0.94-0.90 (m, 18H).

[0292]

[0293] [Synthesis of Compound (4-3o-280)] Compound (G-4) was synthesized in the same manner as compound (4-3o-279). Separately, compound (I-2) was synthesized in the same manner as compound (4-3o-50). 0.062 g (0.05 mmol) of compound (G-4) and 0.033 g (0.13 mmol) of compound (I-2) were placed in a reaction vessel, 1.8 mL of chloroform was added, and the mixture was stirred to dissolve. 0.07 mL of pyridine was then added, and the mixture was stirred at 60°C for 3 hours. After allowing the mixture to cool, the solvent was distilled off, and the resulting crude product was purified using silica gel chromatography to obtain 0.073 g of a solid compound (yield 83%). １ H-NMR analysis confirmed that the obtained compound was compound (4-3o-280). １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CD ２ Cl ２ , ppm): δ8.61 (s, 2H), 8.57 (s, 2H), δ 7.79 (s, 2H), 7.57 (s, 2H), 7.39 (br.s, 2H), 7.01 (d, 4H), 6.67 (d, 4H), 4.34 (t , 2H), 3.13 (t, 8H), 1.80-1.65 (m, 8H), 1.51-1.33 (m, 10H), 1.29-1.20 (m, 34H), 0.95 (t, 6H), 0.82-0.77 (m, 18H).

[0294]

[0295] [Synthesis of Compound (4-3o-281)] Compound (G-4) was synthesized in the same manner as compound (4-3o-279). Separately, compound (I-1) was synthesized in the same manner as compound (4-3o-31). 0.085 g (0.07 mmol) of compound (G-4) and 0.53 g (0.22 mmol) of compound (I-1) were placed in a reaction vessel, and 1.1 mL of toluene and 2.1 mL of ethanol were added to dissolve the mixture. 0.062 g (0.33 mmol) of p-toluenesulfonic acid monohydrate was then added and stirred at 65°C for 3 hours. After cooling, the organic layer was extracted with chloroform and water, the extract was dried over sodium sulfate, and the solids were removed by filtration. The solvent was then distilled off. The resulting crude product was purified using silica gel chromatography to obtain 0.103 g of a solid compound (yield 87%). １ H-NMR analysis confirmed that the obtained compound was compound (4-3o-281). １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CD ２ Cl ２ , ppm): δ8.59 (s, 2H), 8.52 (s, 2H), δ 7.76 (s, 2H), 7.56 (s, 2H), 7.43 (br.s, 2H), 7.04 (d, 4H), 6.58 (d, 4H), 4.34 (t , 2H), 3.13 (t, 8H), 1.80-1.62 (m, 8H), 1.50-1.31 (m, 10H), 1.27-1.12 (m, 34H), 0.94 (t, 6H), 0.84-0.76 (m, 18H).

[0296]

[0297] [Synthesis of Compound (4-3x-2)] 0.50 g (0.57 mmol) of compound (G-1) and 0.42 g (1.25 mmol) of tributyl(1,3-dioxolan-2-ylmethyl)phosphonium bromide were placed in a reaction vessel and added to 32.4 mL of dehydrated tetrahydrofuran under a nitrogen atmosphere. The reaction solution was cooled to 0°C, and then 0.069 g (1.71 mmol) of sodium hydride was added and stirred for 30 minutes. After stirring overnight at room temperature, the solution was cooled again to 0°C, and 6.5 mL of dilute hydrochloric acid was added dropwise, followed by stirring at room temperature for 4 hours. The organic layer was extracted with chloroform and water, and the extract was dried over sodium sulfate. The solids were removed by filtration, and the solvent was evaporated. The resulting crude product was purified using silica gel chromatography to obtain 0.47 g of a solid compound (yield 89%). １ H-NMR analysis confirmed that the resulting compound was compound (G-5). １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CDCl ３ , ppm): δ9.60 (d, 2H), 7.43 (d, 2H), 7.16 (m, 2H), 7.03 (s, 2H), 6.43 (dd, 2H), 4.22 (q, 2H), 1.68 -1.94 (m, 12H), 1.29-1.57 (m, 12H), 0.88-1.05 (m, 28H), 0.69-0.74 (m, 8H), 0.61-0.65 (m, 6H).

[0298]

[0299] 0.044 g (0.047 mmol) of compound (G-5) and 0.030 g (0.011 mmol) of compound (I-2) were placed in a reaction vessel, 1.95 mL of chloroform was added, and the mixture was stirred to dissolve. 0.05 mL of pyridine was then added, and the mixture was stirred at room temperature for 3 hours. The solvent was distilled off, and the resulting crude product was purified by silica gel chromatography to obtain 0.028 g of a solid compound (yield 42%). １ H-NMR analysis confirmed that the resulting compound was compound (4-3x-2). １ The H-NMR measurement data is shown below. １H-NMR (400MHz, solvent: CDCl3, ppm): δ8.74 (s, 2H), 8.41-8.56 (m, 4H), 7.90 (s, 2H), 7.43 (d, 2H), 7.33 (s, 2H), 7 .12 (m, 2H), 4.32 (q, 2H), 1.72-2.01 (m, 12H), 1.34-1.57 (m, 12H), 0.90-1.09 (m, 28H), 0.64-0.75 (m, 14H).

[0300]

[0301] [Synthesis of Compound (4-3x-3)] 0.155 g (0.17 mmol) of compound (G-5) and 0.109 g (0.45 mmol) of compound (I-1) were placed in a reaction vessel, and 3.6 mL of toluene and 7.2 mL of ethanol were added to dissolve the compound. 0.104 g (0.55 mmol) of p-toluenesulfonic acid monohydrate was then added and stirred at room temperature for 3 hours. The organic layer was extracted with chloroform and water, and the extract was dried over sodium sulfate. The solids were then removed by filtration, and the solvent was evaporated to obtain a solid. The resulting crude product was purified using silica gel chromatography to obtain 0.17 g of a solid compound (yield 74%). １ H-NMR analysis confirmed that the resulting compound was compound (4-3x-3). １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CDCl ３ , ppm): δ8.73 (s, 2H), 8.40-8.55 (m, 4H), 7.90 (s, 2H), 7.43 (d, 2H), 7.34 (s, 2H), 7.12 (s, 2H), 4.32 (q, 2H), 1.72-2.00 (m, 12H), 1.35-1.58 (m, 12H), 0.91-1.09 (m, 28H), 0.64-0.74 (m, 14H).

[0302]

[0303] [Synthesis of Compound (4-3o-3x-6)] 0.53 g (0.63 mmol) of compound (G-2) and 0.26 g (0.71 mmol) of tributyl(1,3-dioxolan-2-ylmethyl)phosphonium bromide were placed in a reaction vessel and added to 30 mL of dehydrated tetrahydrofuran under a nitrogen atmosphere. The reaction solution was cooled to 0°C, and 0.037 g (0.92 mmol) of sodium hydride was added and stirred for 30 minutes. After stirring overnight at room temperature, the solution was cooled again to 0°C, and 3.5 mL of dilute hydrochloric acid was added dropwise. The mixture was then stirred at room temperature for 4.5 hours. The organic layer was extracted with chloroform and water, and the extract was dried over sodium sulfate. The solids were removed by filtration, and the solvent was evaporated. The resulting crude product was purified using silica gel chromatography to obtain 0.22 g of the solid compound (40% yield). １ H-NMR analysis confirmed that the resulting compound was compound (G-6). １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CDCl ３ , ppm): δ9.75 (s, 1H), 9.60 (d, 1H), 7.41-7.42 (m, 2H), 7.29 (s, 1H), 7.16 (d, 1H), 7.05 (s, 1H), 6.44 (dd, 1H), 4.37-4.48 (m, 2H), 1.85-1.95 (m, 6H), 1.67-1.77 (m, 2H), 1.35-1.58 (m, 18H), 0.91-0.99 (m, 22H), 0.71-0.80 (m, 8H), 0.63 (t, 6H).

[0304]

[0305] 0.22 g (0.25 mmol) of compound (G-6) and 0.18 g (0.74 mmol) of compound (I-1) were placed in a reaction vessel, and 3.5 mL of toluene and 7.0 mL of ethanol were added to dissolve the compound. 0.21 g (1.1 mmol) of p-toluenesulfonic acid monohydrate was then added and stirred at room temperature for 3.5 hours. The organic layer was extracted with chloroform and water, and the extract was dried over sodium sulfate. The solids were then removed by filtration, and the solvent was evaporated to obtain a solid. The resulting crude product was purified using silica gel chromatography to obtain 0.27 g of the solid compound (yield 82%). １ H-NMR analysis confirmed that the obtained compound was compound (4-3o-3x-6). １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CDCl ３ , ppm): δ8.75 (s, 1H), 8.73 (s, 1H), 8.68 (s, 1H), 8.50-8.57 (m, 1H), 8.43 (d, 1H) H), 7.91 (s, 1H), 7.90 (s, 1H), 7.60-7.62 (m, 1H), 7.42-7.50 (m, 2H), 7.33 (m, 1 H), 7.14 (m, 1H), 4.56 (q, 1H), 4.50 (q, 1H), 1.92-2.03 (m, 6H), 1.72-1.83 (m, 2H), 1.45-1.60 (m, 10H), 1.39 (m, 8H), 0.94-1.02 (m, 22H), 0.63-0.75 (m, 14H)

[0306]

[0307] [Synthesis of Compound (N-1)] Compound (G'-2) of the following formula was synthesized by the method described in a known literature (Adv. Energy Mater., 2018, Vol. 8, p. 1801212.). Separately, compound (I-1) was synthesized in the same manner as in the synthesis of compound (4-3o-31). 0.244 g (0.29 mmol) of compound (G'-2) and 0.350 g (1.43 mmol) of compound (I-1) were placed in a reaction vessel, and 7.0 mL of toluene and 14 mL of ethanol were added to dissolve the mixture. 0.409 g (2.15 mmol) of p-toluenesulfonic acid monohydrate was then added and stirred at 65°C for 1 hour. After cooling, the organic layer was extracted with ethyl acetate and water, and the extract was dried over sodium sulfate. The solids were then removed by filtration, and the solvent of the solution was evaporated to obtain a solid. The resulting solid was dispersed in ethanol and filtered to obtain 0.288 g of a compound as a black solid (yield 77%). １ H-NMR analysis confirmed that the obtained compound was compound (N-1). １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CDCl ３ , ppm): δ8.75 (s, 2H), 8.73 (s, 2H), 7.92 (s, 2H), 7.63-7.64 (m, 2H), 7.51 (br.s., 2H), 4.17 (d, 4H), 1.87- 2.03 (m, 6H), 1.57-1.69 (m, 8H), 1.40-1.42 (m, 8H), 0.89-1.05 (m, 28H), 0.70-0.74 (m, 8H), 0.65 (t, 6H).

[0308]

[0309] [Synthesis of Compound (N-2)] Compound (N-2) of the following formula was synthesized by the method described in a known literature (Chem. Commun., 2022, Vol. 58, p. 6340).

[0310]

[0311] [Synthesis of Compound (N-3)] Compound (N-3) of the following formula was synthesized by the method described in Japanese Patent No. 7448103.

[0312]

[0313] The compound (N-4) will be described later.

[0314] [Synthesis of Compound (N-5)] Using a commercially available compound, a compound (F-2) of the following formula was synthesized by the same method as described in Journal of Materials Chemistry, 2011, Vol. 21, p. 3895. １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CDCl ３ , ppm): δ6.99 (s, 2H), 4.45 (sep, 1H), 2.07-1.98 (m, 2H), 1.86-1.79 (m, 2H), 1.34-1.06 (m, 24H), 0.84 (t, 6H), 0.34 (s, 18H).

[0315]

[0316] Subsequently, 1.70 g (2.29 mmol) of compound (F-2) was reacted with 1.50 g (4.7 mmol) of compound (D-1) by referring to the method described in JP 2022-030124 A. Thereafter, the solvent was removed under reduced pressure, and the resulting mixture was purified by silica gel column chromatography to obtain a compound (yield 93%). １ The resulting compound was confirmed to be compound (G-7) by H-NMR analysis. １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CDCl ３ , ppm): δ9.75 (s, 2H), 7.42 (s, 2H), 7.40 (s, 2H), 4.29 (quin, 2H), 4.19 (sep, 1H), 2.10-1.95 (m, 2H), 1.90-1.74 (m, 10H), 1.54-1.34 (m, 4H), 1.34-1.16 (m, 32H), 1.04 (t, 6H), 0.89 (t, 6H), 0.81 (t, 6H).

[0317]

[0318] 0.22 g (0.24 mmol) of compound (G-7) and 0.11 g (0.58 mmol) of compound (I-6) were placed in a reaction vessel, and 6.2 mL of chloroform was added and the mixture was stirred to dissolve, after which 0.25 mL of pyridine was added and the mixture was stirred for 3 hours at 60° C. The solvent was distilled off to obtain a crude product, which was purified by silica gel chromatography to obtain 0.27 g of a solid compound (yield 90%). １ H-NMR analysis confirmed that the obtained compound was the comparative material (N-5). １ The H-NMR measurement data is shown below. １ H-NMR (400 MHz, solvent: CDCl ３ , ppm): δ8.68 (s, 2H), 8.64-8.66 (m, 2H), 7.88-7.90 (m, 2H), 7.69-7.75 (m, 4H), 7.56 (s, 2H), 7.49 (br.s., 2H), 4 .42 (q, 2H), 4.25 (m, 1H), 2.04-2.13 (m, 2H), 1.78-1.99 (m, 10H), 1.06-1.64 (m, 42H), 0.91 (t, 6H), 0.80 (t, 6H).

[0319]

[0320] Example 1 Preparation of Ink Composition A compound represented by the following formula (P-1) (weight average molecular weight: 80,000) was used as the p-type semiconductor material. Compound (4-3o-31) was used as the n-type semiconductor material. 0.11 g of the p-type semiconductor material and 0.13 g of the n-type semiconductor material were dissolved in 9.68 mL of o-xylene with heating to prepare a composition for forming an active layer (hereinafter also referred to as the "ink composition"), which is an organic semiconductor ink. In the ink composition, the mass ratio of the n-type semiconductor material to the p-type semiconductor material (n-type semiconductor material / p-type semiconductor material) was 1.2. The solids concentration of the ink composition was 25 mg / mL.

[0321]

[0322] The storage stability of the obtained ink compositions was evaluated as follows. <Evaluation> (Evaluation of storage stability) Immediately after preparation, the ink compositions were stored in a nitrogen atmosphere at room temperature (25°C), and the presence or absence of precipitates was visually confirmed, and the storage stability was evaluated according to the following evaluation criteria. The results are shown in Table 1. A: No precipitates were observed even 24 hours after the ink composition was prepared. B: Precipitation or gelation occurred within 24 hours after the ink composition was prepared. Or, the materials did not dissolve, and an ink composition could not be prepared.

[0323] [Examples 2 to 9] Ink compositions were prepared in the same manner as in Example 1, except that compound (4-3o-50), compound (4-3o-57), compound (4-3o-116), compound (4-3o-115), compound (4-3o-237), compound (4-3o-279), compound (4-3o-280), and compound (4-3o-281) were used as the n-type semiconductor material, and the storage stability was evaluated. The results are shown in Table 1. [Examples 22 to 24] Ink compositions were prepared in the same manner as in Example 1, except that compound (4-3x-2), compound (4-3x-3), and compound (4-3o-3x-6) were used as the n-type semiconductor material, and the storage stability was evaluated. The results are shown in Table 1.

[0324] [Comparative Examples 1 to 3] Ink compositions were prepared in the same manner as in Example 1, except that compound (N-1), compound (N-2), or compound (N-3) was used as the n-type semiconductor material, and the storage stability was evaluated. The results are shown in Table 1. [Comparative Examples 4 and 5] Ink compositions were prepared in the same manner as in Example 1, except that compound (N-4) or compound (N-5), which will be described later, was used as the n-type semiconductor material, and the storage stability was evaluated. The results are shown in Table 1.

[0325]

[0326] As is clear from the results in Table 1, compound (1) of the present invention has better solubility than the comparative compounds, compound (N-1), compound (N-2), and compound (N-3), and the ink composition containing the compound of the present invention has excellent storage stability.

[0327] Example 10 Production of Photoelectric Conversion Element (Formation of Hole Transport Layer) A transparent conductive film of indium tin oxide (ITO) was patterned on a glass substrate as a transparent substrate. The surface of the ITO substrate was treated with ozone for 10 minutes using an ultraviolet ozone cleaner (manufactured by Japan Laser Electronics Co., Ltd., product name "NL-UV253"). Separately, 60 mg of a polytriarylamine compound (hole transport polymer) represented by the following formula (H-1) was dissolved in 1 mL of anisole to prepare a hole transport layer-forming composition. The hole transport layer-forming composition was spin-coated on the transparent electrode of the ozone-treated ITO substrate at a rotation speed of 1000 rpm for 60 seconds, and then heated and dried at 240°C for 30 minutes to form a hole transport layer with a thickness of 300 nm.

[0328]

[0329] (Formation of Photoelectric Conversion Layer) An active layer-forming composition (ink composition) was prepared in the same manner as in Example 1. The obtained active layer-forming composition was spin-coated onto the hole transport layer at 1000 rpm, and then heat-treated (thermal annealing treatment) at 120°C for 10 minutes to form a photoelectric conversion layer (active layer) made of an organic thin film with a thickness of 150 nm.

[0330] (Formation of electron transport layer and metal electrode) On the photoelectric conversion layer, C60 fullerene (manufactured by Frontier Carbon Co., Ltd.) was formed as an electron transport material in a vacuum to form a 40 nm thick electron transport layer. Next, on the electron transport layer, aluminum was formed as a metal electrode material in a vacuum to form a 100 nm thick metal electrode, thereby obtaining a photoelectric conversion element. The obtained photoelectric conversion element was evaluated as follows.

[0331] <Evaluation> (Evaluation of external quantum efficiency (EQE)) The photoelectric conversion element was irradiated with a xenon lamp under application of -5 V, and the external quantum efficiency was measured using an action spectrum measurement device (manufactured by Peccell Technologies, Inc., product name "PEC-S20"). The results of the external quantum efficiency at a wavelength of 1100 nm are shown in Table 2. The values ​​shown in Table 2 are relative values ​​(relative EQE values) when the external quantum efficiency at a wavelength of 1100 nm for the photoelectric conversion element obtained in Comparative Example 6 described below is taken as 1.0.

[0332] (Measurement of Dark Current) The dark current was measured using a photoelectric conversion element when a voltage of -5 V was applied. A high-precision current measuring device (manufactured by Keithley Instruments, product name "Keithley 6482") was used to measure the dark current. The results are shown in Table 2. The values ​​shown in Table 2 are relative values ​​(relative dark current values) when the dark current in the photoelectric conversion element obtained in Comparative Example 6 described below is set to 1.00.

[0333] [Examples 11 to 13] Photoelectric conversion elements were manufactured in the same manner as in Example 10, except that compound (4-3o-50), compound (4-3o-57), or compound (4-3o-237) was used as the n-type semiconductor material, and the external quantum efficiency was measured when a voltage of -5 V was applied. The results of the external quantum efficiency at a wavelength of 1100 nm are shown in Table 2. The values ​​shown in Table 2 are relative values ​​(relative EQE values) when the external quantum efficiency at a wavelength of 1100 nm for the photoelectric conversion element obtained in Comparative Example 6 described below was taken as 1.0. Furthermore, the dark current of the obtained photoelectric conversion elements was measured when a voltage of -5 V was applied in the same manner as in Example 10. The results are shown in Table 2. The values ​​shown in Table 2 are relative values ​​(relative dark current values) when the dark current for the photoelectric conversion element obtained in Comparative Example 6 described below was taken as 1.00.

[0334] Comparative Example 6 A photoelectric conversion element was produced in the same manner as in Example 10, except that a compound represented by the following formula (N-4) was used as the n-type semiconductor material, and the external quantum efficiency when −5 V was applied and the dark current when −5 V was applied were measured.

[0335]

[0336] Comparative Example 7 A photoelectric conversion element was produced in the same manner as in Example 10, except that the compound represented by formula (N-5) was used as the n-type semiconductor material, and the external quantum efficiency was measured when a voltage of −5 V was applied, resulting in no photoresponsiveness. Furthermore, since there was no photoresponsiveness in the external quantum efficiency measurement, the dark current was not measured.

[0337] Comparative Example 8 An attempt was made to produce a photoelectric conversion element in the same manner as in Example 10, except that compound (N-1) was used as the n-type semiconductor material. However, compound (N-1) was not dissolved, and an active layer-forming composition (ink composition) could not be prepared, and therefore a photoelectric conversion element could not be produced.

[0338]

[0339] As is clear from the results in Table 2, the photoelectric conversion elements obtained in Examples 10 to 13 had significantly higher EQE at 1100 nm, more than twice that of the photoelectric conversion element obtained in Comparative Example 6, and had higher sensor sensitivity on the longer wavelength side. Furthermore, the photoelectric conversion elements obtained in Examples 10 to 13 had a dark current less than 0.5 times that of the photoelectric conversion element obtained in Comparative Example 6, and significantly lower noise. The photoelectric conversion element obtained in Comparative Example 7 had no photoresponsiveness. When the A portion of the compound having an A-D-A structure is general formula (3o) and the terminal six-membered ring of general formula (3o) is unsubstituted, the electron-withdrawing property of the A portion is low, resulting in a shallower LUMO level. As a result, it is believed that the HOMO-LUMO gap did not decrease, and the absorption wavelength did not extend to the longer wavelength side. Furthermore, in Comparative Example 8, which used compound (N-1), it was not possible to produce a photoelectric conversion element. These results demonstrate that the compound (1) of the present invention can achieve both high sensor sensitivity in the long wavelength region of absorption wavelength and low dark current reduction.

[0340] [Examples 14 and 15] Photoelectric conversion elements were produced in the same manner as in Example 10, except that compound (4-3o-116) or (4-3o-115) was used as the n-type semiconductor material, and the external quantum efficiency when −5 V was applied and the dark current when −5 V was applied were measured. As a result, photoelectric conversion ability was confirmed for light of 400 nm to 1100 nm.

[0341] [Examples 16 to 18] Photoelectric conversion elements were produced in the same manner as in Example 10, except that compound (4-3o-279), compound (4-3o-280), or compound (4-3o-281) was used as the n-type semiconductor material, and the external quantum efficiency when −5 V was applied and the dark current when −5 V was applied were measured. As a result, photoelectric conversion ability was confirmed for light of 400 nm to 1100 nm.

[0342] Example 19 A photoelectric conversion element was produced in the same manner as in Example 10, except that compound (4-3x-2) was used as the n-type semiconductor material, and the external quantum efficiency when −5 V was applied and the dark current when −5 V was applied were measured. As a result, photoelectric conversion ability was confirmed for light of 400 nm to 1350 nm.

[0343] Example 20 A photoelectric conversion element was produced in the same manner as in Example 10, except that compound (4-3x-3) was used as the n-type semiconductor material, and the external quantum efficiency when −5 V was applied and the dark current when −5 V was applied were measured. As a result, photoelectric conversion ability was confirmed for light of 400 nm to 1350 nm.

[0344] Example 21 A photoelectric conversion element was produced in the same manner as in Example 10, except that compound (4-3o-3x-6) was used as the n-type semiconductor material, and the external quantum efficiency when −5 V was applied and the dark current when −5 V was applied were measured. As a result, photoelectric conversion ability was confirmed for light of 400 nm to 1300 nm.

[0345] The compound of the present invention has high solubility and can shift the absorption wavelength to a longer wavelength without impairing the photoelectric conversion properties, and is therefore useful as a semiconductor material used in photoelectric conversion elements.

[0346] REFERENCE SIGNS LIST 10 Photoelectric conversion element 11 Transparent substrate 12 Transparent electrode 13 Hole transport layer 14 Photoelectric conversion layer 15 Electron transport layer 16 Metal electrode

Claims

1. A compound represented by the following general formula (1): A−D−A ··· (1) In general formula (1), A is independently a group represented by any one of the following general formulas (3a), (3c) to (3y), D is an electron-donating group in which four or more rings are connected in the main chain direction of the molecule, and includes a structure represented by the following general formula (2). In general formulas (3a), (3c) to (3y), Z １ to Z ７ are each independently an oxygen atom, a sulfur atom or a dicyanomethylene group, R ３ are each independently a hydrogen atom or an alkyl group, R ４ are each independently a methyl group or a trifluoromethyl group, X １ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or a cyano group, Ar is an aryl group, V is each independently C−X ２ or a nitrogen atom, Q ２ are each independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or CR ５ =CR ５ and Q ３ is a carbon atom substituted with a sulfur atom, an alkyl group or an aryl group, a nitrogen atom substituted with an alkyl group or an aryl group, a silicon atom substituted with an alkyl group or an aryl group or a germanium atom substituted with an alkyl group or an aryl group, X ２ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or a cyano group, R ５ are each independently a hydrogen atom, an alkyl group, an alkoxy group or an ester group (however, in general formula (3o), one of Z ４ and Z ５ is an oxygen atom and the other is a dicyanomethylene group, V are both C−X ２ and X １ and X ２ are not both hydrogen atoms). In general formula (2), Q １ is an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or CR ２ =CR ２ and R １ is each independently a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and R １ Among them, at least two are an alkyl group, an aryl group or a heteroaryl group. However, when at least two are alkyl groups, the carbon number of at least one alkyl group is 2 or more. Further, a plurality of R １ may form a ring structure. R ２ is each independently a hydrogen atom, an alkyl group, an alkoxy group or an ester group. The ring structure containing Q １ may further form a ring structure with an adjacent structure.

2. The compound according to claim 1, wherein D in the general formula (1) contains two structures represented by the general formula (2).

3. The compound according to claim 1, wherein the structure represented by the general formula (2) is a structure represented by the following general formula (2'). In the general formula (2'), Q １ is an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or CR ２ = CR ２ and R １ are each independently an alkyl group, an aryl group or a heteroaryl group. However, when all of R １ are alkyl groups, the carbon number of at least one alkyl group is 2 or more. Also, a plurality of R １ may form a ring structure. R ２ are each independently a hydrogen atom, an alkyl group, an alkoxy group or an ester group.

4. Q in the general formula (2') １ is a sulfur atom, and R １ is each an alkyl group, the compound according to claim 3.

5. Q in the general formula (2) １ is an oxygen atom or a sulfur atom, and R １ is each independently a hydrogen atom or an alkyl group, and among R １ at least two are alkyl groups. The compound according to claim 1.

6. In the general formulas (3a), (3c) to (3y), Z １ is a dicyanomethylene group, Z ２ is an oxygen atom, Z ３ is a sulfur atom or a dicyanomethylene group, Z ４ and Z ５ one of them is an oxygen atom and the other is a dicyanomethylene group, Z ６ and Z ７ are oxygen atoms, the compound according to claim 1.

7. The compound according to claim 1, wherein D in the general formula (1) is a group represented by any one of the following general formulas (4) to (6). In the general formulas (4) to (6), W is C-(R ６ ) ２ , Si-(R ６ ) ２ , Ge-(R ６ ) ２ , N-R ６ , O-CR ６ , or CR ６ -O, and each R ６ is independently an alkyl group, an optionally substituted aryl group or an optionally substituted heteroaryl group, and E, J, K, L are each independently composed of 1 to 5 rings and are an aryl group, a cyclopentadienyl group or a heteroaryl group containing an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, a germanium atom or a selenium atom, G is a heteroaryl ring containing a nitrogen atom, s is a number from 0 to 1, and t is a number from 0 to 3. However, at least one of J and E in the general formula (4) contains the structure represented by the general formula (2), at least one of J, K and L in the general formula (5) contains the structure represented by the general formula (2), and at least one of J and K in the general formula (6) contains the structure represented by the general formula (2).

8. In the general formulas (4) to (6), -(E) ｔ - is an aryl group or heteroaryl group consisting of 3 to 5 condensed rings selected from optionally substituted thiophene, furan, selenophene, thienothiophene, bithiophene or terthiophene, or optionally substituted benzene, thiophene, furan, selenophene, cyclopentadiene, silole and pyrrole; J and K are each independently an optionally substituted phenyl group, furan, thiophene, selenophene or thienothiophene; L is an optionally substituted phenyl group, naphthyl group, thiophene, thienothiophene or heteroaryl group consisting of 1 to 3 condensed rings selected from benzene, thiophene, furan, selenophene, cyclopentadiene, silole and pyrrole; G is thiadiazole, selenadiazole, triazole, benzoquinoxaline or diphenylpyrazine. The compound according to claim 7 9. The compound according to claim 1, which is represented by the following general formula (7). In the general formula (7), each A is independently a group represented by any one of the general formulas (3a), (3c) to (3y), and Y １ ~Y ４ are each independently a hydrogen atom, an alkyl group, an alkoxy group or an ester group, M is a carbon atom substituted with an alkyl group or an aryl group, a nitrogen atom substituted with an alkyl group or an aryl group, a silicon atom substituted with an alkyl group or an aryl group or a germanium atom substituted with an alkyl group or an aryl group, Q １ are each independently an oxygen atom, a sulfur atom, a selenium atom, N-R ３ or CR ６ =CR ６ is, Ar ２ are each independently an aryl group or a heteroaryl group, or Ar ２ may not have, and the total number of rings of two Ar ２ is 0 to 3, and a and b each represent 1 to 2.

10. The compound according to claim 1, which is represented by the following general formula (4a). In the general formula (4a), each A is independently a group represented by any one of the general formulas (3a), (3c) to (3y), and Y １ ~Y ４ are each independently a hydrogen atom, an alkyl group, an alkoxy group or an ester group, and among Y １ ~Y ４ at least one is an alkoxy group branched at the 1-position, and M is a carbon atom substituted with an alkyl group or an aryl group, a nitrogen atom substituted with an alkyl group or an aryl group, a silicon atom substituted with an alkyl group or an aryl group, or a germanium atom substituted with an alkyl group or an aryl group.

11. The compound according to claim 10, wherein M in the general formula (4a) is a carbon atom substituted with an alkyl group or an aryl group, a nitrogen atom substituted with an alkyl group or an aryl group, or a silicon atom substituted with an alkyl group or an aryl group.

12. Y in the general formula (4a) １ is an alkoxy group branched at the 1-position, and one of Y ２ and Y ４ is a hydrogen atom and the other is an alkyl group, an alkoxy group or an ester group, and Y ３ is a hydrogen atom, the compound according to claim 10 13. Y in the general formula (4a) １ and Y ２ are each independently an alkoxy group branched at the 1-position, and Y ３ and Y ４ is a hydrogen atom. The compound according to claim 10 14. In the general formula (4a), each A is independently a group represented by any one of the general formulas (3m), (3n), (3o), (3s), (3v), (3w), (3x), and (3y), and Y １ and Y ２ are the same and are alkoxy groups branched at the 1-position, and Y ３ and Y ４ are hydrogen atoms, and M is a carbon atom substituted with an alkyl group or an aryl group or a nitrogen atom substituted with an alkyl group or an aryl group. The compound according to claim 10.

15. Z in the general formulas (3m), (3n), (3o), (3s), (3v), (3w), (3x) and (3y) ４ and Z ５ wherein one of them is an oxygen atom and the other is a dicyanomethylene group, X １ is a fluorine atom, a chlorine atom or a cyano group, V is C-X ２ or a nitrogen atom, X ２ is a hydrogen atom, and the compound according to claim 14 16. A composition containing the compound according to any one of claims 1 to 15.

17. A film containing the compound according to any one of claims 1 to 15.

18. A photoelectric conversion element provided with the film according to claim 17.

19. A CMOS image sensor provided with the photoelectric conversion element according to claim 18.

Images