Compound, film, photoelectric conversion element, image sensor, fingerprint sensor and pulse wave sensor

Abstract

To provide a compound useful for photoelectric conversion elements with excellent capabilities in intermediate production stability, frontier orbital energy level control, and absorption wavelength control.SOLUTION: The present invention provides a compound represented by A=CH-L-D, wherein D is a heterocyclic group including a thienyl structure, with a thiophene ring being substituted with a mono- or di-substituted amino group having a fluorine-substituted aryl group and / or a fluorine-substituted heteroaryl group; L is a linking group, a single or fused ring including a sulfur-containing heteroaryl ring, or a polycyclic system formed through the combination of these rings; and A is a group represented by formula (2) (Z: a benzene ring or a naphthalene ring optionally having a substituent, and X: an oxygen atom or a dicyanomethylene group).SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a compound, a film, a photoelectric conversion element, an image sensor, a fingerprint sensor, and a pulse wave sensor. [Background technology]

[0002] As we enter the era of digital transformation, there are increasing opportunities to use sensors to obtain data necessary for big data analysis, customization proposals, and more. Photoelectric conversion elements, as sensors capable of converting light into electricity, are used in image sensors, fingerprint sensors, pulse wave sensors, etc. As a result, photoelectric conversion elements are beginning to be incorporated into a variety of devices, and there is an increasing need for sensors suited to each device.

[0003] Against this background, in order to make photoelectric conversion elements suitable for incorporation into a variety of devices, a new lineup of materials contained within the elements (p-type semiconductor materials, n-type semiconductor materials, hole transport materials, electron transport materials, etc.) is required. When the p-type semiconductor material in the photoelectric conversion layer absorbs light in addition to transporting holes, it is known that the material has a structure in which an electron-donating moiety and a potential-withdrawing moiety are linked in order to improve light absorption (e.g., Patent Document 1 and Non-Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 5520560 [Non-patent literature]

[0005] [Non-Patent Document 1] J. Mater. Chem. C, 2016, 4, 1117 Summary of the Invention [Problem to be solved by the invention]

[0006] Conventionally, the light absorption, absorption wavelength, mobility, and energy level of the frontier orbital of p-type semiconductor materials have been controlled by adjusting the strength of electron donating and potential attracting properties, but there is a limit to the range of control. For example, if the electron donating property is increased too much, the p-type semiconductor material becomes more susceptible to oxygen oxidation and becomes unstable. On the other hand, if the electron attracting property is increased too much, the difference in the LUMO level between the p-type semiconductor material and the n-type semiconductor becomes too small, and the photoelectric conversion ability decreases. As a result, it is not possible to fully meet the above-mentioned sensor needs, and new material designs are required.

[0007] A primary object of the present invention is to provide a compound having excellent properties in terms of production stability of an intermediate, control of the energy level of a frontier orbital, and control of absorption wavelength, and a film, a photoelectric conversion element, an image sensor, a fingerprint sensor, and a pulse wave sensor each using said compound. [Means for solving the problem]

[0008] In view of the above-mentioned problems, the present inventors have investigated the manufacturing stability, thermal stability, sublimation property, control of the energy level of the frontier orbital, control of the absorption wavelength, carrier transport property, etc. of the intermediate of the material. Therefore, they came up with the idea of ​​introducing an electron-withdrawing fluorine atom, which has the opposite property, into an amino group, which is an electron-donating site, which has not been investigated in the conventional technology. As a result, they found that a compound containing a thienyl structure substituted with an amino group having an aryl ring or heteroaryl ring substituted with a fluorine atom is particularly useful as a p-type semiconductor material for a photoelectric conversion element, and have completed the present invention.

[0009] That is, the present invention includes the following configurations. [1] A compound represented by the following general formula (1):

[0010] [ka]

[0011] (In the formula (1), D is a monocyclic or fused-ring heterocyclic group containing a thienyl structure, one hydrogen atom of a thiophene ring contained in the heterocyclic group is substituted with an N-monosubstituted amino group or an N,N-disubstituted amino group, and the N-monosubstituted amino group or the N,N-disubstituted amino group has a substituent selected from an alkyl group in which one or more hydrogen atoms may be substituted, an aryl group in which one or more hydrogen atoms may be substituted, and a heteroaryl group in which one or more hydrogen atoms may be substituted, At least one of the substituents is the aryl group or the heteroaryl group, and at least one hydrogen atom of the aryl ring or heteroaryl ring contained in at least one of the substituents is substituted with a fluorine atom. L is a bonding group, a monocyclic or condensed ring containing a sulfur-containing heteroaryl ring, or a polycyclic ring in which two or more rings selected from the monocyclic and condensed rings are bonded. A is a group represented by the following general formula (2). When L in the formula (1) is a bonding group, the group represented by A=CH- bonds to the thiophene ring in D.

[0012] [ka]

[0013] (In the formula (2), Z is a benzene ring or a naphthalene ring in which one or more hydrogen atoms may be substituted. X is an oxygen atom or a dicyanomethylene group.) [2] The compound according to [1], wherein D is any one of groups represented by the following general formulae (3a) to (3c):

[0014] [ka]

[0015] (In the above formulas (3a) to (3c), R 1 and R 2 are each independently a hydrogen atom, a deuterium atom, an alkyl group, an alkoxy group, C(=O)OR (wherein R is an alkyl group or an aryl group), or an amino group. 1and Ar 2 are each independently an alkyl group in which one or more hydrogen atoms may be substituted, an aryl group in which one or more hydrogen atoms may be substituted, or a heteroaryl group in which one or more hydrogen atoms may be substituted, and at least one of them is an aryl group in which at least one hydrogen atom is substituted with a fluorine atom, or a heteroaryl group in which at least one hydrogen atom is substituted with a fluorine atom. 1 is a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a CR 3 R 4 , SiR 3 R 4 , or GeR 3 R 4 R 3 and R 4 are each independently a hydrogen atom, an alkyl group, or an aryl group. [3] The compound according to [1] or [2], wherein L is a bonding group or contains any of the groups represented by the following general formulae (4a) to (4c):

[0016] [ka]

[0017] (In the above formulas (4a) to (4c), R 5 and R 6 are each independently a hydrogen atom, a deuterium atom, an alkyl group, an alkoxy group, C(=O)OR (wherein R is an alkyl group or an aryl group), or an amino group. 2 is a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a CR 7 R 8 , SiR 7 R 8 , or GeR 7 R 8 R 7 and R 8 are each independently a hydrogen atom, an alkyl group, or an aryl group. [4] The compound according to any one of [1] to [3], wherein A is a group represented by the following general formula (2a) or (2b):

[0018] [ka]

[0019] (In the formulas (2a) and (2b), Q 1 ~Q 8 are each independently a hydrogen atom, a chlorine atom, a fluorine atom, a bromine atom, or a cyano group. 1 and X 2 are each independently an oxygen atom or a dicyanomethylene group. [5] The compound according to [1], wherein A is a group represented by the following general formula (2a-1) or (2b-1), D is any of the groups represented by the following general formulas (3a-1) to (3c-1), and L includes a bonding group or any of the groups represented by the following general formulas (4a-1) to (4c-1).

[0020] [ka]

[0021] (In the above formula, Q 11 , Q 41 , Q 51 and Q 81 is a hydrogen atom, Q 21 , Q 31 , Q 61 and Q 71 are each independently a fluorine atom or a chlorine atom, or Q 11 ~Q 81 are each independently a hydrogen atom, a fluorine atom, or a chlorine atom.

[0022] [ka]

[0023] (In the above formula, Ar 11 and Ar 21are each independently a phenyl group in which one or more hydrogen atoms may be substituted, a naphthyl group in which one or more hydrogen atoms may be substituted, an anthracenyl group in which one or more hydrogen atoms may be substituted, a biphenyl group in which one or more hydrogen atoms may be substituted, a terphenyl group in which one or more hydrogen atoms may be substituted, a fluorenyl group in which one or more hydrogen atoms may be substituted, a thienyl group in which one or more hydrogen atoms may be substituted, a thienothienyl group in which one or more hydrogen atoms may be substituted, a benzothienyl group in which one or more hydrogen atoms may be substituted, a benzofuryl group in which one or more hydrogen atoms may be substituted, a dibenzothienyl group in which one or more hydrogen atoms may be substituted, or a dibenzofuryl group in which one or more hydrogen atoms may be substituted. 11 and Ar 21 At least one hydrogen atom in the ring of at least one of M is substituted with a fluorine atom. 1 is a sulfur atom, CR 31 R 41 or SiR 31 R 41 R 31 and R 41 are each independently an alkyl group or an aryl group.

[0024] [ka]

[0025] (In the above formula, M 2 is a sulfur atom, CR 71 R 81 or SiR 71 R 81 R 71 and R 81 are each independently an alkyl group or an aryl group. [6] The compound according to [1], which is a compound represented by the following general formulas (1a) to (1m):

[0026] [ka]

[0027] (In the above formula, A is a group represented by the following general formula (2a-2) or (2b-2): Ar 12 and Ar 22 are each independently a phenyl group in which one or more hydrogen atoms may be substituted, a naphthyl group in which one or more hydrogen atoms may be substituted, a biphenyl group in which one or more hydrogen atoms may be substituted, a fluorenyl group in which one or more hydrogen atoms may be substituted, a benzothienyl group in which one or more hydrogen atoms may be substituted, a benzofuryl group in which one or more hydrogen atoms may be substituted, a dibenzothienyl group in which one or more hydrogen atoms may be substituted, or a dibenzofuryl group in which one or more hydrogen atoms may be substituted. 12 and Ar 22 At least one hydrogen atom in the ring of at least one of M is substituted with a fluorine atom. 1 is a sulfur atom, CR 31 R 41 or SiR 31 R 41 R 31 and R 41 are each independently an alkyl group or an aryl group. 2 is a sulfur atom, CR 71 R 81 or SiR 71 R 81 R 71 and R 81 are each independently an alkyl group or an aryl group.

[0028] [ka]

[0029] (In the above formula, Q 22 , Q 32 , Q 62 and Q 72 are each independently a hydrogen atom, a fluorine atom, or a chlorine atom. [7] A film comprising the compound according to any one of [1] to [6]. [8] A photoelectric conversion element comprising the film according to [7]. [9] An image sensor comprising the photoelectric conversion element according to [8].

[10] A fingerprint sensor comprising the photoelectric conversion element described in [8].

[11] A pulse wave sensor comprising the photoelectric conversion element described in [8]. Effect of the Invention

[0030] According to the present invention, there are provided a compound having excellent properties in terms of production stability of an intermediate, control of the energy level of a frontier orbital, and control of absorption wavelength, as well as a film, a photoelectric conversion element, an image sensor, a fingerprint sensor, and a pulse wave sensor using said compound. [Brief description of the drawings]

[0031] [Figure 1] FIG. 1 is a cross-sectional view illustrating a schematic example of an embodiment of a photoelectric conversion element of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0032] The present invention will be described in further detail below by presenting preferred embodiments of the invention. However, the following description is one example of an embodiment of the present invention, and the present invention is not limited to the contents described below as long as it does not go beyond the gist of the invention. In this specification, the use of "to" indicating a range of values ​​means that the values ​​before and after it are included as the lower limit and upper limit.

[0033] [Compound] The compound of the present invention is a compound represented by the following general formula (1). Hereinafter, the compound represented by formula (1) will also be referred to as "compound (1)", and the same will be applied to compounds represented by other formulas.

[0034] [ka]

[0035] In the formula (1), D is a monocyclic or fused heterocyclic group containing a thienyl structure, one hydrogen atom of a thiophene ring contained in the heterocyclic group is substituted with an N-monosubstituted amino group or an N,N-disubstituted amino group, the N-monosubstituted amino group or the N,N-disubstituted amino group has a substituent selected from an alkyl group in which one or more hydrogen atoms may be substituted, an aryl group in which one or more hydrogen atoms may be substituted, and a heteroaryl group in which one or more hydrogen atoms may be substituted, and at least one of the substituents is the aryl group or the heteroaryl group, and at least one hydrogen atom of the aryl ring or heteroaryl ring contained in at least one of the substituents is substituted with a fluorine atom. L is a bond group, a monocyclic or fused ring containing a sulfur-containing heteroaryl ring, or a polycyclic ring in which two or more rings selected from the monocyclic and fused rings are bonded. A is a group represented by the following general formula (2). When L in the above formula (1) is a bonding group, the group represented by A=CH-- bonds to the thiophene ring in D.

[0036] [ka]

[0037] In the formula (2), Z is a benzene ring or a naphthalene ring in which one or more hydrogen atoms may be substituted, and X is an oxygen atom or a dicyanomethylene group.

[0038] Hereinafter, an N-monosubstituted amino group or an N,N-disubstituted amino group which has one or two substituents selected from an alkyl group in which one or more hydrogen atoms are optionally substituted, an aryl group in which one or more hydrogen atoms are optionally substituted, and a heteroaryl group in which one or more hydrogen atoms are optionally substituted, and in which at least one hydrogen atom of an aryl ring or heteroaryl ring contained in at least one of the substituents is substituted with a fluorine atom, is also referred to as a "substituted amino group (AF)".

[0039] (Bound group or ring L) L is a bonding group, a monocyclic or fused ring containing a sulfur-containing heteroaryl ring, or a polycyclic ring formed by bonding two or more rings selected from such monocyclic and fused rings. When L is a linking group, the group A=CH-- is attached to the thiophene ring of D. The monocyclic or condensed ring containing the sulfur-containing heteroaryl ring is required to have hole transport properties, and therefore preferably contains a thiophene ring.Specific examples thereof include a thiophene ring, a thienothiophene ring, a ring represented by the following general formula (L-1), and a benzothiophene ring, and the like, with the thiophene ring, the thienothiophene ring, and the ring represented by the following general formula (L-1) being preferred. When L is a monocyclic or condensed ring containing a thiophene ring, or a polycyclic ring formed by bonding these, the thiophene ring of L and the thiophene ring of D are preferably bonded to each other.

[0040] [ka]

[0041] In the above formula, M 2 is a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a CR 7 R 8 , SiR 7 R 8 , or GeR 7 R 8 R 7 and R 8 are each independently a hydrogen atom, an alkyl group, or an aryl group.

[0042] M 2 From the viewpoint of synthesis cost, sulfur atom, CR 7 R 8 or SiR 7 R 8 is preferred. R 7 and R 8 From the viewpoint of ease of synthesis, an alkyl group or an aryl group is preferable as the alkyl group.

[0043] R 7 and R 8The alkyl group may be linear, branched, or cyclic. R 7 and R 8 As the alkyl group, from the viewpoint of heat resistance, an alkyl group having 1 to 10 carbon atoms is preferable, and a methyl group, an ethyl group, or a cyclohexyl group is more preferable. R 7 and R 8 As the aryl group, from the viewpoint of heat resistance, an aryl group having 6 to 12 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable.

[0044] One or more hydrogen atoms in the sulfur-containing heteroaryl ring may be substituted with a deuterium atom, an alkyl group, an alkoxy group, C(═O)OR (wherein R is an alkyl group or an aryl group), an amino group, etc. From the viewpoint of ease of synthesis, these substituents are preferably a deuterium atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and more preferably a deuterium atom or an alkyl group having 1 to 10 carbon atoms.

[0045] From the viewpoint of heat resistance, L is preferably a bonding group or contains any of the groups represented by the following general formulae (4a) to (4c), is preferably a bonding group, any of the groups represented by the following general formulae (4a) to (4c), or a group in which two of them are bonded, and is more preferably a bonding group or any of the groups represented by the following general formulae (4a) to (4c). The two bonds of these groups are bonded to the thiophene rings of A=CH- and D, respectively.

[0046] [ka]

[0047] In the above formulas (4a) to (4c), R 5 and R 6 are each independently a hydrogen atom, a deuterium atom, an alkyl group, an alkoxy group, C(=O)OR (wherein R is an alkyl group or an aryl group), or an amino group. 2 is a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a CR7 R 8 , SiR 7 R 8 , or GeR 7 R 8 R 7 and R 8 are each independently a hydrogen atom, an alkyl group, or an aryl group.

[0048] R 5 and R 6 The alkyl group may be linear, branched, or cyclic. R 5 and R 6 As the alkyl group, from the viewpoint of heat resistance, an alkyl group having 1 to 10 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.

[0049] From the viewpoint of thermal stability, L is more preferably a bonding group or contains any of the groups represented by the following general formulae (4a-1) to (4c-1), further preferably any of the groups represented by the following general formulae (4a-1) to (4c-1), or a group in which two of them are bonded, and particularly preferably a bonding group or any of the groups represented by the following general formulae (4a-1) to (4c-1).

[0050] [ka]

[0051] In the above formula, M 2 is a sulfur atom, CR 71 R 81 or SiR 71 R 81 R 71 and R 81 are each independently an alkyl group or an aryl group.

[0052] R 71 and R 81 From the viewpoint of heat resistance, a methyl group or a phenyl group is preferable.

[0053] (Substituent D) D is a monocyclic or fused ring heterocyclic group containing a thienyl structure, and is a monovalent group in which one hydrogen atom of a thiophene ring contained in the heterocyclic group is substituted with a substituted amino group (AF). Examples of the monocyclic or condensed ring heterocyclic group containing a thienyl structure in D include a thienyl group, a thienothienyl group, and a group represented by the following general formula (d-1). In these heterocyclic groups, one or more of the hydrogen atoms other than the one hydrogen atom substituted with the substituted amino group (AF) may be substituted with a deuterium atom, an alkyl group, an alkoxy group, C(═O)OR (wherein R is an alkyl group or an aryl group), an amino group, etc. From the viewpoint of ease of synthesis, the substituents other than these substituted amino groups (AF) are preferably a deuterium atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and more preferably a deuterium atom or an alkyl group having 1 to 10 carbon atoms.

[0054] [ka]

[0055] In the formula (d-1), M 1 is a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a CR 3 R 4 , SiR 3 R 4 , or GeR 3 R 4 R 3 and R 4 are each independently a hydrogen atom, an alkyl group, or an aryl group.

[0056] M 1 From the synthesis cost, sulfur atom, CR 3 R 4 or SiR 3 R 4 is preferred. R 3 and R 4 From the viewpoint of ease of synthesis, the alkyl group or the aryl group is preferable.

[0057] R 3 and R 4 The alkyl group may be linear, branched, or cyclic. R 3 and R 4 As the alkyl group, from the viewpoint of heat resistance, an alkyl group having 1 to 10 carbon atoms is preferable, and a methyl group, an ethyl group, or a cyclohexyl group is more preferable. R 3 and R 4 The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and from the standpoint of heat resistance, a phenyl group or a naphthyl group is more preferable.

[0058] One hydrogen atom of the thiophene ring contained in the heterocyclic group is substituted with a substituted amino group (AF). In the thiophene ring contained in the heterocyclic group, it is preferable that the hydrogen atom at the 2-position is substituted with a substituted amino group (AF), but this is not limited thereto. As the substituted amino group (AF), an N,N-disubstituted amino group is preferable to an N-monosubstituted amino group in terms of the stability of the material.

[0059] Examples of the substituent that may be substituted on the aryl ring or heteroaryl ring of the substituted amino group (AF) include a chlorine atom, a fluorine atom, a bromine atom, an alkyl group, an alkoxy group, a cyano group, etc., and a fluorine atom is preferred because it is electron-withdrawing and has low reactivity.

[0060] The alkyl group in which one or more hydrogen atoms in the substituted amino group (AF) may be substituted may be any of linear, branched, and cyclic. As the alkyl group in which one or more hydrogen atoms in the substituted amino group (AF) may be substituted, from the viewpoint of hole transport properties, an alkyl group having 1 to 10 carbon atoms in which one or more hydrogen atoms may be substituted is preferable, and a methyl group, an ethyl group, or a cyclohexyl group is more preferable.

[0061] Examples of the aryl group in which one or more hydrogen atoms in the substituted amino group (AF) may be substituted include a phenyl group in which one or more hydrogen atoms may be substituted, a naphthyl group in which one or more hydrogen atoms may be substituted, an anthracenyl group in which one or more hydrogen atoms may be substituted, a biphenyl group in which one or more hydrogen atoms may be substituted, a terphenyl group in which one or more hydrogen atoms may be substituted, and a fluorenyl group in which one or more hydrogen atoms may be substituted. Among these, from the viewpoint of heat resistance, a phenyl group in which one or more hydrogen atoms may be substituted, a naphthyl group in which one or more hydrogen atoms may be substituted, a biphenyl group in which one or more hydrogen atoms may be substituted, and a fluorenyl group in which one or more hydrogen atoms may be substituted are preferred, and a phenyl group in which one or more hydrogen atoms may be substituted, a naphthyl group in which one or more hydrogen atoms may be substituted, and a biphenyl group in which one or more hydrogen atoms may be substituted are more preferred.

[0062] Specific examples of the aryl group in which one or more hydrogen atoms in the substituted amino group (AF) may be substituted include unsubstituted aryl groups such as a phenyl group, a naphthyl group, an anthracenyl group, a biphenyl group, a terphenyl group, a fluorenyl group, a 9,9-dimethylfluoren-2-yl group, a biphenylene group, and a triphenylene group; and aryl groups in which one or more hydrogen atoms are substituted with fluorine atoms, such as a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 3,5-difluorophenyl group, a 2,3,5-trifluorophenyl group, a 3,4,5-trifluorophenyl group, a 2,4,6-trifluorophenyl group, a pentafluorophenyl group, a 4'-fluorobiphenyl group, and a 2',3',4',5',6'-pentafluorobiphenyl group. Among these, from the viewpoint of heat resistance, a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, a 9,9-dimethylfluoren-2-yl group, a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 3,5-difluorophenyl group, a 3,4,5-trifluorophenyl group, a pentafluorophenyl group, and a 4'-fluorobiphenyl group are preferred.

[0063] Examples of the heteroaryl group in which one or more hydrogen atoms may be substituted include a thienyl group in which one or more hydrogen atoms may be substituted, a thienothienyl group in which one or more hydrogen atoms may be substituted, a benzothienyl group in which one or more hydrogen atoms may be substituted, a benzofuryl group in which one or more hydrogen atoms may be substituted, a group represented by the following general formula (d-2), a group represented by the following general formula (d-3), and a group represented by the following general formula (d-4). Among these, from the viewpoint of thermal stability, a benzothienyl group in which one or more hydrogen atoms may be substituted, a benzofuryl group in which one or more hydrogen atoms may be substituted, a group represented by the following general formula (d-2), a group represented by the following general formula (d-3), and a group represented by the following general formula (d-4) are preferred, and a group represented by the following general formula (d-2), a group represented by the following general formula (d-3), and a group represented by the following general formula (d-4) are more preferred.

[0064] [ka]

[0065] In the above formula, R 9 ~R 29 are each independently a hydrogen atom, a deuterium atom, an alkyl group, an alkoxy group, C(=O)OR (wherein R is an alkyl group or an aryl group), or an amino group. 3 ~M 5 each independently represents a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, or SiR 50 R 51 , G.E.R. 50 R 51 or NR 52 R 50 ~R 52 are each independently a hydrogen atom, an alkyl group, or an aryl group.

[0066] R 9 ~R 29 The alkyl group may be linear, branched, or cyclic. R 9 ~R 29As the alkyl group, from the viewpoint of heat resistance, an alkyl group having 1 to 10 carbon atoms is preferable, and a methyl group is more preferable. From the viewpoint of heat resistance, R 9 ~R 29 are each independently preferably a hydrogen atom or a deuterium atom.

[0067] M 3 ~M 5 From the viewpoint of synthesis cost, oxygen atoms, sulfur atoms, and SiR 50 R 51 or NR 52 is preferred. Because of its heat resistance, R 50 ~R 52 are each independently preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably a methyl group or a phenyl group.

[0068] Specific examples of the heteroaryl group in which one or more hydrogen atoms may be substituted include heteroaryl groups such as thienyl group, thienothienyl group, furanyl group, benzofuryl group, benzothienyl group, dibenzothienyl group, dibenzofuryl group, N-phenylcarbazolyl group, and N-methylcarbazolyl group, and 2-fluorothienyl group, etc. Among these, the dibenzothienyl group and the dibenzofuryl group are preferred from the viewpoint of ease of synthesis.

[0069] From the viewpoint of hole transport properties, D is preferably any one of the groups represented by the following general formulas (3a) to (3c).

[0070] [ka]

[0071] In the above formulas (3a) to (3c), R 1 and R 2 are each independently a hydrogen atom, a deuterium atom, an alkyl group, an alkoxy group, C(=O)OR (wherein R is an alkyl group or an aryl group), or an amino group. 1 and Ar2 are each independently an alkyl group in which one or more hydrogen atoms may be substituted, an aryl group in which one or more hydrogen atoms may be substituted, or a heteroaryl group in which one or more hydrogen atoms may be substituted, and at least one of them is an aryl group in which at least one hydrogen atom is substituted with a fluorine atom, or a heteroaryl group in which at least one hydrogen atom is substituted with a fluorine atom. 1 is a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a CR 3 R 4 , SiR 3 R 4 , or GeR 3 R 4 R 3 and R 4 are each independently a hydrogen atom, an alkyl group, or an aryl group.

[0072] In the group represented by formula (3a), Ar 1 and Ar 2 is preferably a group other than a naphthyl group in which one or more hydrogen atoms may be substituted. 1 and Ar 2 At least one of the groups may be a naphthyl group in which one or more hydrogen atoms may be substituted.

[0073] From the viewpoint of heat resistance, D is more preferably any of the groups represented by the following general formulas (3a-1) to (3c-1).

[0074] [ka]

[0075] In the above formula, Ar 11 and Ar 21are each independently a phenyl group in which one or more hydrogen atoms may be substituted, a naphthyl group in which one or more hydrogen atoms may be substituted, an anthracenyl group in which one or more hydrogen atoms may be substituted, a biphenyl group in which one or more hydrogen atoms may be substituted, a terphenyl group in which one or more hydrogen atoms may be substituted, a fluorenyl group in which one or more hydrogen atoms may be substituted, a thienyl group in which one or more hydrogen atoms may be substituted, a thienothienyl group in which one or more hydrogen atoms may be substituted, a benzothienyl group in which one or more hydrogen atoms may be substituted, a benzofuryl group in which one or more hydrogen atoms may be substituted, a dibenzothienyl group in which one or more hydrogen atoms may be substituted, or a dibenzofuryl group in which one or more hydrogen atoms may be substituted. 11 and Ar 21 At least one hydrogen atom in the ring of at least one of M is substituted with a fluorine atom. 1 is a sulfur atom, CR 31 R 41 or SiR 31 R 41 R 31 and R 41 are each independently an alkyl group or an aryl group.

[0076] Ar 11 and Ar 21 From the viewpoint of heat resistance, preferred are a phenyl group in which one or more hydrogen atoms may be substituted, a naphthyl group in which one or more hydrogen atoms may be substituted, and a biphenyl group in which one or more hydrogen atoms may be substituted, with a phenyl group, a naphthyl group, a biphenyl group, a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 3,5-difluorophenyl group, a 2,3,5-trifluorophenyl group, a 3,4,5-trifluorophenyl group, a pentafluorophenyl group, and a 4'-fluorobiphenyl group being more preferred. In the group represented by formula (3a-1), Ar 11 and Ar 21is preferably a group other than a naphthyl group in which one or more hydrogen atoms may be substituted. 11 and Ar 21 At least one of the groups may be a naphthyl group in which one or more hydrogen atoms may be substituted.

[0077] R 31 and R 41 From the viewpoint of heat resistance, a methyl group or a phenyl group is preferable.

[0078] (Substituent A) A is a group represented by the following general formula (2).

[0079] [ka]

[0080] In the formula (2), Z is a benzene ring or a naphthalene ring in which one or more hydrogen atoms may be substituted, and X is an oxygen atom or a dicyanomethylene group.

[0081] Substituents for Z which may be substituted on the benzene ring or naphthalene ring include a fluorine atom, a chlorine atom, a bromine atom, and a cyano group, with a fluorine atom and a chlorine atom being preferred from the standpoint of ease of synthesis. From the viewpoint of heat resistance, X is preferably an oxygen atom.

[0082] From the viewpoint of ease of synthesis, A is preferably a group represented by the following general formula (2a) or (2b).

[0083] [ka]

[0084] In the formulas (2a) and (2b), Q 1 ~Q 8are each independently a hydrogen atom, a chlorine atom, a fluorine atom, a bromine atom, or a cyano group. 1 and X 2 are each independently an oxygen atom or a dicyanomethylene group.

[0085] A is more preferably a group represented by the following general formula (2a-1) or (2b-1).

[0086] [ka]

[0087] In the above formula, Q 11 , Q 41 , Q 51 and Q 81 is a hydrogen atom, Q 21 , Q 31 , Q 61 and Q 71 are each independently a fluorine atom or a chlorine atom, or Q 11 ~Q 81 each independently represents a hydrogen atom, a fluorine atom or a chlorine atom.

[0088] From the viewpoint of hole transport properties, the compound (1) is preferably a compound represented by the following general formulas (1a) to (1m).

[0089] [ka]

[0090] In the formulas (1a) to (1m), A is a group represented by the following general formula (2a-2) or (2b-2). 12 and Ar 22are each independently a phenyl group in which one or more hydrogen atoms may be substituted, a naphthyl group in which one or more hydrogen atoms may be substituted, a biphenyl group in which one or more hydrogen atoms may be substituted, a fluorenyl group in which one or more hydrogen atoms may be substituted, a benzothienyl group in which one or more hydrogen atoms may be substituted, a benzofuryl group in which one or more hydrogen atoms may be substituted, a dibenzothienyl group in which one or more hydrogen atoms may be substituted, or a dibenzofuryl group in which one or more hydrogen atoms may be substituted. 12 and Ar 22 At least one hydrogen atom in the ring of at least one of M is substituted with a fluorine atom. 1 is a sulfur atom, CR 31 R 41 or SiR 31 R 41 R 31 and R 41 are each independently an alkyl group or an aryl group. 2 is a sulfur atom, CR 71 R 81 or SiR 71 R 81 R 71 and R 81 are each independently an alkyl group or an aryl group.

[0091] [ka]

[0092] In the above formula, Q 22 , Q 32 , Q 62 and Q 72 are each independently a hydrogen atom, a fluorine atom or a chlorine atom.

[0093] Specific examples of the compound (1a) include the compounds (1a-1) to (1a-43).

[0094] [ka]

[0095] [ka]

[0096] [ka]

[0097] [ka]

[0098] [ka]

[0099] [ka]

[0100] Specific examples of the compound (1b) include the compounds (1b-1) to (1b-11).

[0101] [ka]

[0102] [ka]

[0103] Specific examples of the compound (1c) include the compounds (1c-1) to (1c-14).

[0104] [ka]

[0105] [ka]

[0106] Specific examples of the compound (1d) include the compounds (1d-1) to (1d-6).

[0107] [ka]

[0108] Specific examples of the compound (1e) include the compounds (1e-1) to (1e-12).

[0109] [ka]

[0110] [ka]

[0111] Specific examples of the compound (1f) include the compounds (1f-1) to (1f-10).

[0112] [ka]

[0113] [ka]

[0114] Specific examples of compound (1g) include compounds (1g-1) to (1g-7).

[0115] [ka]

[0116] [ka]

[0117] Specific examples of the compound (1h) include the compounds (1h-1) to (1h-7).

[0118] [ka]

[0119] [ka]

[0120] Specific examples of compound (1i) include compounds (1i-1) to (1i-7).

[0121] [ka]

[0122] [ka]

[0123] Specific examples of compound (1j) include compounds (1j-1) to (1j-7).

[0124] [ka]

[0125] [ka]

[0126] Specific examples of compound (1k) include compounds (1k-1) to (1k-5).

[0127] [ka]

[0128] Specific examples of the compound (1l) include the compounds (1l-1) to (1l-5).

[0129] [ka]

[0130] Specific examples of compound (1m) include compounds (1m-1) to (1m-5).

[0131] [ka]

[0132] (Manufacturing method) The method for producing compound (1) is not particularly limited. Hereinafter, as an example of the method for producing compound (1), a method for producing compound (1a-A) will be specifically described. 1 , Ar 12 and Ar 22 is as described above.

[0133] [ka]

[0134] First, compound (B) is reacted with 2-bromothiophene to obtain compound (C).

[0135] [ka]

[0136] Compound (B) may be synthesized by a known method (for example, the method described in J. Med. Chem. 2004, 47, 25, 6128) or a commercially available product may be used. The reaction conditions can be determined by reference to those described in, for example, J. Org. Chem. 2003, 68, 2861. The equivalent ratio of 2-bromothiophene to compound (B) is preferably 0.8 to 1.2 equivalents. The reaction temperature is preferably from room temperature to 180°C. The reaction time is preferably 0.5 to 48 hours.

[0137] Next, compound (C) is reacted with lithium diisopropylamide (LDA) in a solvent, and then further reacted with N,N-dimethylformamide (DMF) to obtain compound (D). Note that N-formylpiperidine may be used instead of DMF.

[0138] [ka]

[0139] The equivalent ratio of LDA to compound (C) is preferably 0.9 to 1.5 equivalents. The equivalent ratio of DMF to compound (C) is preferably 0.9 equivalents or more. The reaction temperature is preferably from -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 DMF.

[0140] The solvent used in the reaction of compound (C) with LDA and DMF is not particularly limited as long as it is a solvent that does not react with the raw material compounds, and examples thereof 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.

[0141] Next, compound (D) is reacted with compound (E) in a solvent in the presence of an acid catalyst to obtain compound (A).

[0142] [ka]

[0143] Compound (E) may be a commercially available product or may be synthesized by a known method (e.g., Angew.Chem.Int.Ed.2017,56,304, Angew.Chem.Int.Ed.2017,56,15746, JP2022-511781A, JP2023-500815A, etc.).

[0144] Examples of basic catalysts include piperidine and pyridine, and examples of acid catalysts include p-toluenesulfonic acid hydrate (PTSA·H2O). The equivalent ratio of compound (E) to compound (D) is preferably 0.8 to 1.5 equivalents. The equivalent ratio of the acid catalyst to the compound (D) is preferably 0.1 to 10 equivalents.

[0145] The solvent used in the reaction of compound (D) with compound (E) is not particularly limited as long as it does not react with the raw material compounds, and examples thereof include chloroform, methanol, and ethanol. The reaction temperature is preferably from room temperature to 100°C. The reaction time is preferably 0.5 to 24 hours.

[0146] (Action and effect) Compound (1) has excellent properties in terms of the manufacturing stability of the intermediate, the control of the energy level of the frontier orbital, and the control of the absorption wavelength. Compound (1) is also considered to be excellent in terms of thermal stability, sublimation property, and carrier transport property. The reason why compound (1) has particularly useful properties as a p-type semiconductor material for such photoelectric conversion elements is not clear, but is presumed to be as follows.

[0147] For example, J.Org.Chem.,2002,67,6091. reports that fluorine atom substitution can thermally stabilize highly distorted compounds and induce a packed structure in a π-stack structure due to phenyl-perfluorophenyl interactions. J.Am.Chem.Soc.,2023,145,29,15702. reports that fluorinated compounds show high stability against oxidation, light, and heat in solutions and solids, and that perfluorinated compounds show the lowest sublimation points. J.Am.Chem.Soc.2015,137,7616. mentions that the non-covalent interactions of fluorine atoms in polymers play an important role in determining the conformation of the polymer and affect the frontier orbitals. On the other hand, JP 2018-14426 A describes that compounds having a 2-(diphenylamino)thiophene moiety that is not substituted with fluorine have low electrochemical stability, and US Patent Application Publication No. 2016 / 0211465 A describes that 2-(diphenylamino)thiophene derivatives have poor thermal stability.

[0148] In consideration of these, it is believed that compound (1) has excellent properties in terms of the production stability of intermediates, control of the energy level of the frontier orbital, and control of the absorption wavelength due to the following (i) and (ii). (i) The electron-withdrawing effect of the fluorine atom substituted on the aryl or heteroaryl ring of the substituent of the substituted amino group (AF) causes density relaxation at the electron-dense sites in the molecule and a lowering of the HOMO level. (ii) The intermolecular interactions change due to the change in quadrupole moment and the weakening or inhibition of CH-π interactions caused by the fluorine atom substitution of the substituted amino group (AF).

[0149] [film] The film of the present invention is a film containing the above-mentioned compound (1), and is also called an organic thin film. The film of the present invention is suitable as a photoelectric conversion layer (active layer) of a photoelectric conversion element. The film of the present invention may contain components other than compound (1). The components other than compound (1) are not particularly limited, and examples thereof include n-type semiconductor materials such as C60 fullerene and non-fullerene acceptors when compound (1) is used in a photoelectric conversion layer of a photoelectric conversion element.

[0150] The content of compound (1) in the film is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, based on the total mass of the film. The content of compound (1) in the film is preferably 100% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, based on the total mass of the film. The preferred lower and upper limits of the content of compound (1) in the film can be arbitrarily combined, and for example, 30 to 100% by mass is preferred.

[0151] The film thickness is preferably 1 nm or more, more preferably 10 nm or more. If the film thickness is equal to or more than the lower limit, it is easy to obtain a sufficient amount of light absorption. On the other hand, the film thickness is preferably 1000 nm or less, more preferably 500 nm or less, and even more preferably 250 nm or less. If the film thickness is equal to or less than the upper limit, it is preferable in terms of external quantum efficiency (EQE) when the film is used as a photoelectric conversion layer (active layer) of a photoelectric conversion element. The preferable lower limit and upper limit of the film thickness can be arbitrarily combined, and for example, 10 to 250 nm are preferable.

[0152] The film of the present invention can be formed by a dry process such as vacuum deposition or sputtering. Alternatively, the film of the present invention may be formed by applying a composition containing compound (1) and a solvent onto a substrate and then drying to remove the solvent. Methods for applying the composition include brush coating, bar coating, spray coating, dip coating, spin coating, curtain coating, inkjet printing, and the like.

[0153] [Photoelectric conversion element] The photoelectric conversion element of the present invention is an element including the above-mentioned film of the present invention, and is also called an organic photoelectric conversion element. Specifically, the photoelectric conversion element of the present invention includes 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, the description in JP-A-2007-324587 can be referred to. The specific structure is not particularly limited, but examples thereof include an element having a laminated structure in which a photoelectric conversion layer (active layer) is sandwiched between a pair of electrodes.

[0154] Hereinafter, an example of the photoelectric conversion element of the present invention will be described with reference to FIG. In addition, in each drawing used in the following description, characteristic parts 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, and can be appropriately changed and implemented within the scope of the present invention.

[0155] A photoelectric conversion element 10 shown in FIG. 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.

[0156] The transparent substrate 11 may be a base material 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.

[0157] The transparent electrode 12 may be an electrode having an average transmittance of 80% or more for 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, but examples include tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), tungsten-doped indium oxide (IWO), zinc aluminum oxide (AZO), indium oxide (In2O3), zinc oxide (ZnO), titanium oxide (TiO2), and the like.

[0158] The metal electrode 16 is an electrode that forms a pair 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.

[0159] The thickness of the metal electrode 16 is not particularly limited, but is preferably about 10 nm from the viewpoint of enhancing transparency. If transparency is not required, the thickness is preferably 40 nm or more, and more preferably 100 nm or more, taking into consideration durability and the like.

[0160] 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 a conductive ink or the like.

[0161] When the hole transport layer 13 and the electron transport layer 15 are provided, the constituent members and the manufacturing method thereof are not particularly limited, and known techniques can be used. For example, the members and the manufacturing methods thereof described in known documents such as WO 2013 / 171517, WO 2013 / 180230, or JP 2012-191194 A can be used.

[0162] The photoelectric conversion layer 14 is a layer that absorbs light and separates electric charges. The photoelectric conversion layer 14 of the photoelectric conversion element of the present invention is a layer containing the above-mentioned compound (1) of the present invention, more specifically, the above-mentioned film of the present invention. The photoelectric conversion layer 14 may be formed, for example, by co-evaporating compound (1) as a p-type semiconductor material and an n-type semiconductor material on a layer that is to be an underlying layer of the photoelectric conversion layer 14, such as the hole transport layer 13, or two layers may be formed by sequentially vapor-depositing compound (1) as a p-type semiconductor material and an n-type semiconductor material.

[0163] 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 on a transparent substrate 11 in this order.

[0164] The photoelectric conversion element of the present invention has high photoelectric conversion ability because the photoelectric conversion layer 14 contains, as a p-type semiconductor material, compound (1) in which the HOMO level and LUMO level are lowered while suppressing a change in absorption wavelength.

[0165] [Image sensor, fingerprint sensor, pulse wave sensor] The use of the photoelectric conversion element of the present invention is not particularly limited, but it is suitable for an image sensor, a fingerprint sensor, and a pulse wave sensor. The image sensor, fingerprint sensor, and pulse wave sensor may have a known structure. Specifically, the image sensor may have a structure in which metal wiring, the photoelectric conversion element of the present invention, a color filter, and a microlens are laminated in this order on a substrate such as a silicon substrate. EXAMPLES

[0166] The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following description.

[0167] [Synthesis Example 1] A reaction was carried out using 2.05 g (10 mmol) of compound (1a-1-1) synthesized by the method described in J. Med. Chem. 2004, 47, 25, 6128. and 1.63 g (10 mmol) of 2-bromothiophene under reaction conditions based on the method described in J. Org. Chem. 2003, 68, 2861. The reaction was purified by silica gel chromatography to obtain 4.06 g (yield 62%) of compound (1a-1-2). The obtained compound (1a-1-2) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: CDCl3, ppm): δ7.06-7.02(m,4H), 6.98-6.92(m,5H), 6.86(dd,1H), 2.05(dd,1H).

[0168] [ka]

[0169] 1.80 g (6.26 mmol) of compound (1a-1-2) was dissolved in 30 mL of tetrahydrofuran (THF) and cooled in a dry ice acetone bath. 5.98 mL (1.17 M, 6.58 mmol) of lithium diisopropylamide (LDA) was slowly added dropwise thereto. After stirring for 1 hour, 5.98 mL of N,N-dimethylformamide (DMF) was slowly added. After stirring for 1 hour while cooling in a dry ice acetone bath, the temperature was raised to room temperature. Water and ethyl acetate were added, and the organic layer was washed with a saturated aqueous sodium chloride solution to obtain 1.95 g of compound (1a-1-3). The obtained compound (1a-1-3) 1 Identification was performed by H-NMR analysis. 1The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: CDCl3, ppm): δ9.61 (s, 1H), 7.45 (d, 1H), 7.23-7.27 (m, 4H), 7.03-7.10 (m, 4H), 6.29 (d, 1H).

[0170] [ka]

[0171] 1.88 g (5.96 mmol) of compound (1a-1-3), 1.05 g (7.15 mmol) of commercially available 1,3-indandione, and 54 mL of chloroform were placed in a reaction vessel, stirred to dissolve, and then 2.2 mL of piperidine was added and stirred at 60° C. for 1 hour. After cooling, the solvent was distilled off, and methanol was added instead to disperse the solid and filter, obtaining 2.44 g (yield 92%) of solid compound (1a-1). The resulting compound (1a-1) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: CDCl3, ppm): δ7.83-7.86(s,1H), 7.79-7.81(m,1H), 7.78( s,1H), 7.64-7.69(m,3H), 7.30-7.35(m,4H), 7.09-7.15(m,4H), 6.36(d,1H).

[0172] [ka]

[0173] [Synthesis Example 2] 2.05 g (6.50 mmol) of compound (1a-1-3) synthesized by the same method as in Synthesis Example 1, 1.42 g (7.80 mmol) of 5,6-difluoro-1,3-indandione synthesized by the method described in JP 2021-132132 A, and 59 mL of chloroform were placed in a reaction vessel and stirred to dissolve, and then 2.3 mL of piperidine was added and stirred at 60 ° C. for 1 hour. After cooling, the solvent was distilled off, methanol was added instead, the solid was dispersed, and filtered to obtain 2.70 g (yield 87%) of solid compound (1a-2). The resulting compound (1a-2) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: CDCl3, ppm): δ7.67(d,1H), δ7.59-7.60(m,1H), 7.28-7.45(m,6H), 7.08-7.14(m,4H), 6.34(dd,1H).

[0174] [ka]

[0175] [Synthesis Example 3] A reaction was carried out using 1.03 g (5.0 mmol) of compound (1a-1-1) synthesized by the method described in J. Med. Chem. 2004, 47, 25, 6128. and 1.08 g (5.0 mmol) of compound (1b-1-1) synthesized by the method described in International Publication No. 2021 / 112020, with the reaction conditions being based on the method described in J. Org. Chem. 2003, 68, 2861-2873. Compound (1b-1-2) was obtained by purifying the product by silica gel chromatography (yield 64%). The resulting compound (1b-1-2) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1H-NMR (400MHz, solvent: CDCl3, ppm): δ7.54(d,1H), 7.32(d,1H), 7.20-7.15(m,4H), 7.14-7.09(m,5H).

[0176] [ka]

[0177] 1.55 g (4.50 mmol) of compound (1b-1-2) was dissolved in 20 mL of THF and cooled with acetone / dry ice. 4.30 mL (1.10 M, 4.70 mmol) of LDA was slowly added dropwise thereto. After stirring for 1 hour, 2.00 mL of N,N-dimethylformamide (DMF) was slowly added, and after stirring for 30 minutes, the temperature was raised to room temperature. A saturated aqueous solution of ammonium chloride and diethyl ether were added, and the organic phase was washed three times with water and dried over sodium sulfate. The solvent was distilled off, and diethyl ether was added to the obtained solid, followed by filtration to obtain 1.09 g of compound (1b-1-3) (yield 65%). The resulting compound (1b-1-3) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1 H-NMR (400 MHz, solvent: acetone-d, ppm): δ 9.89 (s, 1H), 8.09 (d, 1H), 7.39-7.36 (m, 4H), 7.23-7.18 (m, 4H), 6.80 (d, 1H).

[0178] [ka]

[0179] 36.6 mg (0.10 mmol) of compound (1b-1-3) and 21.7 mg (0.12 mmol) of commercially available 1,3-indandione were dissolved in 1 mL of chloroform and heated to 40° C. 50 microliters of piperidine was added dropwise, stirred at 40° C. for 1 hour, and then cooled to room temperature. The solvent was distilled off, and methanol was added to the resulting solid, followed by filtration to obtain 20 mg of compound (1b-1) (yield 40%). The resulting compound (1b-1) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1H-NMR (400MHz, solvent: heavy acetone, ppm): δ8.15 (brs, 1H), 7.91-7.86 (m, 3H), 7.77-7.72 (m, 2H), 7.33-7.27 (m, 4H), 7.14-7.07 (m, 4H), 6.60 (s, 1H).

[0180] [ka]

[0181] [Synthesis Example 4] Compound (X-1) was synthesized with reference to the description in Z. Naturforsch., 2016, 71, 651.

[0182] [ka]

[0183] [Synthesis Example 5] Compound (X-2) was the target compound, and synthesis was performed in the same manner as in Synthesis Example 3, except that diphenylamine was used instead of compound (1a-1-1). However, compound (X-2) was not obtained.

[0184] [ka]

[0185] [Comparison of compound (1b-1-2) and compound (X-2) by theoretical calculation] The electrostatic potential of the nitrogen atom of the amino group of compound (1b-1-2) and compound (X-2) was estimated by theoretical calculation (B3LYP / 6-31G(d)@Spartan'20), and the results are shown in Table 1. Note that Table 1 shows the electrostatic potential of the nitrogen atom of compound (1b-1-2) based on the electrostatic potential of the nitrogen atom of compound (X-2).

[0186] [Table 1]

[0187] As shown in Table 1, the nitrogen atom of compound (1b-1-2) had a much lower electron density than the nitrogen atom of compound (X-2). This is thought to be because the localization of electrons on the nitrogen atom in compound (1b-1-2) was alleviated by the fluorine atom substitution. As a result, the electron-donating contribution of the amino group to the thiophene ring was reduced, and it is presumed that compound (1a-1-2) was stabilized and easily produced.

[0188] [Comparison of Compound (1a-1), Compound (1a-2), and Compound (X-1) by Theoretical Calculation] The HOMO and LUMO levels of compounds (1a-1), (1a-2) and (X-1) were calculated by theoretical calculation (B3LYP / 6-31G(d)@Spartan'20). The absorption wavelengths of each compound were measured in methylene chloride. The results are shown in Table 2.

[0189] [Table 2]

[0190] As shown in Table 2, compound (1a-1) was able to lower the HOMO and LUMO levels by merely shifting the absorption wavelength slightly to the shorter wavelength side compared to compound (X-1). Moreover, compound (1a-2) succeeded in further lowering the HOMO and LUMO levels without changing the absorption wavelength compared to compound (X-1). Thus, it was confirmed that the present invention makes it possible to obtain a compound suitable for a p-type semiconductor material, which has deep HOMO and LUMO levels, with almost no change in the absorption wavelength.

[0191] [Synthesis Example 6] A reaction was carried out using 8.54 g (45.6 mmol) of commercially available compound (1a-23-1) and 7.49 g (45.6 mmol) of 2-bromothiophene under reaction conditions according to the method described in J. Org. Chem. 2003, 68, 2861. The product was purified by silica gel chromatography to obtain 6.72 g (yield 54%) of compound (1a-23-2). The obtained compound (1a-23-2) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: heavy acetone, ppm): δ7.30-7.26(m,2H), 7.19(dd,1H), 7.17-7.08(m,4H), 7.30-6.99(m,3H), 6.95(dd,1H), 6.76(dd,1H).

[0192] [ka]

[0193] 2.69 g (10.0 mmol) of compound (1a-23-2) was dissolved in 40 mL of THF and cooled in a dry ice acetone bath. 9.55 mL (1.10 M, 10.5 mmol) of LDA was slowly added dropwise thereto. After stirring for 1 hour, 5 mL of DMF was slowly added. After stirring for 1 hour while cooling in a dry ice acetone bath, the temperature was raised to room temperature. A saturated aqueous solution of ammonium chloride and ethyl acetate were added, and the organic layer was washed twice with a saturated aqueous solution of ammonium chloride and dried over sodium sulfate. The solvent was distilled off, and the compound (1a-23-3) was obtained in an amount of 2.64 g (yield 88%) by purifying it by silica gel chromatography. The obtained compound (1a-23-3) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1H-NMR (400MHz, solvent: heavy acetone, ppm): δ9.63(s,1H), 7.65(d,1H), 7.48-7.40(m,4H), 7.37-7.34(m,2H), 7.31-7.21(m,3H), 6.36(d,1H).

[0194] [ka]

[0195] 2.60 g (8.74 mmol) of compound (1a-23-3), 1.91 g (10.5 mmol) of commercially available 1,3-indandione, and 80 mL of chloroform were placed in a reaction vessel and stirred to dissolve, after which 4.3 mL of piperidine was added and stirred at 40° C. for 1 hour. After cooling, the solvent was distilled off, methanol was added to disperse the solid, and the mixture was filtered to obtain 3.69 g (yield 99%) of solid compound (1a-23). The resulting compound (1a-23) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: CD2Cl2, ppm): δ7.81-7.67(m,6H), 7.48-7.44(m,2H), 7.40-7.32(m,5H), 7.20-7.15(m,2H), 6.42(d,1H).

[0196] [ka]

[0197] [Synthesis Example 7] A reaction was carried out using 3.71 g (39.8 mmol) of aniline and 5.00 g (19.9 mmol) of 4-bromo-4'-fluorobiphenyl, with the reaction conditions being based on the method described in a patent document (JP 2019-175970 A). The reaction was purified by silica gel chromatography to obtain 5.16 g (yield 98%) of compound (1a-22-1). The obtained compound (1a-22-1) 1Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: CDCl3, ppm): δ7.49-7.53(m,2H), 7.43-7.47(m,2H), 7.27-7.31(m,2H), 7.08-7.15(m,6H), 6.94-6.98(m,1H), 5.77(s,1H).

[0198] [ka]

[0199] A reaction was carried out using 2.05 g (9.51 mmol) of compound (1a-22-1) and 1.55 g (9.51 mmol) of 2-thiophene under reaction conditions according to the method described in J. Org. Chem. 2003, 68, 2861. The reaction was purified by silica gel chromatography to obtain 1.97 g (yield 60%) of compound (1a-22-2). The obtained compound (1a-22-2) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: CDCl3, ppm): δ7.48-7.53(m,2H), 7.40-7.43(m,2H), 7.23-7 .30(m,2H), 7.14-7.18(m,5H), 7.02-7.12(m,3H), 6.90(dd,1H), 6.45(dd,1H).

[0200] [ka]

[0201] 3.30 g (9.55 mmol) of compound (1a-22-2) was dissolved in 48 mL of THF and cooled in a dry ice acetone bath. 9.55 mL (1.10 M, 10.51 mmol) of LDA was slowly added dropwise thereto. After stirring for 1 hour, 0.88 mL of DMF was slowly added dropwise. After stirring for 1 hour while cooling in a dry ice acetone bath, the temperature was raised to room temperature. Water and ethyl acetate were added, and the organic layer was washed with a saturated aqueous sodium chloride solution to obtain 3.33 g (yield 93%) of compound (1a-22-3). The obtained compound (1a-22-3) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: CDCl3, ppm): δ9.63(s,1H), 7.51-7.55(m,4H), 7.48(d,1H), 7.37-7.41(m,2H), 7.30-7.35(m,4H), 7.11-7.16(m,3H), 6.45(dd,1H).

[0202] [ka]

[0203] 3.33 g (8.92 mmol) of compound (1a-22-3), 1.95 g (10.70 mmol) of commercially available 1,3-indandione, and 95 mL of chloroform were placed in a reaction vessel and stirred to dissolve, after which 3.8 mL of piperidine was added and stirred at 60° C. for 1 hour. After cooling, the solvent was distilled off, and methanol was added instead to disperse the solid and filter, obtaining 4.00 g (yield 89%) of solid compound (1a-22). The resulting compound (1a-22) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1H-NMR (400MHz, solvent: CDCl3, ppm): δ7.84-7.86(m,1H), 7.78-7.81(m,2H), 7.65-7.68(m,2H), 7.54-7.59(m,4H), 7.37-7.45(m,6H), 7.30-7.34(m,1H), 7.13-7.17(m,3H), 6.50(dd,1H).

[0204] [ka]

[0205] [Synthesis Example 8] A reaction was carried out using 7.90 g (30 mmol) of compound (1a-17-1) synthesized by the method described in Korean Patent Publication No. 2013-0106255 and 7.40 g (45 mmol) of 2-bromothiophene, with the reaction conditions described in J. Org. Chem. 2003, 68, 2861 as reference. The reaction was purified by silica gel chromatography to obtain 2.62 g (yield 25%) of compound (1a-17-2). The obtained compound (1a-17-2) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: heavy acetone, ppm): δ7.64-7.57(m,2H), 7.45-7.41(m,2H), 7.33-7 .29(m,1H), 7.24-7.21(m,4H), 7.18-7.08(m,5H), 6.98(dd,1H), 6.82(dd,1H).

[0206] [ka]

[0207] 2.62 g (7.58 mmol) of compound (1a-17-2) was dissolved in 30 mL of THF and cooled in a dry ice acetone bath. 7.30 mL (1.10 M, 8.00 mmol) of LDA was slowly added dropwise thereto. After stirring for 1 hour, 4.00 mL of DMF was slowly added. After stirring for 30 minutes while cooling in a dry ice acetone bath, the temperature was raised to room temperature. A saturated aqueous solution of ammonium chloride and ethyl acetate were added, and the organic layer was washed three times with a saturated aqueous solution of ammonium chloride and dried over sodium sulfate. The solvent was distilled off, and the compound (1a-17-3) was obtained in an amount of 2.58 g (yield 90%) by purifying it by silica gel chromatography. The obtained compound (1a-17-3) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1 The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: heavy acetone, ppm): δ9.66(s,1H), 7.76-7.72(m,2H), 7.70-7.68( m,3H), 7.49-7.41(m,6H), 7.39-7.35(m,1H), 7.30-7.18(m,2H), 6.45(d,1H).

[0208] [ka]

[0209] 2.58 g (6.91 mmol) of compound (1a-17-3), 1.51 g (8.29 mmol) of commercially available 1,3-indandione, and 60 mL of chloroform were placed in a reaction vessel and stirred to dissolve, after which 1.4 mL of piperidine was added and stirred at 40° C. for 1 hour. After cooling, the solvent was distilled off, methanol was added to disperse the solid, and the mixture was filtered to obtain 3.13 g (yield 90%) of solid compound (1a-17). The resulting compound (1a-17) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1H-NMR (400MHz, solvent: CD2Cl2, ppm): δ7.82-7.63 (m, 10H), 7.49-7.38 (m, 7H), 7.21-7.17 (m, 2H), 6.49 (d, 1H).

[0210] [ka]

[0211] [Synthesis Example 9] 3.78 g (12.7 mmol) of compound (1a-23-3), 3.00 g (15.2 mmol) of 1H-cyclopenta[b]naphthalene-1,3(2H)-dione synthesized by the method described in J. Mater. Chem. A. 2017, 5, 23926., and 50 mL of chloroform were placed in a reaction vessel, stirred to dissolve, and then 2.5 mL of piperidine was added and stirred at 50 ° C for 2 hours. After cooling, the solvent was distilled off, methanol was added to disperse the solid, and the mixture was filtered to obtain 5.61 g (yield 92%) of solid compound (1a-34). The resulting compound (1a-34) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: CD2Cl2, ppm): δ8.24(d,2H), 8.05-8.03(m,2H), 7.84(s,1H), 7.77(brs,1 H), 7.65-7.61(m,2H), 7.51-7.46(m,2H), 7.43-7.32(m,5H), 7.22-7.17(m,2H), 6.45(d,1H).

[0212] [ka]

[0213] [Synthesis Example 10] 0.35g (1.00mmol) of compound (1a-23-3) obtained by the same method as in Synthesis Example 6, 0.24g (1.20mmol) of 1H-cyclopenta[b]naphthalene-1,3(2H)-dione synthesized by the method described in J.Mater.Chem.A.2017,5,23926., and 5mL of chloroform were placed in a reaction vessel, stirred to dissolve, and then 0.2mL of piperidine was added and stirred at 50°C for 2 hours. After cooling, the solvent was distilled off, methanol was added to disperse the solid, and the mixture was filtered to obtain 0.45g (yield 91%) of solid compound (1a-29). The resulting compound (1a-29) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: CD2Cl2, ppm): δ8.25(d,2H), 8.06-8.04(m,2H), 7.84(s,1H), 7. 77(brs,1H), 7.66-7.62(m,2H), 7.43-7.37(m,4H), 7.22-7.16(m,4H), 6.42(d,1H).

[0214] [ka]

[0215] [Synthesis Example 11] The reaction was carried out using 11.1 g (100 mmol) of 4-fluoroaniline and 8.75 g (50 mmol) of 3-bromo-fluorobenzene under reaction conditions according to the method described in a patent document (JP 2019-175970 A). The product was purified by silica gel chromatography to obtain 8.51 g (yield 83%) of compound (1a-31-1). The obtained compound (1a-31-1) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1H-NMR (400MHz, solvent: heavy acetone, ppm): δ7.57(s,1H), 7.24-7.18(m,3H), 7.10-7.06(m,2H), 6.83-6.81(m,1H), 6.76-6.72(m,1H), 6.56-6.51(m,1H).

[0216] [ka]

[0217] A reaction was carried out using 2.80 g (15.0 mmol) of compound (1a-31-1) and 3.19 g (15.0 mmol) of 2-bromothiophene under reaction conditions according to the method described in J. Org. Chem. 2003, 68, 2861. The reaction was purified by silica gel chromatography to obtain 1.28 g (yield 31%) of compound (1a-31-2). The obtained compound (1a-31-2) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: heavy acetone, ppm): δ7.29-7.24(m,4H), 7.20-7.15(m,2H), 6.99(dd,1H), 6.87(dd,1H), 6.75-6.67(m,2H), 6.64-6.60(m,1H).

[0218] [ka]

[0219] 1.28 g (4.45 mmol) of compound (1a-31-2) was dissolved in 15 mL of THF and cooled in a dry ice acetone bath. 4.37 mL (1.07 M, 4.68 mmol) of LDA was slowly added dropwise thereto. After stirring for 1 hour, 1.00 mL of DMF was slowly added. After stirring for 30 minutes while cooling in a dry ice acetone bath, the temperature was raised to room temperature. A saturated aqueous solution of ammonium chloride and ethyl acetate were added, and the organic layer was washed three times with a saturated aqueous solution of ammonium chloride and dried over sodium sulfate. The solvent was distilled off, and the compound (1a-31-3) was obtained in an amount of 1.37 g (yield 97%) by purifying it by silica gel chromatography. The obtained compound (1a-31-3) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: CDCl3, ppm): δ9.69(s,1H), 7.70(d,1H), 7.46-7.43(m,3H), 7.30 -7.24(m,2H), 7.16-7.13(m,1H), 7.10-7.07(m,1H), 7.03-6.98(m,1H), 6.52(d,1H).

[0220] [ka]

[0221] 1.37 g (4.34 mmol) of compound (1a-31-3), 1.02 g (5.21 mmol) of 1H-cyclopenta[b]naphthalene-1,3(2H)-dione synthesized by the method described in J. Mater. Chem. A. 2017, 5, 23926., and 20 mL of chloroform were placed in a reaction vessel, stirred to dissolve, and then 0.86 mL of piperidine was added and stirred at 50 ° C for 2 hours. After cooling, the solvent was distilled off, methanol was added to disperse the solid, and the mixture was filtered to obtain 1.67 g (77% yield) of solid compound (1a-31). The resulting compound (1a-31) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: CDCl3, ppm): δ8.28(d,2H), 8.05(brs,2H), 7.86(s,1H), 7.79(brs,1H) , 7.67-7.63(m,2H), 7.46-7.38(m,3H), 7.23-7.19(m,3H), 7.08-7.00(m,2H), 6.54(d,1H).

[0222] [ka]

[0223] [Synthesis Example 12] A reaction was carried out using 3.06 g (14.9 mmol) of compound (1a-1-1) synthesized by the method described in J. Med. Chem. 2004, 47, 25, 6128. and 3.40 g (11.9 mmol) of 2-bromo-4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b']dithiophene synthesized by the method described in Korean Patent Publication No. 2013-0020739, with reference to the reaction conditions described in J. Org. Chem. 2003, 68, 2861. The reaction was purified by silica gel chromatography to obtain 4.03 g (yield 83%) of compound (1c-1-2). The resulting compound (1c-1-2) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: CDCl3, ppm): δ7.07-7.13(m,5H), 6.94-6.99(m,5H), 6.66(s,1H), 1.42(s,6H).

[0224] [ka]

[0225] 4.03 g (9.84 mmol) of compound (1c-1-2) was dissolved in 47 mL of THF and cooled in a dry ice acetone bath. 9.39 mL (1.10 M, 10.33 mmol) of LDA was slowly added dropwise thereto. After stirring for 1 hour, 0.91 mL of DMF was slowly added dropwise. After stirring for 1 hour while cooling in a dry ice acetone bath, the temperature was raised to room temperature. Water and ethyl acetate were added, and the organic layer was washed with a saturated aqueous sodium chloride solution to obtain 4.25 g (yield 98%) of compound (1c-1-3). The resulting compound (1c-1-3) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: CDCl3, ppm): δ9.77(s,1H), 7.57(s,1H), 7.13-7.17(m,4H), 6.99-7.03(m,4H), 6.53(s,1H), 1.45(s,6H).

[0226] [ka]

[0227] 3.97 g (9.07 mmol) of compound (1c-1-3), 1.59 g (10.89 mmol) of commercially available 1,3-indandione, and 113 mL of chloroform were placed in a reaction vessel and stirred to dissolve, after which 4.5 mL of piperidine was added and stirred for 1 hour at 60° C. After cooling, the solvent was distilled off, and methanol was added instead to disperse the solid and filter, obtaining 4.20 g (yield 82%) of solid compound (1c-1). The obtained compound (1c-1) was identified by LC-MS (m / z 566.1 ([M+H] + )).

[0228] [ka]

[0229] [Synthesis Example 13] Compound (X-3) was synthesized with reference to the description in U.S. Patent Application Publication No. 2017 / 0346016.

[0230] [ka]

[0231] [Synthesis Example 14] The reaction was carried out using 7.23 g (30.0 mmol) of compound (1a-39-1), which was synthesized with reference to the method described in the patent document (JP 2023-104057), and 5.38 g (33.0 mmol) of 2-bromothiophene, with the reaction conditions being based on the method described in J. Org. Chem. 2003, 68, 2861. The product was purified by silica gel chromatography to obtain 5.90 g (yield 60%) of compound (1a-39-2). The obtained compound (1a-39-2) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1 H-NMR (400 MHz, solvent: acetone-d, ppm): δ 7.43 (dd, 1H), 7.08-7.04 (m, 2H), 6.77-6.71 (m, 6H).

[0232] [ka]

[0233] Under a nitrogen atmosphere, 5.90 g (18.2 mmol) of compound (1a-39-2) was dissolved in 36 mL of dichloromethane, and 2.80 g (20.1 mmol) of Vilsmeier reagent (Tokyo Chemical Industry Co., Ltd.) was added. After stirring at room temperature for 1 hour, saturated aqueous sodium bicarbonate solution and ethyl acetate were added, and the organic layer was washed twice with saturated aqueous sodium bicarbonate solution and dried over sodium sulfate. The solvent was removed, and the solution was purified by silica gel chromatography to obtain compound (1a-39-3). The obtained compound (1a-39-3) 1 Identification was performed by H-NMR analysis. 1The H-NMR measurement data is shown below. 1 H-NMR (400 MHz, solvent: acetone-d, ppm): δ 9.81 (s, 1H), 7.83 (d, 1H), 7.00-6.89 (m, 7H).

[0234] [ka]

[0235] Compound (1a-39-3), 4.27 g (21.8 mmol) of 1H-cyclopenta[b]naphthalene-1,3(2H)-dione synthesized by the method described in J. Mater. Chem. A. 2017, 5, 23926., and 50 mL of chloroform were placed in a reaction vessel, 3.6 mL of piperidine was added, and the mixture was stirred at 60 ° C. for 3 hours. After cooling, the solvent was distilled off, methanol was added, and the solid was dispersed and filtered to obtain 6.1 g (yield 61%) of compound (1a-39). The resulting compound (1a-39) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: CD2Cl2, ppm): δ8.36(d,2H), 8.10-8.07(m,2H), 7.93(s, 1H), 7.83(d,1H), 7.70-7.66(m,2H), 6.89-6.85(m,4H), 6.80-6.75(m,3H).

[0236] [ka]

[0237] [Synthesis Example 15] A reaction was carried out using 2.80 g (25.2 mmol) of 4-fluoroaniline and 2.92 g (15 mmol) of 3,5-difluorobromobenzene, with reference to the method described in a patent document (JP 2019-175970) as the reaction conditions, and 3.32 g (yield 98%) of compound (1a-43-1) was obtained by purifying the product by silica gel chromatography. The obtained compound (1a-43-1) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: heavy acetone, ppm): δ8.32 (brs, 1H), 7.26-7.22 (m, 2H), 7.16-7.11 (m, 2H), 6.57-6.51 (m, 2H), 6.34 (tt, 1H).

[0238] [ka]

[0239] A reaction was carried out using 2.96 g (13.3 mmol) of compound (1a-43-1) and 2.25 g (13.9 mmol) of 2-bromothiophene under reaction conditions according to the method described in J. Org. Chem. 2003, 68, 2861. The product was purified by silica gel chromatography to obtain 3.65 g (yield 90%) of compound (1a-43-2). The obtained compound (1a-43-2) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: heavy acetone, ppm): δ7.41-7.34(m,3H), 7.25-7.19(m,2H), 7.03-6.98(m,2H), 6.49(tt,1H), 6.40-6.34(m,2H).

[0240] [ka]

[0241] Under a nitrogen atmosphere, 2.87 g (9.40 mmol) of compound (1a-43-2) was dissolved in 20 mL of dichloromethane, and 1.33 g (10.3 mmol) of Vilsmeier reagent (Tokyo Chemical Industry Co., Ltd.) was added. After stirring at room temperature for 1 hour, saturated aqueous sodium bicarbonate solution and ethyl acetate were added, and the organic layer was washed twice with saturated aqueous sodium bicarbonate solution and dried over sodium sulfate. The solvent was removed, and the solution was purified by silica gel chromatography to obtain compound (1a-43-3). The obtained compound (1a-43-3) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: heavy acetone, ppm): δ9.74(s,1H), 7.76(d,1H), 7.50-7.44(m,2H), 7.33-7.27(m,2H), 6.89-6.72(m,3H), 6.73(d,1H).

[0242] [ka]

[0243] Compound (1a-43-3), 2.21 g (11.3 mmol) of 1H-cyclopenta[b]naphthalene-1,3(2H)-dione synthesized by the method described in J. Mater. Chem. A. 2017, 5, 23926., and 28 mL of chloroform were placed in a reaction vessel, and 1.86 mL of piperidine was added and stirred at 60 ° C. for 3 hours. After cooling, the solvent was distilled off, methanol was added to disperse the solid, and the mixture was filtered to obtain 1.6 g (yield 33%) of compound (1a-43). The resulting compound (1a-43) 1 Identification was performed by H-NMR analysis. 1 The H-NMR measurement data is shown below. 1H-NMR (400MHz, solvent: CD2Cl2, ppm): δ8.32(d,2H), 8.08-8.04(m,2H), 7.88(s,1H), 7.80(d,1H), 7.67-7 .63(m,2H), 7.40-7.35(m,2H), 7.25-7.20(m,2H), 6.89-6.85(m,2H), 6.74-6.69(m,1H), 6.25(d,1H).

[0244] [ka]

[0245] [Experimental Example 1] For the compounds (1a-1), (1a-2), (1a-23) and (X-1) obtained in each synthesis example, TG-DTA measurements were performed under normal pressure at a heating rate of 10°C / min, and the temperature at which the weight loss reached 5% was observed. The results were evaluated based on the following evaluation criteria. In the evaluation, the temperature at which the weight loss of compound (X-1) reached 5% was used as the standard. (Evaluation Criteria) Good: The temperature at which the weight loss was 5% lower than the standard decreased by more than 10°C. △: The temperature at which the weight was reduced by 5% was 5 to 10°C lower than the standard.

[0246] [Table 3]

[0247] As shown in Table 3, compounds (1a-1), (1a-2) and (1a-23) all showed a lower temperature for 5% weight loss than compound (X-1), and it was revealed that they could be vacuum-deposited under milder conditions. Thus, due to the effect of fluorine substitution, these compounds of the present invention can form a vapor-deposited film with less thermal load than compound (X-1).

[0248] [Experimental Example 2] For the compounds (1a-34), (1a-29), and (X-3) obtained in each synthesis example, TG-DTA measurement was performed in the same manner as in Experimental Example 1, and the 5% weight loss temperature was evaluated. In the evaluation, the temperature at which the compound (X-3) experienced a 5% weight loss was used as the standard.

[0249] [Table 4]

[0250] As shown in Table 4, both compounds (1a-34) and (1a-29) showed a lower temperature for 5% weight loss than compound (X-3), and it was revealed that they could be vacuum-deposited under milder conditions. Thus, due to the effect of fluorine substitution, these compounds of the present invention can form a vapor-deposited film with a reduced thermal load compared to compound (X-3).

[0251] [Experimental Example 3] The ionization potential and absorption spectrum of the thin films of the compounds (1a-39), (1a-43) and (X-3) obtained in each synthesis example were measured. More specifically, the glass substrate was treated with ozone for 20 minutes using an ultraviolet ozone cleaner (manufactured by Japan Laser Electronics Co., Ltd., product name "NL-UV253"), and then the compounds (1a-39), (1a-43) and (X-3) were deposited as p-type semiconductor materials to form thin films with a thickness of 70 nm. The obtained thin film was measured using an air photoelectron yield spectrometer (manufactured by Riken Keiki Co., Ltd., product name "AC-3") to estimate the ionization potential. The obtained results were evaluated based on the following criteria. The evaluation was based on the ionization potential of the compound (X-3). (Evaluation Criteria) ⊚: The ionization potential was 0.4 eV or more smaller than the standard. ◯: The ionization potential was 0.2 eV or more smaller than the reference. △: The ionization potential was smaller than the reference by 0.1 eV or more.

[0252] The absorption spectrum of the obtained thin film was measured using a spectrophotometer (manufactured by Hitachi, Ltd., product name "U-4100"). The obtained results were evaluated based on the following evaluation criteria, where the maximum absorption wavelength of the compound (X-3) was used as the standard. (Evaluation Criteria) ◯: The maximum absorption wavelength was within ±0.2 eV of the standard. △: The maximum absorption wavelength was within ±0.2 to ±0.4 eV from the reference.

[0253] [Table 5]

[0254] As shown in Table 5, it was revealed that both compounds (1a-39) and (1a-43) can lower the ionization potential more than that of compound (X-3) without almost changing the maximum absorption wavelength from compound (X-3). From these results, it was found that the compounds of the present invention have a deep HOMO level and are therefore more stable against air oxidation. Furthermore, since these compounds of the present invention have a deep HOMO level due to the effect of fluorine substitution, it is possible to extract holes even in a photoelectric conversion element using a hole transport material having a deep HOMO level, and it was found that light detection can be performed without almost changing the light detection wavelength of maximum sensitivity.

[0255] [Evaluation of photoelectric conversion ability] The photoelectric conversion element obtained in each example was irradiated with light under an applied voltage of -3 V, and evaluated using an action spectrum measuring device (manufactured by Peccell Technologies, product name "PEC-S20").

[0256] [Example 1] A transparent conductive film of indium tin oxide (ITO) was patterned on a transparent glass substrate as a transparent electrode. The electrode surface of the ITO substrate was treated with ozone for 20 minutes using an ultraviolet ozone cleaner (manufactured by Japan Laser Electronics Co., Ltd., product name "NL-UV253"). Next, compound (1a-1) as a p-type semiconductor material and C60 fullerene (manufactured by Frontier Carbon Corporation) as an n-type semiconductor material were co-deposited to form a photoelectric conversion layer having a thickness of 120 nm. On the photoelectric conversion layer, C60 fullerene (manufactured by Frontier Carbon Corporation) was deposited as an electron transport material in a vacuum to form an electron transport layer having a thickness of 40 nm. Finally, aluminum was deposited as a metal electrode material on the electron transport layer in a vacuum to form a metal electrode having a thickness of 100 nm, thereby obtaining a photoelectric conversion element. The photoelectric conversion element thus fabricated was confirmed to function as a photoelectric conversion element in an evaluation of its photoelectric conversion ability.

[0257] [Example 2] A photoelectric conversion element was prepared in the same manner as in Example 1 except that the compound (1a-1) was changed to the compound (1b-1), and the photoelectric conversion performance was evaluated. As a result, it was confirmed that the fabricated photoelectric conversion element functions as a photoelectric conversion element in the evaluation of its photoelectric conversion ability.

[0258] [Example 3] A photoelectric conversion element was prepared in the same manner as in Example 1 except that the compound (1a-1) was changed to the compound (1a-23), and the photoelectric conversion performance was evaluated. As a result, it was confirmed that the fabricated photoelectric conversion element functions as a photoelectric conversion element in the evaluation of its photoelectric conversion ability.

[0259] [Example 4] A photoelectric conversion element was prepared in the same manner as in Example 1 except that the compound (1a-1) was changed to the compound (1a-34), and the photoelectric conversion performance was evaluated. As a result, it was confirmed that the fabricated photoelectric conversion element functions as a photoelectric conversion element in the evaluation of its photoelectric conversion ability.

[0260] [Example 5] A photoelectric conversion element was prepared in the same manner as in Example 1 except that the compound (1a-1) was changed to the compound (1c-1), and the photoelectric conversion performance was evaluated. As a result, it was confirmed that the fabricated photoelectric conversion element functions as a photoelectric conversion element in the evaluation of its photoelectric conversion ability.

[0261] [Example 6] A photoelectric conversion element was prepared in the same manner as in Example 1 except that the compound (1a-1) was changed to the compound (1a-39), and the photoelectric conversion ability was evaluated. As a result, it was confirmed that the fabricated photoelectric conversion element functions as a photoelectric conversion element in the evaluation of its photoelectric conversion ability.

[0262] [Example 7] A photoelectric conversion element was prepared in the same manner as in Example 1 except that the compound (1a-1) was changed to the compound (1a-43), and the photoelectric conversion performance was evaluated. As a result, it was confirmed that the fabricated photoelectric conversion element functions as a photoelectric conversion element in the evaluation of its photoelectric conversion ability. [Explanation of symbols]

[0263] 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): 【Chemistry 1】 (In the formula (1), D represents a monocyclic or fused-ring heterocyclic group containing a thienyl structure, one hydrogen atom of a thiophene ring contained in the heterocyclic group is substituted with an N-monosubstituted amino group or an N,N-disubstituted amino group, and the N-monosubstituted amino group or the N,N-disubstituted amino group has a substituent selected from an alkyl group in which one or more hydrogen atoms may be substituted, an aryl group in which one or more hydrogen atoms may be substituted, and a heteroaryl group in which one or more hydrogen atoms may be substituted, At least one of the substituents is the aryl group or the heteroaryl group, and at least one hydrogen atom of the aryl ring or heteroaryl ring contained in at least one of the substituents is substituted with a fluorine atom. L is a bonding group, a monocycle or condensed ring containing a sulfur-containing heteroaryl ring, or a polycycle in which two or more rings selected from the monocycle and condensed ring are bonded. A is a group represented by the following general formula (2). When L in formula (1) is a bonding group, the group represented by A=CH- bonds to the thiophene ring in D. 【Chemistry 2】 (In the formula (2), Z is a benzene ring or a naphthalene ring in which one or more hydrogen atoms may be substituted. X is an oxygen atom or a dicyanomethylene group.)

2. The compound according to claim 1, wherein D is any one of groups represented by the following general formulas (3a) to (3c): 【Chemistry 3】 (In the above formulas (3a) to (3c), R １ and R ２ are each independently a hydrogen atom, a deuterium atom, an alkyl group, an alkoxy group, C(=O)OR (wherein R is an alkyl group or an aryl group), or an amino group. １ and Ar ２ and each independently represent an alkyl group in which one or more hydrogen atoms may be substituted, an aryl group in which one or more hydrogen atoms may be substituted, or a heteroaryl group in which one or more hydrogen atoms may be substituted, and at least one of them is an aryl group in which at least one hydrogen atom is substituted with a fluorine atom, or a heteroaryl group in which at least one hydrogen atom is substituted with a fluorine atom. １ is a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, CR ３ R ４ , SiR ３ R ４ , or GeR ３ R ４ It is. ３ and R ４ are each independently a hydrogen atom, an alkyl group, or an aryl group.

3. The compound according to claim 1, wherein L is a bonding group or contains any one of groups represented by the following general formulas (4a) to (4c): 【Chemistry 4】 (In the above formulas (4a) to (4c), R ５ and R ６ are each independently a hydrogen atom, a deuterium atom, an alkyl group, an alkoxy group, C(=O)OR (wherein R is an alkyl group or an aryl group), or an amino group. ２ is a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, CR ７ R ８ , SiR ７ R ８ , or GeR ７ R ８ It is. ７ and R ８ are each independently a hydrogen atom, an alkyl group, or an aryl group.

4. The compound according to claim 1, wherein A is a group represented by the following general formula (2a) or (2b): 【Chemistry 5】 (In the above formulas (2a) and (2b), Q １ ~Q ８ are each independently a hydrogen atom, a chlorine atom, a fluorine atom, a bromine atom, or a cyano group. １ and X ２ are each independently an oxygen atom or a dicyanomethylene group.

5. The compound according to claim 1, wherein A is a group represented by the following general formula (2a-1) or (2b-1), D is any of the groups represented by the following general formulas (3a-1) to (3c-1), and L includes a bonding group or any of the groups represented by the following general formulas (4a-1) to (4c-1). 【Chemistry 6】 (In the above formula, Q １１ , Q ４１ , Q ５１ and Q. ８１ is a hydrogen atom, Q ２１ , Q ３１ , Q ６１ and Q. ７１ are each independently a fluorine atom or a chlorine atom, or Q １１ ~Q ８１ are each independently a hydrogen atom, a fluorine atom, or a chlorine atom. 【Chemistry 7】 (In the above formula, Ar １１ and Ar ２１ are each independently a phenyl group in which one or more hydrogen atoms may be substituted, a naphthyl group in which one or more hydrogen atoms may be substituted, an anthracenyl group in which one or more hydrogen atoms may be substituted, a biphenyl group in which one or more hydrogen atoms may be substituted, a terphenyl group in which one or more hydrogen atoms may be substituted, a fluorenyl group in which one or more hydrogen atoms may be substituted, a thienyl group in which one or more hydrogen atoms may be substituted, a thienothienyl group in which one or more hydrogen atoms may be substituted, a benzothienyl group in which one or more hydrogen atoms may be substituted, a benzofuryl group in which one or more hydrogen atoms may be substituted, a dibenzothienyl group in which one or more hydrogen atoms may be substituted, or a dibenzofuryl group in which one or more hydrogen atoms may be substituted. １１ and Ar ２１ At least one hydrogen atom in the ring of at least one of M is substituted with a fluorine atom. １ is a sulfur atom, CR ３１ R ４１ or SiR ３１ R ４１ It is. ３１ and R ４１ are each independently an alkyl group or an aryl group. 【Chemistry 8】 (In the above formula, M ２ is a sulfur atom, CR ７１ R ８１ or SiR ７１ R ８１ It is. ７１ and R ８１ are each independently an alkyl group or an aryl group.

6. The compound according to claim 1, which is a compound represented by the following general formulas (1a) to (1m): 【Chemistry 9】 (In the above formula, A is a group represented by the following general formula (2a-2) or (2b-2). １２ and Ar ２２ are each independently a phenyl group in which one or more hydrogen atoms may be substituted, a naphthyl group in which one or more hydrogen atoms may be substituted, a biphenyl group in which one or more hydrogen atoms may be substituted, a fluorenyl group in which one or more hydrogen atoms may be substituted, a benzothienyl group in which one or more hydrogen atoms may be substituted, a benzofuryl group in which one or more hydrogen atoms may be substituted, a dibenzothienyl group in which one or more hydrogen atoms may be substituted, or a dibenzofuryl group in which one or more hydrogen atoms may be substituted. １２ and Ar ２２ At least one hydrogen atom in the ring of at least one of M is substituted with a fluorine atom. １ is a sulfur atom, CR ３１ R ４１ or SiR ３１ R ４１ It is. ３１ and R ４１ are each independently an alkyl group or an aryl group. ２ is a sulfur atom, CR ７１ R ８１ or SiR ７１ R ８１ It is. ７１ and R ８１ are each independently an alkyl group or an aryl group. 【Chemistry 10】 (In the above formula, Q ２２ , Q ３２ , Q ６２ and Q. ７２ are each independently a hydrogen atom, a fluorine atom, or a chlorine atom.

7. A membrane comprising a compound according to any one of claims 1 to 6.

8. A photoelectric conversion element comprising the film according to claim 7.

9. An image sensor comprising the photoelectric conversion element according to claim 8.

10. A fingerprint sensor comprising the photoelectric conversion element according to claim 8.

11. A pulse wave sensor comprising the photoelectric conversion element according to claim 8.

Images