Compound and component containing said compound

Abstract

To provide a compound suitable for organic electronics, etc.SOLUTION: A compound is represented by the formula (1). [ R1 to R8 are independently organic groups; R7 and R8 may be connected; m is an integer of 0-3, and n is an integer of 2 or more; a ring A may have a substituent and is the divalent group of an aromatic hydrocarbon ring or a heteroaromatic ring; Z1 and Z2 are independently a direct bond, an alkenylene group, an alkynylene group or an imino group; X1 and X2 are independently NR100, O, S, S(=O) or S(=O)2; and R100 is an alkyl group, an aryl group or a heteroaryl group.].SELECTED DRAWING: Figure 3

Description

[Technical field]

[0001] The present invention relates to a novel compound and a member containing the compound. The compound of the present invention can be suitably used as a member for organic electronics, all-solid-state batteries, recording memories, specific wavelength luminescent markers, specific molecular sensor materials, etc. [Background technology]

[0002] Compounds with a thiophene skeleton have attracted much attention as compounds that can be used for various applications, such as organic electronic materials for OLEDs and OPVs, negative electrode active materials for all-solid-state batteries, near-infrared light-emitting materials, etc. In particular, compounds with an extended planar benzothiophene skeleton have attracted much attention as units that improve carrier mobility and packing properties.

[0003] For example, Patent Document 1 discloses that a compound having a highly planar skeleton in which thiophene rings are fused to the 9th and 8th positions, and the 10th and 1st positions of phenanthrene, has high carrier mobility and packing properties and is useful as an organic semiconductor material. In addition, Non-Patent Document 1 shows that 2,9-bis(tert-butyldimethylsilyl)phenanthro[9,8-bc:10,1-b'c']dithiophene (PHDT-Si) has high rigidity, a planar extended π-conjugated structure, and strong light absorption and fluorescence properties. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2018-150248 A [Non-patent literature]

[0005] [Non-Patent Document 1] Synthesis and optical and electrochemical properties of a phenanthrodithiophene(fused-bibenzo[c]thiophene) derivative, Yousuke Ooyama etc., Org. Biomol. Chem., 2017,15,7302-7307 Summary of the Invention [Problem to be solved by the invention]

[0006] The phenanthrobithiophene compounds reported so far have a tendency to aggregate due to their high planarity, and when used as luminescent materials, they have the problem of being prone to concentration quenching. In addition, the sites for introducing substituents into the thiophene moiety are limited, making it difficult to optimize the physical properties through chemical modification.

[0007] An object of the present invention is to provide a compound that solves the problems associated with conventional phenanthrobithiophene compounds. [Means for solving the problem]

[0008] As a result of extensive research aimed at solving the above problems, the present inventors have succeeded in synthesizing a novel benzo[c]thiophene derivative, and further succeeded in introducing an aldehyde group and polymerizing the derivative using this skeleton. The present invention has been achieved based on these findings, and is summarized as follows.

[0009] [1] A compound represented by the following formula (1):

[0010] [ka]

[0011] [In formula (1), R 1 ~R 8 each independently represents an organic group; R 7 and R 8may be linked, m represents an integer from 0 to 3. n represents an integer of 2 or more, Ring A represents a divalent group of an aromatic hydrocarbon ring or an aromatic heterocycle which may have a substituent; Z 1 and Z 2 each independently represents a direct bond, an alkenylene group, an alkynylene group, or an imino group, X 1 and X 2 are each independently, NR 100 , O, S, S(=O) or S(=O)2, R 100 represents an alkyl group, an aryl group, or a heteroaryl group.

[0012] [2] The compound according to [1], having a weight average molecular weight of 500 or more.

[0013] [3] A component containing the compound according to [1] or [2].

[0014] [4] A compound represented by the following formula (3):

[0015] [ka]

[0016] [In formula (3), R 17 ~R 24 each independently represents an organic group; Y 1 and Y 2 each independently represents a formyl group, an imino group, or an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group which may have a substituent; X 5 and X 6 are each independently, NR 102 , O, S, S(=O) or S(=O)2, R 102 represents an alkyl group. Effect of the Invention

[0017] The compound of the present invention has a benzo[c]heterole as the main skeleton, and when used as a light-emitting material by extending the conjugation, it is expected to have high light-emitting efficiency, and since it has a twisted structure, it is expected to have high solvent solubility. Alternatively, it can form a cavity, has excellent ion conductivity, or has a twisted structure, so it can be highly purified, and can be melted into resins, etc. Furthermore, the compound of the present invention has a high degree of freedom in introducing substituents, and the physical properties can be easily optimized by chemical modification or the molecular weight can be easily increased by polymerization, making it possible to realize a compound having desired physical properties and molecular weight depending on the application. Therefore, the compound of the present invention can be suitably used as a component of organic electronics, all-solid-state batteries, recording memories, specific wavelength luminescent markers, specific molecular sensor materials, and the like. [Brief description of the drawings]

[0018] [Figure 1] 1 is a chart showing the absorption spectrum and emission spectrum of compound b obtained in Synthesis Example 1. [Diagram 2] 1 is a chart showing the absorption spectrum and emission spectrum of the compound (3-1) obtained in Synthesis Example 1. [Diagram 3] 2 is a chart showing the absorption spectrum and emission spectrum of the compound (1-1) obtained in Synthesis Example 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] The following describes in detail the embodiments of the present invention, but the present invention is not limited to the following embodiments and can be modified in various ways within the scope of the invention.

[0020] [Compound represented by formula (1)] The compound according to the first aspect of the present invention is a novel compound represented by the following formula (1) (hereinafter, sometimes referred to as "compound (1)").

[0021] [ka]

[0022] [In formula (1), R 1 ~R 8 each independently represents an organic group; R 7 and R 8 may be linked, m represents an integer from 0 to 3. n represents an integer of 2 or more, Ring A represents a divalent group of an aromatic hydrocarbon ring or an aromatic heterocycle which may have a substituent; Z 1 and Z 2 each independently represents a direct bond, an alkenylene group, an alkynylene group, or an imino group, X 1 and X 2 are each independently, NR 100 , O, S, S(=O) or S(=O)2, R 100 represents an alkyl group, an aryl group, or a heteroaryl group.

[0023] Compound (1) has a benzo[c]heterole backbone, which is expected to expand conjugation and achieve high luminescence efficiency, and has a twisted structure, which is expected to provide high solvent solubility. In addition, the compound has a high degree of freedom in the introduction of substituents, and can be easily polymerized to obtain a high molecular weight.

[0024] [R in formula (1)] 1 ~R 8 , Ring A, Z 1 and Z 2 , X 1 and X 2 , m, n] (R 1 ~R 8 ) R 1 ~R 8Each independently represents an organic group. The organic group is not particularly limited, but examples thereof include a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, a halogen atom, an amino group, a carbonyl group, a carboxyl group, a cyano group, and a silyl group (hereinafter, an aryl group and a heteroaryl group may be referred to as "(hetero)aryl group"). 7 and R 8 may be linked.

[0025] Examples of the halogen include a fluoro group, a chloro group, and a bromo group. The alkyl group is not particularly limited, but may be branched or substituted. The number of carbon atoms in the alkyl group is not particularly limited, but is 1 or more, preferably 20 or less, and more preferably 12 or less. The number of carbon atoms in these ranges tends to improve the solvent solubility. The alkoxy group is not particularly limited, but may be branched or substituted. The number of carbon atoms in the alkoxy group is also not particularly limited, but is 1 or more, preferably 20 or less, more preferably 12 or less. The number of carbon atoms in this range tends to improve the solvent solubility. The (hetero)aryl group is not particularly limited, but is composed of a single ring or a condensed ring, and specific examples thereof include a phenyl group, a naphthyl group, an anthranyl group, a thiazolyl group, an oxazolyl group, and a pyridyl group. The number of carbon atoms in the (hetero)aryl group is also not particularly limited, but is 4 or more, preferably 6 or more, and preferably 26 or less, and more preferably 18 or less. The number of carbon atoms within these ranges tends to provide an extension of conjugation and appropriate solvent solubility.

[0026] The alkyl group, alkoxy group and (hetero)aryl group may have a substituent, and examples of the substituent that may be used include an alkyl group, an alkoxy group, an amino group, a silyl group, etc. Among these, the alkyl group is preferred from the viewpoint of improving durability and solubility in a solvent.

[0027] R 1 ~R 8Among the above, R is preferably a hydrogen atom, an alkyl group, or a (hetero)aryl group. 1 ~R 8 The combination of R 7 and R 8 , R 3 and R 6 , R 2 and R 5 , R 1 and R 4 It is preferable that they are the same.

[0028] Also, R 7 and R 8 R may be linked, and when linked, it tends to contribute to the longer wavelength of compound (1). 7 and R 8 When the bond is made, it is preferably directly bonded from the viewpoint of reducing distortion.

[0029] (Ring A) Ring A represents a divalent aromatic hydrocarbon ring or aromatic heterocyclic ring which may have a substituent.

[0030] The aromatic hydrocarbon ring is not particularly limited, but preferably has 5 or more carbon atoms and 20 or less carbon atoms. Specific examples include divalent groups such as a benzene ring, a naphthalene ring, a fluorene ring, and a phenanthrene ring.

[0031] The aromatic heterocycle is not particularly limited, but preferably has 3 or more carbon atoms and 20 or less carbon atoms. Specific examples include divalent groups such as 5-membered rings such as thiophene, thiazole, oxazole, and thiadiazole; condensed rings containing a 5-membered ring such as thienothiophene and benzothiadiazole; rings having a nitrogen atom as a hetero atom such as carbazole, pyridine, pyrazine, pyrimidine, quinazoline, and quinoxaline; and rings having a silicon atom such as dithienosilole.

[0032] Among these, from the viewpoints of solvent solubility and ease of synthesis, ring A is preferably an aromatic heterocyclic group, more preferably a 5-membered aromatic heterocyclic group, and even more preferably a divalent group of a thiophene ring.

[0033] The substituent that the ring A may have is R 1 ~R 8 The substituents which the alkyl group etc. may have are also included, and preferred ones are also the same.

[0034] (X 1 and X 2 ) X 1 and X 2 are each independently, NR 100 , O, S, S(=O) or S(=O)2. X 1 and X 2 may be the same or different, but are preferably the same from the viewpoint of synthesis. Among these, S is preferred from the viewpoint of the stability of compound (1). R 100 represents an alkyl group or a (hetero)aryl group. The number of carbon atoms in the alkyl group is preferably 1 or more and 20 or less, and may be branched or straight-chained. The (hetero)aryl group is composed of a single ring or a condensed ring, and the number of carbon atoms is not particularly limited, but is 4 or more, preferably 6 or more, and preferably 26 or less, and more preferably 18 or less. Specific examples include a phenyl group, a naphthyl group, an anthranyl group, a thiazolyl group, an oxazolyl group, and a pyridyl group. In addition, X 1 and X 2 NR 100 If so, X 1 and X 2 Each R 100 may be the same or different, but from the viewpoint of synthesis, it is preferable that they are the same.

[0035] (Z 1 and Z 2 ) Z 1 and Z 2each independently represents a direct bond, an alkenylene group, an alkynylene group, or an imino group. The number of carbon atoms in the alkenylene group and the alkenylene group is not particularly limited, but from the viewpoint of stability, it is preferably from 2 to 6, and more preferably 4 or less. 1 and Z 2 may be the same or different, but is preferably the same from the viewpoint of ease of synthesis.

[0036] Among the above, Z 1 and Z 2 is preferably a direct bond from the viewpoint of ease of synthesis, but is preferably an alkenylene group from the viewpoint of increasing the wavelength of compound (1).

[0037] (m) m represents an integer of 0 to 3, and is preferably 0 from the viewpoint of ease of synthesis, but is preferably 1 from the viewpoint of a tendency for conjugation to be extended.

[0038] (n) n represents an integer of 2 or more. There is no particular upper limit to n, but it is preferably 100 or less from the viewpoint of solvent solubility.

[0039] (R 1 ~R 8 , m, n, ring A, X 1 , X 2 , Z 1 and Z 2 combination of R 1 ~R 8 , m, n, ring A, X 1 , X 2 , Z 1 and Z 2 The combination of R 1 ~R 8 is a hydrogen atom, and X 1 and X 2 are the same, m is 0, n is 2 or more and 100 or less, ring A is a divalent group of an aromatic hydrocarbon ring having 5 to 20 carbon atoms or an aromatic heterocyclic ring which is a 5-membered ring having 3 to 20 carbon atoms, which may have a substituent, and Z 1 and Z 2is preferably a direct bond from the viewpoint of ease of synthesis.

[0040] [Method for producing compound (1)] The method for producing compound (1) is not particularly limited, but examples thereof include the following schemes 1 and 2.

[0041] [ka]

[0042] The compound represented by the above formula (10) can be obtained by the method described in JP 2018-150248 A, etc. The compound represented by formula (10) and the compound represented by formula (11) can be reacted in the presence of a catalyst to obtain the compound represented by formula (12), which is compound (1).

[0043] [ka]

[0044] The compound represented by the above formula (13) can be obtained by the method described in JP-A-2018-150248 and the like. The compound represented by formula (13) and the compound represented by formula (14) are reacted in the presence of a catalyst to obtain a compound represented by formula (15), which is compound (1). In addition, Z in formula (13) represents a halide, a trialkylstannyl group, a boryl group which may have a substituent, an ethynyl group, a vinyl group which may have a substituent, an amino group which may have a substituent, or a boronic acid ester group, and W in formula (14) represents a trialkylstannyl group, a boryl group which may have a substituent, an ethynyl group, a vinyl group which may have a substituent, an amino group which may have a substituent, or a halide. When Z is a halide, W is preferably a trialkylstannyl group or a boryl group which may have a substituent, and when Z is a trialkylstannyl group, a boryl group which may have a substituent, an ethynyl group, a vinyl group which may have a substituent, or an amino group which may have a substituent, W is preferably a halide.

[0045] In either scheme, the reaction conditions vary depending on the substrate, but the reaction temperature is 10°C to 200°C, the reaction time is 10 minutes to 24 hours, and the reaction solvent is not particularly limited, but examples thereof include toluene, N,N-dimethylformamide (DMF), methylene chloride, and tetrahydrofuran (THF). As the catalyst, a palladium-based catalyst, a nickel-based catalyst, a copper-based catalyst, and the like can be used.

[0046] [Specific examples of compound (1)] Specific examples of compound (1) are shown below, but compound (1) of the present invention is not limited to the following exemplary compounds.

[0047] [ka]

[0048] [Weight average molecular weight] The weight-average molecular weight of compound (1) is not particularly limited, but is preferably 1,000,000 or less, more preferably 500,000 or less. Also, it is preferably 500 or more, more preferably 1,000 or more. When the weight-average molecular weight is within these ranges, it tends to be possible to achieve both solvent solubility and extended conjugation. The method for measuring the weight average molecular weight is not particularly limited, but GPC analysis can be used.

[0049] [Maximum absorption wavelength] When compound (1) has absorption, the maximum absorption wavelength is preferably 340 nm or more, more preferably 370 nm or more. Also, it is preferably 1500 nm or less, more preferably 1400 nm or less. When the maximum absorption wavelength is in these ranges, the conjugation tends to be expanded. The method for measuring the maximum absorption wavelength is not particularly limited, but a spectrophotometer can be used.

[0050] [Compound represented by formula (2)] The compound according to the second aspect of the present invention is a novel compound represented by the following formula (2) (hereinafter, sometimes referred to as "compound (2)").

[0051] [ka]

[0052] [In formula (2), R 10 ~R 16 each independently represents an organic group; k represents an integer from 0 to 3. l represents an integer of 2 or more, Ring B represents a divalent group of an aromatic hydrocarbon ring or an aromatic heterocycle which may have a substituent, Z 3 and Z 4 each independently represents a direct bond, an alkenylene group, an alkynylene group, or an imino group, X 3 and X 4 are each independently, NR 101 , O, S, S(=O) or S(=O)2, R 101 represents an alkyl group.

[0053] Compound (2) has a twisted structure, which gives it high solvent solubility, and it also forms cavities and has excellent ionic conductivity. In addition, it has a high degree of freedom in introducing substituents, and it can be easily polymerized to obtain a high molecular weight.

[0054] [R in formula (2)] 10 ~R 16 , ring B, Z 3 and Z 4 , X 3 and X 4 , k, l] (R 10 ~R 16 ) R 10 ~R 16 Each independently represents an organic group. The organic group is, for example, R 1 ~R 8The preferred ranges are also the same as those listed above.

[0055] (ring B) Ring B represents a divalent aromatic hydrocarbon ring or aromatic heterocyclic ring which may have a substituent. The divalent aromatic hydrocarbon ring or aromatic heterocyclic ring which may have a substituent has the same meaning as that exemplified for ring A in formula (1), and the preferred range is also the same.

[0056] (X 3 and X 4 ) X 3 and X 4 are each independently, NR 101 , O, S, S(=O) or S(=O)2. X 3 and X 4 may be the same or different, but are preferably the same from the viewpoint of synthesis. Among these, S is preferred from the viewpoint of the stability of compound (2).

[0057] R 101 represents an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 or more and 20 or less, and the alkyl group may be branched or linear. 3 and X 4 NR 101 If so, X 3 and X 4 Each R 101 may be the same or different, but from the viewpoint of synthesis, it is preferable that they are the same.

[0058] (Z 3 and Z 4 ) Z 3 and Z 4 each independently represents a direct bond, an alkenylene group, an alkynylene group, or an imino group. The number of carbon atoms in the alkenylene group and the alkenylene group is not particularly limited, but from the viewpoint of stability, it is preferably from 2 to 6, and more preferably 4 or less. 1 and Z 2 may be the same or different, but is preferably the same from the viewpoint of ease of synthesis. Among these, the imino group is preferred from the viewpoint of ease of synthesis.

[0059] (k) k represents an integer of 0 to 3, and is preferably 1 from the viewpoint of extending conjugation.

[0060] (l) l represents an integer of 2 or more. There is no particular upper limit for l, but it is preferably 100 or less from the viewpoint of solvent solubility.

[0061] (R 10 ~R 16 ,k,l,ring B,X 3 , X 4 , Z 3 and Z 4 combination of R 10 ~R 16 ,k,l,ring B,X 3 , X 4 , Z 3 and Z 4 The combination of is not particularly limited, but k is 1, l is 2 or more and 100 or less, and X 3 and X 4 are the same, ring B is a divalent group of an aromatic hydrocarbon ring having 5 to 20 carbon atoms or an aromatic heterocyclic ring which is a 5-membered ring having 3 to 20 carbon atoms, which may have a substituent, and R 9 =R 12 , R 10 =R 13 , R 11 =R 14 , R 15 =R 16 and Z 3 and Z 4 is preferably an imino group from the viewpoint of ease of synthesis.

[0062] [Method for producing compound (2)] The method for producing compound (2) is not particularly limited, but may be, for example, the following Scheme 3.

[0063] [ka]

[0064] The compound represented by the above formula (16) can be obtained by a method of lithiating the compound represented by the formula (10) in the above scheme 1 using LDA (lithium diisopropylamide) or the like, and reacting it with a reagent. The compound represented by the formula (16) and the compound represented by the formula (17) are reacted using a catalyst to obtain the compound represented by the formula (18), which is the compound (2). Z in the formula (16) can be obtained by a method of reacting the compound represented by the formula (16) and the compound represented by the formula (17) using a catalyst. a and Z b represents a halide, a trialkylstannyl group, a boryl group, or a boronic acid ester group, and W in formula (17) represents a 2 represents a trialkylstannyl group, a boryl group, a boronic acid ester group, an ethynyl group, a vinyl group which may have a substituent, an amino group which may have a substituent, or a halide. 3 ,Z 4 is a direct bond, an alkenylene group, an alkynylene group, or an imino group.

[0065] The reaction conditions vary depending on the substrate, but the reaction temperature is 10°C to 200°C, and the reaction time is 10 minutes to 24 hours. There are no particular restrictions on the solvent, but examples include toluene, N,N-dimethylformamide (DMF), methylene chloride, and tetrahydrofuran (THF). As the catalyst, a palladium-based catalyst, a nickel-based catalyst, a copper-based catalyst, and the like can be used.

[0066] [Specific examples of compound (2)] Specific examples of compound (2) are shown below, but compound (2) of the present invention is not limited to the following exemplary compounds.

[0067] [ka]

[0068] [Weight average molecular weight] The weight-average molecular weight of the compound (2) is not particularly limited, but is preferably 1,000,000 or less, more preferably 500,000 or less. Also, it is preferably 500 or more, more preferably 1,000 or more. When the weight-average molecular weight is within these ranges, it tends to be possible to achieve both solvent solubility and extended conjugation. The method for measuring the weight average molecular weight is not particularly limited, but GPC analysis can be used.

[0069] [Maximum absorption wavelength] When compound (2) has absorption, the maximum absorption wavelength is preferably 650 nm or more, more preferably 680 nm or more. Also, it is preferably 1500 nm or less, more preferably 1400 nm or less. When the maximum absorption wavelength is in these ranges, the conjugation tends to be expanded. The method for measuring the maximum absorption wavelength is not particularly limited, but a spectrophotometer can be used.

[0070] [Compound represented by formula (3)] The compound according to the third aspect of the present invention is a novel compound represented by the following formula (3) (hereinafter, sometimes referred to as "compound (3)").

[0071] [ka]

[0072] [In formula (3), R 17 ~R 24 each independently represents an organic group; Y 1 and Y 2 each independently represents a formyl group, an imino group, or an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group which may have a substituent; X 5 and X 6 are each independently, NR 102 , O, S, S(=O) or S(=O)2, R 102represents an alkyl group.

[0073] Compound (3) has a twisted structure and is therefore highly compatible, making it possible to dissolve it in resins, etc. Compound (3) can be used in indicators, bioimaging, additives, etc.

[0074] [R in formula (3)] 17 ~R 24 , Y 1 and Y 2 , X 5 and X 6 ] (R 17 ~R 24 ) R 17 ~R 24 Each independently represents an organic group. The organic group is, for example, R 1 ~R 8 The preferred ranges are also the same as those listed above.

[0075] (Y 1 and Y 2 ) Y 1 and Y 2 each independently represents a formyl group, an imino group, or an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group which may have a substituent.

[0076] The alkenyl group and alkynyl group are not particularly limited, but from the viewpoint of ease of synthesis, they preferably have 2 to 10 carbon atoms, more preferably 5 or less, and even more preferably 3 or less.

[0077] The (hetero)aryl group is not particularly limited, but is composed of a single ring or a condensed ring, and specific examples thereof include a phenyl group, a naphthyl group, an anthranyl group, a thiazolyl group, an oxazolyl group, a pyridyl group, a thienyl group, and a thienothienyl group. The number of carbon atoms is also not particularly limited, but is 4 or more, preferably 6 or more, and preferably 26 or less, and more preferably 18 or less. The number of carbon atoms within these ranges tends to provide an extension of conjugation and appropriate solvent solubility.

[0078] Substituents that the alkenyl group, alkynyl group, or (hetero)aryl group may have include an alkyl group, a cyano group, a halide, an alkoxyl group, an alkylamino group, an aryl group, or a heteroaryl group.

[0079] Among the above, Y 1 and Y 2 From the viewpoint of stability, Y is preferably a heteroaryl group. 1 and Y 2 may be the same or different, but it is preferable that they are the same from the viewpoint of ease of synthesis.

[0080] (X 5 and X 6 ) X 5 and X 6 are each independently, NR 102 , O, S, S(=O) or S(=O)2. X 5 and X 6 may be the same or different, but is preferably the same from the viewpoint of ease of synthesis. Among these, S is preferred from the viewpoints of aromaticity and stability.

[0081] R 102 represents an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 or more and 20 or less, and the alkyl group may be branched or linear. 5 and X 6 NR 102 If so, X 5 and X 6 Each R 102 may be the same or different, but from the viewpoint of synthesis, it is preferable that they are the same.

[0082] (R 17 ~R 24 , Y 1 , Y 2 , X 5 and X 6 combination of R 17 ~R 24 , Y1 , Y 2 , X 5 and X 6 The combination of X is not particularly limited. 5 and X 6 are the same, and Y 1 and Y 2 is an optionally substituted (hetero)aryl group, R 17 =R 20 , R 18 =R 21 , R 19 =R 22 , R 23 =R 24 From the viewpoint of ease of synthesis, it is preferable that

[0083] [Method for producing compound (3)] The method for producing compound (3) is not particularly limited, but examples thereof include the following schemes 4 to 6. The compound represented by formula (19) in the following schemes 4 and 5 also corresponds to compound (3).

[0084] [ka]

[0085] The compound represented by the above formula (19) can be obtained by lithiating the compound represented by the formula (10) in the above scheme 1 using LDA (lithium diisopropylamide) or the like, and reacting it with DMF. The compound represented by the formula (19) and the compound represented by the formula (20) can be reacted in an organic solvent such as THF under basic conditions at 10°C to 100°C to obtain the compound represented by the formula (21), which is the compound (3). In the formula (20), R is a phenyl group, and Y 100 is an aryl or heteroaryl group.

[0086] [ka]

[0087] The compound represented by formula (19) and the compound represented by formula (23) are reacted in an organic solvent such as toluene or ethanol at 0°C to 150°C for about 10 minutes to 24 hours to obtain the compound represented by formula (24), which is compound (3). 101 is an alkyl group.

[0088] [ka]

[0089] The compound represented by the above formula (25) can be obtained by lithiating the compound represented by formula (10) in the above scheme 1 using LDA (lithium diisopropylamide) or the like, and reacting it with a reagent. The compound represented by formula (25) can be reacted with the compound represented by formula (26) to obtain the compound represented by formula (27), which is compound (3). Note that Z in formula (25) is c and Q in formula (26) represents a halide, a trialkylstannyl group, a boryl group, or a boronic acid ester group, and Y in formula (26) represents a 102 represents an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group, each of which may have a substituent.

[0090] [Specific examples of compound (3)] Specific examples of compound (3) are shown below, but compound (3) of the present invention is not limited to the following exemplary compounds.

[0091] [ka]

[0092] [Part] Compound (1) or compound (2) can be used as a component for organic electronics, all-solid-state batteries, recording memories, specific wavelength luminescent markers, specific molecular sensor materials, and the like, more specifically, as a component for near-infrared luminescent markers, indicators, sensors, wavelength conversion films, and the like. EXAMPLES

[0093] The present invention will be described in more detail below with reference to synthetic examples instead of examples, but the present invention is not limited to the following synthetic examples and synthetic compounds as long as it does not deviate from the gist of the present invention. Note that the values ​​of various conditions and evaluation results in the following synthetic examples indicate the preferred ranges of the present invention, similar to the preferred ranges in the embodiments of the present invention, and the preferred ranges of the present invention can be determined by taking into consideration the preferred ranges in the above-mentioned embodiments and the values ​​in the following synthetic examples or the ranges indicated by a combination of the values ​​of the synthetic examples.

[0094] In this synthesis example, the following measuring instruments were used. FT-IR spectrum measurement: SHIMADZU IR Tracker-100ATR. 1 H NMR spectrum measurement: Varian-500 (500 MHz) FT NMR instrument. High performance hybrid mass spectrometry systems (APCI and GC-EI): Thermo Fisher Scientific LTQ Orbitrap XL and JEOL JMS-T100 GCV 4G. Absorption spectrum: SHIMADZU UV-3150 spectrophotometer. Emission spectrum: HORIBA FluoroMax-4 fluorescence measurement device. Fluorescence quantum yield: HORIBA FluoroMax-4 Fluorescence Measurement Instrument (includes integrating sphere and Nano LED 318nm). Cyclic voltammetry: Hokuto Denko Electrochemical Analysis System HZ-7000.

[0095] [Synthesis Example 1] <Synthesis of compound a> Compound a was synthesized according to the method described in JP 2018-150248 A (Synthesis of Compound 3).

[0096] <Synthesis of compound b> [ka]

[0097] Dry THF (100 ml) and compound a (3.3 mmol, 1 g) were added to a 200 ml three-neck flask purged with N2. After cooling to -20°C, n-BuLi (1.59 M, 13 mmol, 8.4 mL) was slowly added dropwise. After 1 hour, the mixture was quenched with water and concentrated. The concentrate was dissolved in an aqueous CH2Cl2 solution and neutralized with an aqueous NH4Cl solution. After washing with water and saturated saline, the mixture was dried over MgSO4 and the solvent was concentrated. Reprecipitation yielded 550 mg of a yellow solid that was thought to be an oligomer. The remaining solution was concentrated (450 mg) and purified with an alumina column (chloroform:hexane = 1:30) to obtain compound b. The yield of compound b was 40 mg, which was 4.5%. In addition, the FT-IR spectrum of the obtained compound b was measured, 1 H NMR spectroscopy and gas chromatographic analysis were performed, with the results shown below.

[0098] FT-IR(ATR):ν ~ =3103,1503,1334 cm -1 · 1 H NMR(500MHz,acetone-d6)δ=7.10-7.17(m,4H),7.51(d,J=3.4Hz,2H),7.67(d,J=8.8Hz,2H),8.55(d,J=7.6Hz,2H),7.92(d,J=3.4Hz 2H)ppm · 13 C NMR(125MHz,Acetone)δ=117.96,118.31,122.51,124.29,124.35,134.56,13845,139.91ppm ·GC-EI:m / z(%):[MH]+ calcd for C 16 H9S2,265.01457;found,265.01442

[0099] <Synthesis of compound (3-1)> [ka]

[0100] Compound b (0.94 mmol, 250 mg) dissolved in dry THF (2.5 ml) was added to a Schlenk flask purged with N2. After cooling to -20°C, LDA was slowly added dropwise, and after 3 hours, DMF was added. After 1 hour, the mixture was quenched with water and extracted with ethyl acetate, but a black solid was found that did not dissolve during this process. After extraction with ethyl acetate, the mixture was washed with water and saturated saline, dried over MgSO4, and the solvent was concentrated (240 mg). The mixture was purified using an alumina column (ethyl acetate:hexane = 1:5) to obtain compound (3-1). The yield of compound (3-1) was 30 mg, and the yield was 10%. In addition, the FT-IR spectrum of the obtained compound (3-1) was measured, 1 H NMR spectroscopy and gas chromatographic analysis were performed, with the results shown below.

[0101] FT-IR(ATR):ν ~ =2723,1636,1497cm -1 · 1 H NMR(500MHz,acetone-d6)δ=7.48(d,J=6.7Hz,2H),7.62-7.65(m,2H),8.38(s,2H),8.55(d,J=8.8Hz,2H),10.45(s,2H)ppm · 13 C NMR(125MHz,CDCl3)δ=120.85,126.04,126.75,130.47,132.74,133.51,139.52,140.75,181.05 ppm ·HRMS(APCI):m / z(%):[M+H+]calcd for C18H11O2S2,323.01950;found,323.01993

[0102] The photoelectric properties of compound b and compound (3-1) in THF solvent are shown in Table 1 below. The absorption spectrum and emission spectrum of compound b and compound (3-1) are shown in Figures 1 and 2, respectively. The CV measurements were carried out in AN (0.01 M) containing 0.1 M Bu4NClO4. The oxidation potential is corrected based on the redox potential of ferrocene.

[0103] [Table 1]

[0104] [Synthesis Example 2] <Synthesis of compound c> Compound c was obtained as a by-product during the synthesis of compound b from compound a.

[0105] <Synthesis of compound (1-1)> [ka]

[0106] Compound c (yellow) and THF (3.7 ml) were added to a Schlenk flask purged with N2, and FeCl3 dissolved in CH3NO2 (3.7 ml) was then added. After 2 hours, the reaction was stopped and the solution was concentrated. The compound was dissolved in CH2Cl2, but some compounds were not soluble in either water or CH2Cl2, so they were filtered. The compound dissolved in CH2Cl2 was washed with water and saturated saline, and dried over MgSO4. After concentration, 25 mg of compound (1-1) was obtained as a red-black solid. The weight-average molecular weight of compound (1-1) was 800.

[0107] The photoelectric properties of compound (1-1) in THF solvent are shown in Table 2 below. The absorption spectrum and emission spectrum are shown in FIG.

[0108] [Table 2]

Claims

1. A compound represented by the following formula (1): 【Chemistry 1】 [In formula (1), R １ ~R ８ each independently represents a group selected from a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, a halogen atom, an amino group, a carboxyl group, a cyano group, and a silyl group; R ７ and R ８ may be linked, m represents an integer from 0 to 3; n represents an integer of 2 or more; Ring A represents a divalent aromatic hydrocarbon ring or aromatic heterocyclic ring which may have a substituent; Z １ and Z ２ each independently represents a direct bond, an alkenylene group, an alkynylene group, or an imino group, X １ and X ２ are each independently: NR １００ , O, S, S(=O) or S(=O) ２ represents R １００ represents an alkyl group, an aryl group, or a heteroaryl group.

2. The compound according to claim 1 , having a weight average molecular weight of 500 or more.

3. A member comprising the compound according to claim 1 or 2.

4. A compound represented by the following formula (3): 【Chemistry 2】 [In formula (3), R １７ ~R ２４ each independently represents a group selected from a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, a halogen atom, an amino group, a carboxyl group, a cyano group, and a silyl group; Y １ and Y ２ each independently represents a formyl group, an imino group, or an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group which may have a substituent; X ５ and X ６ represents S.

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