JP2017059668A - Polymer and organic thin-film solar battery arranged by use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer easy to control in solubility while having functions of light absorbability, charge transportability, photoelectric conversion, etc.SOLUTION: A polymer comprises a structural unit expressed by the general formula (1). [In the formula, Rrepresents O, S, Se or Te; Rrepresents a group expressed by -SR(where Ris an alkyl group), or a group expressed by -SOR(where Ris an alkyl group); and "*" represents a bonding position.]SELECTED DRAWING: None

Description

  The present invention relates to a polymer and an organic thin film solar cell using the polymer.

  In recent years, attention has been focused on electronic devices (organic electronic devices) using organic materials, typified by organic transistors, organic electroluminescent devices, organic thin film solar cells and the like. For this reason, active research has been conducted on organic materials used in these organic electronic devices. The organic material used for the organic electronic device is specifically an organic material having functions such as light absorption characteristics, charge transport characteristics, photoelectric conversion characteristics, etc., and a compound having a benzothiadiazole skeleton as such a functional organic material A polymer having a benzothiadiazole skeleton as a structural unit has been proposed.

  For example, Patent Document 1 discloses the following general formula:

It is described that the compound having a structural unit represented by the formula has excellent charge mobility. In the above general formula, R ¹ represents an oxygen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an arylalkyl group, an aryl group, an alkoxy group, an aryloxy group, a cycloalkyl group, a cycloalkyloxy group, a heteroaryl group, An acyl group, a sulfonyl group, or a carbamate group is shown, and Ar ₁ and Ar ₂ represent an aromatic ring, a heteroaromatic ring, or a polycyclic fused ring containing a heteroaromatic ring. However, Patent Document 1 does not mention at all the optical properties (particularly light absorption properties) of this compound, and the optical properties of the compound having the structural unit represented by the above general formula and its similar compounds are unknown. is there. In addition, the polymer actually synthesized in Patent Document 1 is composed of a structural unit represented by the above general formula, in which a tricyclic structure in which a thiazole ring is condensed to a benzothiadiazole skeleton and a structure in which four thiophene rings are connected. This is only a polymer, and Patent Document 1 does not describe synthesis examples of other polymers.

US Patent Publication US2013 / 0137848

  As described above, Patent Document 1 describes a polymer composed of a structural unit having a structure in which four thiophene rings are linked to a benzothiadiazole skeleton having a thiazole ring condensed.

  However, the polymer described in Patent Document 1 is difficult to control the solubility, and has practical problems. Therefore, an object of the present invention is to provide a polymer that has functions such as a light absorption property, a charge transport property, and a photoelectric conversion property and can easily control the solubility.

  As a result of intensive studies in view of the above problems, the present inventors have found that a polymer having a structural unit or a similar structural unit in which a specific sulfur-containing group is bonded to a thiazole ring of a benzothiadiazole skeleton has light absorption characteristics, charge transport It was found that the solubility can be easily controlled while having functions such as characteristics and photoelectric conversion characteristics. Based on such knowledge, the present inventors have further studied and completed the present invention. That is, the present invention includes the following configurations.

  Item 1. General formula (1):

[Wherein R ¹ represents O, S, Se or Te. R ² represents a group represented by —SR ³ (R ³ is an alkyl group) or a group represented by —SO ₂ R ⁴ (R ⁴ is an alkyl group). * Indicates a binding position. ]
The polymer which has a structural unit represented by these.

  Item 2. General formula (2):

[Wherein, R ¹ and R ² are the same as defined above. D represents a donor linking group. * Indicates a binding position. ]
The polymer which has a structural unit represented by these.

  Item 3. Item 3. The polymer according to Item 1 or 2, which is a regioregular polymer.

  Item 4. General formula (3):

[Wherein, R ¹ and R ² are the same or different and the same as above. D is the same or different and represents a donor linking group. * Indicates a binding position. ]
The polymer in any one of claim | item 1 -3 which has a repeating unit represented by these.

Item 5. Item 5. The polymer according to any one of Items 1 to 4, wherein R ¹ is S.

  Item 6. Item 6. A charge transport material comprising the polymer according to any one of Items 1 to 5.

  Item 7. Item 6. An organic thin film solar cell material comprising the polymer according to any one of Items 1 to 5.

  Item 8. Item 8. An organic thin-film solar cell using the polymer according to any one of Items 1 to 5, the charge transport material according to Item 6, or the material for an organic solar cell according to Item 7.

  Item 9. General formula (4):

[Wherein R ¹ represents O, S, Se or Te. R ² represents a group represented by —SR ³ (R ³ is an alkyl group) or a group represented by —SO ₂ R ⁴ (R ⁴ is an alkyl group). X ¹ and X ² are the same or different and represent H or a halogen atom. ]
A compound represented by

Item 10. Item 10. The compound according to Item 9, wherein R ¹ is S.

Item 11. Item 11. The compound according to Item 9 or 10, wherein X ² is a halogen atom.

According to the present invention, since it has a structural unit to which a specific sulfur-containing group is bonded, it has functions such as light absorption characteristics, charge transport characteristics, and photoelectric conversion characteristics, and by appropriately selecting an alkyl group in R ² , Solubility can be easily controlled. Further, when R ² is a group represented by —SO ₂ R ⁴ , it is possible to further improve electron acceptability. The polymer of the present invention has a simpler skeleton than a conventional polymer having a benzothiadiazole skeleton, and is economical because it can be synthesized in large quantities from inexpensive raw materials.

It is a graph which shows the light absorption characteristic of the spin coat film of the polymer 21 obtained by the synthesis example 3-13. It is a graph which shows the light absorption characteristic of the spin coat film of the polymer 23 obtained by the synthesis example 3-15. It is a graph which shows the evaluation result (current-voltage curve) of the element (organic thin-film solar cell) obtained in Example 1. It is a graph which shows the evaluation result (IPCE spectrum) of the element (organic thin-film solar cell) obtained in Example 1. It is a graph which shows the evaluation result (current-voltage curve) of the element (organic thin-film solar cell) obtained in Example 2.

1. Polymer The polymer of the present invention has the general formula (1):

[Wherein R ¹ represents O, S, Se or Te. R ² represents a group represented by —SR ³ (R ³ is an alkyl group) or a group represented by —SO ₂ R ⁴ (R ⁴ is an alkyl group). * Indicates a binding position. ]
It has the structural unit represented by these.

Since it has such a structural unit, the polymer of the present invention has functions such as light absorption characteristics, charge transport characteristics, and photoelectric conversion characteristics. Further, by appropriately selecting the alkyl group in R ^2, the control of solubility can be easily performed. Therefore, by appropriately selecting an alkyl group in R ² depending on the solvent to be used, it is possible to easily improve the solubility.

In the general formula (1), R ¹ represents O, S, Se, or Te, and O or S is preferable and S is more preferable from the viewpoint of light absorption characteristics, charge transport characteristics, photoelectric conversion characteristics, and the like.

In the general formula (1), R ² represents a group represented by —SR ³ or a group represented by —SO ₂ R ⁴ , and R ³ and R ⁴ represent an alkyl group. The alkyl group may be linear, branched or cyclic, but is preferably a linear or branched alkyl group. 1-40 are preferable, as for carbon number of an alkyl group, 1-30 are more preferable, and 1-25 are more preferable. Of these, a methyl group or a long-chain linear or branched alkyl group (for example, a linear or branched alkyl group having 6 to 25 carbon atoms) is preferable. Examples of the cyclic alkyl group include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.

  The alkyl group may be substituted or unsubstituted. Examples of the substituent when substituted include a halogen atom (a chlorine atom, a bromine atom, an iodine atom, etc.), a cyano group, an alkoxy group (an alkoxy group having 1 to 40 carbon atoms such as a methoxy group and an ethoxy group), An aryl group (phenyl group, naphthyl group, etc.), an amino group, etc. are mentioned. The number of substituents is not particularly limited, but 0 to 3 is preferable.

  Among these, as the alkyl group, from the viewpoint of solubility,

[In formula, m shows the integer of 1-18. ]
Is preferably a group represented by

Etc. are preferred.

That is, as R ² , from the viewpoint of solubility,

Etc. are preferred.

Among the ^{R 2,} a group represented by _-SO 2 ^{R 4} are obtained by oxidizing a group represented by -SR ^3, as compared to the group represented by -SR ^3, the present invention The electron acceptability of the polymer can be further improved.

  In the general formula (1), * indicates a bonding position. The structural unit constituting the polymer of the present invention is bonded to *. However, when the structural unit represented by the general formula (1) is a terminal, a hydrogen atom or a halogen atom (chlorine atom, bromine atom, iodine atom, etc.) may be bonded with *.

  The number of structural units represented by the general formula (1) in the polymer of the present invention is not particularly limited. For example, 4-200 is preferable and 6-100 is more preferable.

  The polymer of the present invention may be a homopolymer having the structural unit represented by the general formula (1) as a repeating unit, but from the viewpoint of more easily absorbing light in the long wavelength region, a donor and an acceptor in the molecule. A donor-acceptor type polymer having both

  When the polymer of the present invention is a donor / acceptor type polymer, the structural unit represented by the general formula (1) functions as an acceptor unit. For this reason, it is preferable that the structural unit represented by General formula (1) has couple | bonded the polymer of this invention through the donor coupling group.

  That is, the polymer of the present invention has the general formula (2):

[Wherein, R ¹ and R ² are the same as defined above. D represents a donor linking group. * Indicates a binding position. ]
It is preferable to have a structural unit represented by

In the general formula (2), R ¹ and R ² are the same as described above. The same applies to preferred embodiments.

  In General formula (2), D shows a donor coupling group. In the present invention, the “donor linking group” means a linking group having donor properties (electron donating properties) and is a linking group having strong electron donating properties.

  The structural unit represented by the general formula (1) is bonded via a donor linking group, so that the polymer of the present invention is a donor-acceptor type polymer, and the absorption wavelength of the polymer of the present invention is longer. Can be

  In the general formula (2), as the donor linking group represented by D, donor linking groups employed in organic semiconductor compounds can be widely employed, and linking groups having a polycyclic structure are also preferably employed. In addition, it can be widely adopted from a linking group having a weak donor property to a linking group having a strong donor property.

  Examples of donor linking groups include:

[Wherein R ⁵ are the same or different,

^(Wherein, R ^{18, R 19,} and ^{R 20} are the same or different, represent an alkyl group of carbon number 1 to 40 (especially from 1 to 20).)
The group represented by these is shown. R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different and each represents an alkyl group having 1 to 40 carbon atoms (particularly 1 to 20). R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 40 (particularly 1 to 20) carbon atoms. Y represents O, Si or Ge. ]
The donor coupling group represented by these is mentioned. Above all, from the viewpoint of light absorption characteristics in the long wavelength region, ease of synthesis, etc.

[Wherein, R ⁵ , R ¹⁶ and R ¹⁷ are the same or different and the same as above. ]
The donor coupling group represented by these is preferable.

  The number of structural units represented by general formula (2) in the polymer of the present invention is not particularly limited. For example, 4-200 is preferable and 6-100 is more preferable.

  When the polymer of the present invention is a donor-acceptor type polymer, it may be a regiorandom polymer in which the orientation of the acceptor unit is random, but usually has high conductivity, excellent solubility, etc. It is preferably a regioregular polymer in which the direction of the unit is opposed.

  That is, the polymer of the present invention has the general formula (3):

[Wherein, R ¹ and R ² are the same or different and the same as above. D is the same as above. * Indicates a binding position. ]
It is preferable to have a repeating unit represented by

In the general formula (3), R ¹ , R ² and D are the same as described above. The same applies to preferred embodiments.

  The number of repeating units represented by formula (3) in the polymer of the present invention is not particularly limited. For example, 2-100 are preferable and 3-50 are more preferable.

  The molecular weight (weight average molecular weight) of the polymer of the present invention is, for example, preferably 1,000 to 1,000,000, more preferably 1500 to 500,000, and still more preferably 2000 to 100,000.

  Such a polymer of the present invention includes, for example, the general formula (5):

[Wherein, R ¹ is the same or different and is the same as defined above. R ² is the same or different and is the same as described above. R ⁵ is the same or different and is the same as described above. ]
It is a polymer which has a repeating unit represented by these.

2. Production Method of Polymer The method for synthesizing the polymer of the present invention is not particularly limited as long as a desired polymer can be synthesized. For example, a polymer having a repeating unit represented by the general formula (3) is represented by the following reaction formula 1:

[Wherein, R ¹ , R ² and D are the same as defined above. R ²¹ and R ²² are the same or different and each represents an alkyl group. X ³ , X ⁴ and X ⁵ are the same or different and are a halogen atom. n is an integer of 2 to 100. ]
It can synthesize | combine by reaction represented by these. Hereinafter, one embodiment of the method for producing the polymer of the present invention will be described, but the present invention is not limited thereto, and the polymer of the present invention can be synthesized by various methods.

In Reaction Scheme 1, R ¹ , R ² and D are the same as described above. The same applies to preferred embodiments.

In Reaction Scheme 1, the alkyl group represented by R ²¹ and R ²² may be linear or branched, but is preferably a linear or branched alkyl group. 1-20 are preferable, as for carbon number of an alkyl group, 1-12 are more preferable, and 1-6 are more preferable. R ²¹ and R ²² may be the same or different.

In Reaction Scheme 1, the halogen atom represented by X ³ , X ⁴ , and X ⁵ is not limited, and examples include a chlorine atom, a bromine atom, and an iodine atom, and a bromine atom is preferable from the viewpoint of yield and the like. X ² , X ³ , and X ⁴ may be the same or different.

  In Reaction Formula 1, n is not particularly limited, and is preferably an integer of 2 to 100, and more preferably an integer of 3 to 50.

  In addition, the compound represented by general formula (4A) is a compound included by the compound represented by general formula (4) mentioned later.

Compound (4A) → Compound (7)
This reaction can usually employ Ueda / Kosugi / Still coupling. Specifically, the compound represented by the general formula (4A) and the compound represented by the general formula (6) can be reacted in the presence of a palladium catalyst.

  There is no restriction | limiting in particular in the addition amount of the compound represented by General formula (6), From viewpoints, such as a yield, 0.1-2 mol is with respect to 1 mol of compounds represented by General formula (4A). Preferably, 0.2-1 mol is more preferable.

Examples of the palladium catalyst include metal palladium and palladium compounds known as synthesis catalysts for organic compounds (including polymer compounds). In the present invention, a palladium catalyst (palladium compound) used in the right rice / Kosugi / still coupling reaction can be used. Specifically, tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ), dichlorobis (triphenylphosphine) palladium (II) (PdCl ₂ (PPh ₃ ) ₂ ), palladium acetate (Pd (OAc ₂ ), [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (II) (Pd (dppf) Cl ₂ ), tris (dibenzylideneacetone) dipalladium (0) (Pd ₂ (dba) ₃ ), Tris (dibenzylideneacetone) dipalladium (0) chloroform complex (Pd ₂ (dba) ₃ · CHCl ₃ ), bis (dibenzylideneacetone) palladium (0), bis (trit-butylphosphino) palladium (0 ), [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II) dichloromethane complex (Pd (dppf) Cl ₂ .CH ₂ Cl ₂ etc. In this step, from the viewpoint of yield etc. _{, Pd 2 (dba) 3,} Pd 2 (dba) 3 · CHCl 3 and the like are preferable _{Pd 2 (dba) 3 · CHCl} 3 is more preferable.

  From the viewpoint of yield, the amount of the palladium catalyst used is usually preferably 0.01 to 0.2 mol, preferably 0.02 to 0.1 mol, relative to 1 mol of the compound represented by the general formula (4A). Is more preferable.

  Some of the palladium catalysts described above contain a ligand, but a phosphorus ligand compound capable of coordinating with a palladium atom can be used separately from the palladium catalyst. Examples of the phosphorus ligand compound include triphenylphosphine, tri (o-tolyl) phosphine, tri (m-tolyl) phosphine, tri (p-tolyl) phosphine, tris (2,6-dimethoxyphenyl) phosphine, Tris [2- (diphenylphosphino) ethyl] phosphine, bis (2-methoxyphenyl) phenylphosphine, 2- (di-t-butylphosphino) biphenyl, 2- (dicyclohexylphosphino) biphenyl, 2- (diphenylphosphino) ) -2 '-(N, N-dimethylamino) biphenyl, tri-t-butylphosphine, bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,2-bis (dimethylphosphino) ) Ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,5-bis (diphenylphosphine) B) pentane, 1,6-bis (diphenylphosphino) hexane, 1,2-bis (dimethylphosphino) ethane, 1,1'-bis (diphenylphosphino) ferrocene (dppf), bis (2-diphenylphos Phinoethyl) phenylphosphine, 2- (dicyclohexylphosphino) -2 ', 6'-dimethoxy-1,1'-biphenyl (S-Phos), 2- (dicyclohexylphosphino) -2', 4 ', 6' -Triisopropyl-1,1'-biphenyl (X-Phos), bis (2-diphenylphosphinophenyl) ether (DPEPhos) and the like. In this step, from the viewpoint of yield and the like, tri (o-tolyl) phosphine, tri (m-tolyl) phosphine, tri (p-tolyl) phosphine and the like are preferable, and tri (o-tolyl) phosphine is more preferable.

  When using a phosphorus ligand compound, the amount used is preferably 1 to 20 moles and more preferably 2 to 10 moles per mole of palladium catalyst.

  The reaction is usually performed in the presence of a reaction solvent. Examples of the reaction solvent include aromatic hydrocarbons such as toluene, xylene and benzene; esters such as methyl acetate, ethyl acetate and butyl acetate; ethers such as diethyl ether, tetrahydrofuran (THF), dioxane, dimethoxyethane and diisopropyl ether; chloroform Halogenated hydrocarbons such as dichloromethane, dichloroethane and dibromoethane; amides such as dimethylformamide and dimethylacetamide; nitriles such as acetonitrile; dimethyl sulfoxide and the like. These may be used alone or in combination of two or more. In this step, an aromatic hydrocarbon is preferable, and toluene is more preferable.

  The reaction atmosphere is not particularly limited, and an inert gas atmosphere is preferable, and an argon gas atmosphere, a nitrogen gas atmosphere, and the like are more preferable.

  The reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent (including the environment in the Schlenk closed system). Moreover, reaction time can be made into time for reaction to fully advance.

  After completion of the reaction, normal isolation and purification steps may be performed as necessary, or the next step may be performed without purification.

Compound (7) → Compound (8)
In this step, a desired halogenation reaction can proceed by reacting the compound represented by the general formula (7) with a halogenated succinimide compound.

  There is no restriction | limiting in particular as a halogenated succinimide compound, A well-known thing can be employ | adopted, for example, N-bromosuccinimide, N-chlorosuccinimide, etc. are mentioned. Among these, N-bromosuccinimide is preferable in this step from the viewpoint of yield.

  In the above reaction formula 1, the addition amount of the halogenated succinimide compound is not particularly limited, and is preferably 1 to 5 mol with respect to 1 mol of the compound represented by the general formula (7) from the viewpoint of yield and the like. 1.5-3 mol is more preferable.

  The reaction is usually performed in the presence of a reaction solvent. Examples of the reaction solvent include aromatic hydrocarbons such as toluene, xylene and benzene; esters such as methyl acetate, ethyl acetate and butyl acetate; ethers such as diethyl ether, tetrahydrofuran (THF), dioxane, dimethoxyethane and diisopropyl ether; chloroform Halogenated hydrocarbons such as dichloromethane, dichloroethane and dibromoethane; amides such as dimethylformamide and dimethylacetamide; nitriles such as acetonitrile; alcohols such as methanol, ethanol and isopropyl alcohol; dimethyl sulfoxide; acetic acid and the like. These may be used alone or in combination of two or more. In this step, ether, halogenated hydrocarbon, amide, acetic acid and the like are preferable, tetrahydrofuran (THF), chloroform, dichloromethane, dimethylformamide, acetic acid and the like are more preferable, and dichloromethane is more preferable.

  The reaction atmosphere is not particularly limited, and an inert gas atmosphere is preferable, and an argon gas atmosphere, a nitrogen gas atmosphere, and the like are more preferable.

  The reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent (including the environment in the Schlenk closed system). Moreover, reaction time can be made into time for reaction to fully advance.

  After completion of the reaction, normal isolation and purification steps may be performed as necessary, or the next step may be performed without purification.

Compound (8) → Compound (3)
In this reaction, as in the above case, usually, right rice, Kosugi and Stille coupling can be employed. Specifically, the compound represented by the general formula (8) and the compound represented by the general formula (6) can be reacted in the presence of a palladium catalyst.

  In the above reaction formula 1, the amount of the compound represented by the general formula (6) is not particularly limited, and is 0 with respect to 1 mol of the compound represented by the general formula (8) from the viewpoint of yield and the like. .2 to 5 mol is preferable, and 0.5 to 2 mol is more preferable.

  As the palladium catalyst, those described above can be adopted. The same applies to preferred embodiments.

  The amount of the palladium catalyst used is usually preferably 0.005 to 0.1 mol, preferably 0.01 to 0.05 mol with respect to 1 mol of the compound represented by the general formula (8) from the viewpoint of yield. Is more preferable.

  Some of the palladium catalysts described above contain a ligand, but a phosphorus ligand compound capable of coordinating with a palladium atom can be used separately from the palladium catalyst. As the phosphorus ligand compound, those described above can be adopted. The same applies to preferred embodiments. When using a phosphorus ligand compound, the amount used is preferably 1 to 20 moles and more preferably 2 to 10 moles per mole of palladium catalyst.

  The reaction is usually performed in the presence of a reaction solvent. Examples of the reaction solvent include aromatic hydrocarbons such as toluene, xylene and benzene; esters such as methyl acetate, ethyl acetate and butyl acetate; ethers such as diethyl ether, tetrahydrofuran (THF), dioxane, dimethoxyethane and diisopropyl ether; chloroform Halogenated hydrocarbons such as dichloromethane, dichloroethane and dibromoethane; amides such as dimethylformamide and dimethylacetamide; nitriles such as acetonitrile; dimethyl sulfoxide and the like. These may be used alone or in combination of two or more. In this step, an aromatic hydrocarbon is preferable, and toluene is more preferable.

  The reaction atmosphere is not particularly limited, and an inert gas atmosphere is preferable, and an argon gas atmosphere, a nitrogen gas atmosphere, and the like are more preferable.

  The reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent (including the environment in the Schlenk closed system). Moreover, reaction time can be made into time for reaction to fully advance.

  After completion of the reaction, the usual polymer of the present invention can be obtained by performing usual isolation and purification steps as necessary.

3. Compound The compound of the present invention has the general formula (4):

[Wherein, R ¹ and R ² are the same as defined above. X ¹ and X ² are the same or different and represent H or a halogen atom. ]
It is a compound represented by these.

In the general formula (4), R ¹ and R ² are the same as described above. The same applies to preferred embodiments.

In the general formula (4), the halogen atom represented by X ¹ and X ² is not limited, and examples include a chlorine atom, a bromine atom, and an iodine atom, and a bromine atom is preferable from the viewpoint of yield and the like. X ¹ and X ² may be the same or different.

  Examples of the compound represented by the general formula (4) include general formulas (4A) to (4C):

[Wherein, X ¹ , X ² and X ³ are the same as defined above. X ⁶ is a halogen atom (a chlorine atom, a bromine atom, an iodine atom, etc.). ]
The compound represented by these is mentioned. Any compound is a compound that can be a monomer for synthesizing the polymer of the present invention, and is a novel compound not described in any literature.

4). Compound Production Method The method for synthesizing the compound of the present invention is not particularly limited as long as a desired compound can be synthesized. For example, among the compounds of the present invention, the compound of the present invention in which R ¹ is S has the following reaction formula 2:

[Wherein, R ¹ , R ² , X ³ and X ⁶ are the same as defined above. R ²³ and R ²⁴ are the same or different and each represents an alkyl group. X ⁷ , X ⁸ , X ⁹ and X ¹⁰ are the same or different and represent a halogen atom. ]
It can synthesize | combine by reaction represented by these. Hereinafter, one embodiment of the method for producing the compound of the present invention will be described, but the present invention is not limited thereto, and the compound of the present invention can be synthesized by various methods.

In Reaction Scheme 2, R ¹ , R ² , X ³ and X ⁶ are the same as described above. The same applies to preferred embodiments.

In Reaction Scheme 2, the alkyl group represented by R ²³ and R ²⁴ may be linear or branched, but is preferably a linear or branched alkyl group. 1-20 are preferable, as for carbon number of an alkyl group, 1-12 are more preferable, and 1-6 are more preferable. R ²³ and R ²⁴ may be the same or different.

In the reaction formula 2, the halogen atom represented by X ⁷ , X ⁸ , X ⁹ and X ¹⁰ is not limited, and examples thereof include a chlorine atom, a bromine atom and an iodine atom. From the viewpoint of yield and the like, X ⁷ is A chlorine atom is preferable, and X ⁸ , X ⁹ and X ¹⁰ are preferably bromine atoms. X ⁷ , X ⁸ , X ⁹ and X ¹⁰ may be the same or different.

Compound (9) → Compound (12)
In this reaction, first, the compound represented by the general formula (9) is reacted with the compound represented by the general formula (10).

  The addition amount of the compound represented by the general formula (10) is not particularly limited, and is preferably 1 to 5 mol with respect to 1 mol of the compound represented by the general formula (9) from the viewpoint of yield and the like. 1.5-3 mol is more preferable.

  The reaction is usually performed in the presence of a reaction solvent. Examples of the reaction solvent include aromatic hydrocarbons such as toluene, xylene and benzene; esters such as methyl acetate, ethyl acetate and butyl acetate; ethers such as diethyl ether, tetrahydrofuran (THF), dioxane, dimethoxyethane and diisopropyl ether; chloroform Halogenated hydrocarbons such as dichloromethane, dichloroethane and dibromoethane; ketones such as acetone and methyl ethyl ketone; amides such as dimethylformamide and dimethylacetamide; nitriles such as acetonitrile; alcohols such as methanol, ethanol and isopropyl alcohol; dimethyl sulfoxide and the like It is done. These may be used alone or in combination of two or more. In this step, amide is preferable, and dimethylformamide is more preferable.

  The reaction atmosphere is not particularly limited, and an inert gas atmosphere is preferable, and an argon gas atmosphere, a nitrogen gas atmosphere, and the like are more preferable.

  The reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent (including the environment in the Schlenk closed system). Moreover, reaction time can be made into time for reaction to fully advance.

  After completion of the reaction, normal isolation and purification steps may be performed as necessary, or the next step may be performed without purification.

  In this step, next, the compound represented by the general formula (11) is added.

  The addition amount of the compound represented by the general formula (11) is not particularly limited, and is preferably 1 to 10 mol with respect to 1 mol of the compound represented by the general formula (9) from the viewpoint of yield and the like. 2-5 mol is more preferable.

  The reaction is usually performed in the presence of a reaction solvent. Examples of the reaction solvent include aromatic hydrocarbons such as toluene, xylene and benzene; ethers such as diethyl ether, tetrahydrofuran (THF), dioxane, dimethoxyethane and diisopropyl ether; amides such as dimethylformamide and dimethylacetamide; nitriles such as acetonitrile. Dimethyl sulfoxide and the like. These may be used alone or in combination of two or more. In this step, amide is preferable, and dimethylformamide is more preferable.

  The reaction atmosphere is not particularly limited, and an inert gas atmosphere is preferable, and an argon gas atmosphere, a nitrogen gas atmosphere, and the like are more preferable.

  The reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent (including the environment in the Schlenk closed system). Moreover, reaction time can be made into time for reaction to fully advance.

  After completion of the reaction, normal isolation and purification steps may be performed as necessary, or the next step may be performed without purification.

Compound (12) → Compound (13)
In this reaction, the compound represented by the general formula (12) is reduced by reacting the compound represented by the general formula (12) with hydrogen chloride using tin halide to obtain the compound represented by the general formula (13).

  The tin halide is not particularly limited and includes tin (II) chloride, tin (II) bromide, tin (II) iodide, etc., and tin (II) chloride is preferred from the viewpoint of yield and the like.

  There is no restriction | limiting in particular in the addition amount of a halogenated tin, 2-20 mol is preferable with respect to 1 mol of compounds represented by General formula (12) from viewpoints, such as a yield, and 3-10 mol is more preferable. . Further, as hydrogen chloride, it is preferable to use hydrochloric acid having a desired concentration to make it excessive.

  The reaction is usually performed in the presence of a reaction solvent. Examples of the reaction solvent include aromatic hydrocarbons such as toluene, xylene and benzene; esters such as methyl acetate, ethyl acetate and butyl acetate; ethers such as diethyl ether, tetrahydrofuran (THF), dioxane, dimethoxyethane and diisopropyl ether; chloroform Halogenated hydrocarbons such as dichloromethane, dichloroethane and dibromoethane; amides such as dimethylformamide and dimethylacetamide; alcohols such as methanol, ethanol and isopropyl alcohol; dimethyl sulfoxide and the like. These may be used alone or in combination of two or more. In this step, alcohol is preferable and methanol is more preferable.

  The reaction atmosphere is not particularly limited, and an inert gas atmosphere is preferable, and an argon gas atmosphere, a nitrogen gas atmosphere, and the like are more preferable.

  The reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent (including the environment in the Schlenk closed system). Moreover, reaction time can be made into time for reaction to fully advance.

  After completion of the reaction, normal isolation and purification steps may be performed as necessary, or the next step may be performed without purification.

Compound (13) → Compound (4B1)
In this reaction, in the presence of a base, the compound represented by the general formula (13) and the compound represented by the general formula (14) are reacted to cause a cyclization reaction, which is represented by the general formula (4B1). To obtain the compound.

  The addition amount of the compound represented by the general formula (14) is not particularly limited, and is preferably 2 to 10 mol based on 1 mol of the compound represented by the general formula (13) from the viewpoint of yield and the like. 3-5 mol is more preferable.

  The base is not particularly limited, and alkali metal halides such as potassium fluoride and cesium fluoride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal alkoxides such as sodium methoxide; sodium hydrogen carbonate Alkali metal hydrogen carbonates such as potassium bicarbonate; metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate; alkali metal phosphates such as potassium phosphate; alkalis such as sodium acetate, potassium acetate and calcium acetate (soil And the like) amines such as metal acetates and triethylamine. Among these, from the viewpoint of yield and the like, an amine is preferable, and triethylamine is more preferable.

  The amount of the base used is preferably an excess amount with respect to the compound represented by the general formula (13), and specifically, with respect to 1 mol of the compound represented by the general formula (13), 2-50 mol is preferable and 3-20 mol is more preferable.

  The reaction is usually performed in the presence of a reaction solvent. Examples of the reaction solvent include aromatic hydrocarbons such as toluene, xylene and benzene; esters such as methyl acetate, ethyl acetate and butyl acetate; ethers such as diethyl ether, tetrahydrofuran (THF), dioxane, dimethoxyethane and diisopropyl ether; chloroform Halogenated hydrocarbons such as dichloromethane, dichloroethane and dibromoethane; nitriles such as acetonitrile and the like. These may be used alone or in combination of two or more. In this step, a halogenated hydrocarbon is preferable, and dichloromethane is more preferable.

  The reaction atmosphere is not particularly limited, and an inert gas atmosphere is preferable, and an argon gas atmosphere, a nitrogen gas atmosphere, and the like are more preferable.

  The reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent (including the environment in the Schlenk closed system). Moreover, reaction time can be made into time for reaction to fully advance.

  After completion of the reaction, normal isolation and purification steps may be performed as necessary, or the next step may be performed without purification. This compound is also a compound of the present invention.

Compound (4B1) → Compound (4A1), (4C1)
In this step, a desired halogenation reaction can proceed by reacting the compound represented by the general formula (4B1) with the halogenated succinimide compound. Although both the compound represented by the general formula (4A1) and the compound represented by the general formula (4C1) can be synthesized by this reaction, the compound represented by the general formula (4A1) is usually synthesized.

  There is no restriction | limiting in particular as a halogenated succinimide compound, A well-known thing can be employ | adopted, for example, N-bromosuccinimide, N-chlorosuccinimide, etc. are mentioned. Among these, N-bromosuccinimide is preferable in this step from the viewpoint of yield.

  In the above reaction formula 2, the addition amount of the halogenated succinimide compound is not particularly limited, and is preferably 1 to 5 mol with respect to 1 mol of the compound represented by the general formula (4B1) from the viewpoint of yield and the like. 1.5-3 mol is more preferable.

  The reaction is usually performed in the presence of a reaction solvent. Examples of the reaction solvent include aromatic hydrocarbons such as toluene, xylene and benzene; esters such as methyl acetate, ethyl acetate and butyl acetate; ethers such as diethyl ether, tetrahydrofuran (THF), dioxane, dimethoxyethane and diisopropyl ether; chloroform Halogenated hydrocarbons such as dichloromethane, dichloroethane, dibromoethane; ketones such as acetone and methyl ethyl ketone; amides such as dimethylformamide and dimethylacetamide; nitriles such as acetonitrile; alcohols such as methanol, ethanol and isopropyl alcohol; dimethyl sulfoxide; Is mentioned. These may be used alone or in combination of two or more. In this step, ether, halogenated hydrocarbon, amide, acetic acid and the like are preferable, tetrahydrofuran (THF), chloroform, dichloromethane, dimethylformamide, acetic acid and the like are more preferable, and dichloromethane is more preferable.

  The reaction atmosphere is not particularly limited, and an inert gas atmosphere is preferable, and an argon gas atmosphere, a nitrogen gas atmosphere, and the like are more preferable.

  The reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent (including the environment in the Schlenk closed system). Moreover, reaction time can be made into time for reaction to fully advance.

  After the completion of the reaction, the usual compound of the present invention can be obtained by performing usual isolation and purification steps as necessary.

5. Applications of the Polymer of the Present Invention The polymer of the present invention has functions such as light absorption characteristics, charge transport characteristics, and photoelectric conversion characteristics. Further, by appropriately selecting the alkyl group in R ^2, the control of solubility can be easily performed. Therefore, by appropriately selecting an alkyl group in R ² depending on the solvent to be used, it is possible to easily improve the solubility.

For this reason, the polymer of this invention is useful as a light absorption material, a photoelectric conversion material, a charge transport material, etc. Therefore, it can be effectively used as a light-absorbing material for organic thin film solar cells, a photoelectric conversion material, etc., a charge transport material for organic transistors and organic electroluminescent elements, and the like. In particular, when used for light-absorbing materials, photoelectric conversion materials, etc. of organic thin film solar cells, solar energy can be efficiently collected and used for photoelectric conversion, and conventional organic thin film solar cell materials are used. Compared to the case, the photoelectric conversion efficiency can be dramatically improved. For example, a hole transport layer may be formed on a substrate by, for example, spin coating, a photoelectric conversion layer containing the polymer of the present invention may be formed thereon by, for example, spin coating, and an upper electrode may be formed thereon by, for example, vapor deposition. it can. As the substrate, the hole transport layer and the upper electrode, for example, conventionally used materials such as a glass-ITO substrate as the substrate, PEDOT-PSS as the hole transport layer, and aluminum as the upper electrode can be used. In addition, the photoelectric conversion layer may be a layer composed of only the polymer of the present invention, or 1 to 99% by weight (particularly 10 to 90% by weight) of the polymer of the present invention, an electron accepting material (phenyl C ₆₁ butyric acid methyl ester ( A layer containing 1 to 99% by weight (especially 10 to 90% by weight) of a fullerene derivative such as PCBM). In addition, when using the polymer of this invention as a light absorption material, a charge transport material, etc., other structures, such as an organic transistor and an organic electroluminescent element, can be made the same as that of the past.

  In addition, the compound of the present invention can be used as a monomer for synthesizing the polymer of the present invention, but since it has a thioalkyl group, it can also be used as a substrate for a coupling reaction.

  EXAMPLES Hereinafter, although an Example etc. are shown and this invention is demonstrated in detail, this invention is not limited to these.

Synthesis Example 1-1 (Compound 1)

2-Chloro-5-nitro-1,4-phenylenediamine (1.00 g, 5.33 mmol) and sodium ethyl xanthate (1.70 g, 11.8 mmol) were added to the two-necked flask, and deaeration and Ar substitution were performed. Dehydrated dimethylformamide (dehydrated DMF; 3.5 mL) was added, and the mixture was heated and stirred at 100 to 120 ° C. for 4.5 hours. After cooling to room temperature, iodomethane (0.85 mL, 14 mmol) was added dropwise and stirred for 7 hours. A saturated aqueous NaHCO ₃ solution (50 mL) and a saturated aqueous NaCl solution (50 mL) were added, and the aqueous layer was extracted with ethyl acetate (EtOAc; 100 mL × 4). The organic layers were combined, dried over NaSO ₄ and filtered. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, hexane / ethyl acetate = 3: 1 → 2: 1, Rf = 0.50 (hexane / ethyl acetate = 2: 1)), and compound 1 (533 mg, 2.21 mmol) was obtained as a red solid in a yield of 41%.
¹ H NMR (500 MHz, DMSO-d ₆ ) δ 8.31 (s, 1H), 7.46 (s, 1H), 7.33 (brs, 2H), 2.75 (s, 3H).

Synthesis Example 1-2 (Compound 2)

Compound 1 (3.33 g, 13.8 mmol) obtained in Synthesis Example 1-1 was added to the two-necked flask, and deaeration and Ar substitution were performed. Methanol (MeOH; 150 mL), SnCl ₂ (13.1 g, 69.1 mmol), distilled water (15 mL), and 1M HCl (7 mL) were added, and the mixture was heated and stirred at 70 ° C. for 16 hours. After cooling to room temperature, the reaction mixture was added to saturated aqueous NaHCO ₃ (250 mL) and filtered. The residue was washed with ethyl acetate (EtOAc; 100 mL × 3) and filtered, and the solvent was distilled off under reduced pressure to obtain Compound 2 (2.20 g, 10.4 mmol) as an orange solid in a yield of 75%.
¹ H NMR (500 MHz, CDCl ₃ ) δ 7.23 (s, 1H), 7.03 (s, 1H), 3.53 (brs, 4H).

Synthesis Example 1-3 (Compound 3)

The compound 2 (2.20 g, 10.4 mmol) obtained in Synthesis Example 1-2 was added to the two-necked flask, and deaeration and Ar substitution were performed. After adding dehydrated CH ₂ Cl ₂ (150 mL) and triethylamine (Et ₃ N; 11.6 mL, 83.3 mmol), the mixture was cooled to 0 ° C., SOCl ₂ (3.0 mL, 41.6 mmol) was added dropwise, and the mixture was warmed to room temperature. And stirred for 18 hours. A saturated aqueous NaHCO ₃ solution (100 mL) was added, the aqueous layer was extracted with CH ₂ Cl ₂ (25 mL × 3), and the organic layer was extracted with saturated brine (100 mL). The organic layer was dried over NaSO ₄ and filtered. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, CH ₂ Cl ₂ , Rf = 0.70 (CH ₂ Cl ₂ )) to obtain Compound 3 (1.82 g, 7.76 mmol) as a light brown solid in a yield of 73%. Got in.
¹ H NMR (500 MHz, CDCl ₃ ) δ 8.36 (s, 1H), 8.32 (s, 1H).

Synthesis Example 1-4 (Compound 4)

Compound 3 (7.23 g, 30.2 mmol) obtained in Synthesis Example 1-3 was added to the two-necked flask, and deaeration and Ar substitution were performed. Dehydrated CH ₂ Cl ₂ (430 mL) and N-bromosuccinimide (NBS; 6.46 g, 36.3 mmol) were added, protected from light, and stirred at room temperature for 17 hours. Distilled water (300 mL) and CH ₂ Cl ₂ (200 mL) were added, the aqueous layer was extracted with CH ₂ Cl ₂ (30 mL × 3), and the organic layer was extracted with distilled water (20 mL × 3). The organic layer was dried over Na ₂ SO ₄ and filtered. The solvent was removed under reduced pressure. Washing with methanol (MeOH; 100 mL) and filtration gave Compound 4 (8.17 g, 25.7 mmol) as a yellow solid in a yield of 85%.
¹ H NMR (600 MHz, CDCl ₃ ) δ 8.24 (s, 1H), 2.91 (s, 3H).

Synthesis Example 2-1 (Compound 5)

2-Chloro-5-nitro-1,4-phenylenediamine (8.26 g, 44.1 mmol) and sodium ethyl xanthate (12.7 g, 88.1 mmol) were added to the two-necked flask, and deaeration and Ar substitution were performed. Dehydrated dimethylformamide (dehydrated DMF; 50 mL) was added, and the mixture was heated and stirred at 120 ° C. for 22 hours. It cooled to 0 degreeC, 2-ethylhexyl bromide (15.5 mL, 88.1 mmol) was added, and it heated up to room temperature, and stirred for 4 hours. A saturated aqueous NaHCO ₃ solution (100 mL) and a saturated aqueous NaCl solution (50 mL) were added, and the aqueous layer was extracted with ethyl acetate (EtOAc; 150 mL × 2). The organic layers were combined, dried over NaSO ₄ and filtered. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (alumina, hexane / CH ₂ Cl ₂ = 1: 1, Rf = 0.3 (hexane / CH ₂ Cl ₂ = 1: 1)), and compound 5 (4.92 g, 14.5 mmol) was obtained as an orange solid in a yield of 33%.
¹ H NMR (500 MHz, DMSO-d ₆ ) δ 8.28 (s, 1H), 7.44 (s, 1H), 7.34 (brs, 2H), 3.32 (dd, ² J _HH = 4.6 Hz, J _HH = 6.5 Hz , 2H), 1.65-1.72 (sept, J _HH = 6.5 Hz, 1H), 1.36-1.42 (quint, J _HH = 6.9 Hz, 2H), 1.31-1.36 (m, 2H), 1.21-1.31 (m, 4H ), 0.83-0.90 (t, overlapped, 6H).

Synthesis Example 2-2 (Compound 6)

Compound 5 (3.14 g, 9.26 mmol) obtained in Synthesis Example 2-1 was added to the two-necked flask, and deaeration and Ar substitution were performed. Methanol (MeOH; 150 mL), SnCl ₂ (8.81 g, 46.5 mmol), distilled water (15 mL), and 1M HCl (5 mL) were added, and the mixture was heated and stirred at 70 ° C. for 21 hours. After cooling to room temperature, the reaction solution was added to saturated aqueous NaHCO ₃ solution (200 mL), the aqueous layer was extracted with CH ₂ Cl ₂ (100 mL × 2), and the organic layer was extracted with saturated brine (100 mL). The organic layer was dried over Na ₂ SO ₄ and filtered. The solvent was distilled off under reduced pressure to obtain Compound 6 (2.82 g, 9.11 mmol) as a dark brown liquid in a yield of 98%.
¹ H NMR (500 MHz, CDCl ₃ ) δ 7.22 (s, 1H), 7.02 (s, 1H), 3.52 (brs, 4H), 3.26-3.29 (dd, 2H), 1.69-1.74 (m, 1H), 1.24-1.51 (m, 8H), 0.88-0.93 (t, overlapped, 6H).

Synthesis Example 2-3 (Compound 7)

Compound 6 (2.36 g, 7.62 mmol) obtained in Synthesis Example 2-2 was added to the two-necked flask, and deaeration and Ar substitution were performed. After adding dehydrated CH ₂ Cl ₂ (150 mL) and triethylamine (Et ₃ N; 8.5 mL, 60.9 mmol), the mixture was cooled to 0 ° C., SOCl ₂ (2.2 mL, 30.5 mmol) was added dropwise, and the temperature was raised to room temperature. And stirred for 17 hours. A saturated aqueous NaHCO ₃ solution (80 mL) was added, the aqueous layer was extracted with CH ₂ Cl ₂ (50 mL × 3), and the organic layer was extracted with saturated brine (100 mL). The organic layer was dried over NaSO ₄ and filtered. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, CH ₂ Cl ₂ , Rf = 0.63 (CH ₂ Cl ₂ )) to obtain Compound 7 (2.00 g, 5.93 mmol) as a dark brown oily liquid with a yield of 78 Obtained in%.
¹ H NMR (500 MHz, CDCl ₃ ) δ 8.33 (s, 1H), 8.29 (s, 1H), 3.43-3.51 (dd, 2H), 1.78-1.83 (m, 1H), 1.31-1.53 (m, 8H ), 0.91-0.99 (t, overlapped, 6H).

Synthesis Example 2-4 (Compound 8)

Compound 7 (1.66 g, 4.93 mmol) obtained in Synthesis Example 2-3 was added to the two-necked flask, and deaeration and Ar substitution were performed. Dehydrated CH ₂ Cl ₂ (100 mL) and N-bromosuccinimide (NBS; 1.94 g, 10.9 mmol) were added, protected from light, and stirred at room temperature for 17 hours. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, toluene / hexane = 2: 1, Rf = 0.4 (toluene / hexane = 2: 1)) to give compound 8 (1.93 g, 4.62 mmol) as a yellow oil A 94% yield was obtained as a liquid.
¹ H NMR (500 MHz, CDCl ₃ ) δ 8.23 (s, 1H), 3.52 (d, 2H), 1.82-1.87 (m, 1H), 1.32-1.54 (m, 8H), 0.98-1.01 (t, 3H ), 0.91-0.93 (t, 3H).

Synthesis Example 3-1 (Compound 9)

2-Chloro-5-nitro-1,4-phenylenediamine (9.0 g, 48.0 mmol) and sodium ethyl xanthate (13.8 g, 96.0 mmol) were added to the two-neck flask, and deaeration and Ar substitution were performed. Dehydrated dimethylformamide (dehydrated DMF; 480 mL) was added, and the mixture was heated and stirred at 120 ° C. for 150 minutes. It cooled to 0 degreeC, 2-decyl tetradecyl bromide (29.9 g, 71.7 mmol) was added, and it heated up to room temperature, and stirred for 17 hours. The solvent was distilled off under reduced pressure, distilled water (300 mL) and diethyl ether (300 mL) were added, the aqueous layer was extracted with diethyl ether (200 mL x 3), and the organic layer was extracted with saturated brine (300 mL). did. The organic layer was dried over NaSO ₄ and filtered. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, toluene / hexane = 2: 1, Rf = 0.25 (toluene / hexane = 2: 1)), and compound 8 (6.20 g, 11.0 mmol) was dark red Obtained as an oily liquid in 68% yield.
¹ H NMR (500 MHz, CDCl ₃ ) δ 8.55 (s, 1H), 7.08 (s, 1H), 5.97 (brs, 2H), 3.36 (d, 2H), 1.78-1.81 (m, 1H), 1.25- 1.43 (m, 40H), 0.86-0.89 (t, overlapped, 6H).

Synthesis Example 3-2 (Compound 10)

Compound 9 (18.3 g, 32.5 mmol) obtained in Synthesis Example 3-1 was added to the two-necked flask, and deaeration and Ar substitution were performed. Methanol (MeOH; 900 mL), SnCl ₂ .2H ₂ O (36.8 g, 16.3 mmol), distilled water (90 mL), and 1M HCl (16.3 mL) were added, and the mixture was heated and stirred at 70 ° C. for 22 hours. After cooling to room temperature, the solvent was distilled off under reduced pressure. CH ₂ Cl ₂ (200 mL) was added, and the solution was added to a saturated aqueous NaHCO ₃ solution (400 mL), followed by extraction with 2M NaOH (200 mL). The aqueous layer was extracted with CH ₂ Cl ₂ (200 mL × 3), and the organic layer was extracted with 2M NaOH (200 mL) and saturated brine (300 mL). The organic layer was dried over Na ₂ SO ₄ and filtered. The solvent was distilled off under reduced pressure to obtain Compound 10 (15.9 g) as a brown oily liquid in a yield of 92%.
¹ H NMR (500 MHz, CDCl ₃ ) δ 7.21 (s, 1H), 7.00 (s, 1H), 3.52 (brs, 4H), 3.27 (d, 2H), 1.75-1.77 (m, 1H), 1.25- 1.43 (m, 40H), 0.87-0.89 (t, overlapped, 6H).

Synthesis Example 3-3 (Compound 11)

The compound 10 (15.9 g) obtained in Synthesis Example 3-2 was added to a two-necked flask, and deaeration and Ar substitution were performed. After adding dehydrated CH ₂ Cl ₂ (500 mL) and triethylamine (Et ₃ N; 23.7 mL, 170 mmol), the mixture was cooled to 0 ° C., SOCl ₂ (6.16 mL, 85.0 mmol) was added dropwise, and the mixture was warmed to room temperature. And stirred for 2 hours. A saturated aqueous NaHCO ₃ solution (300 mL) was added, the aqueous layer was extracted with CH ₂ Cl ₂ (100 mL × 3), and the organic layer was extracted with saturated brine (200 mL). The organic layer was dried over NaSO ₄ and filtered. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, toluene / hexane = 1: 1, Rf = 0.42 (toluene / hexane = 1: 1)), and compound 11 (14.0 g, 24.9 mmol) was dark brown Obtained as an oily liquid in 88% yield.
¹ H NMR (500 MHz, CDCl ₃ ) δ 8.32 (s, 1H), 8.29 (s, 1H), 3.47 (d, 2H), 1.84-1.86 (m, 1H), 1.24-1.46 (m, 40H), 0.85-0.89 (t, overlapped, 6H).

Synthesis Example 3-4 (Compound 12)

Compound 11 (1.51 g, 2.69 mmol) obtained in Synthesis Example 3-3 was added to the two-neck flask, and deaeration and Ar substitution were performed. Dehydrated CH ₂ Cl ₂ (80 mL) and N-bromosuccinimide (NBS; 1.06 g, 5.94 mmol) were added, protected from light, and stirred at room temperature for 17 hours. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, toluene / hexane = 2: 1, Rf = 0.5 (toluene / hexane = 2: 1)) to give Compound 12 (1.65 g, 2.57 mmol) as a yellow oil Obtained as a liquid in 96% yield.
¹ H NMR (500 MHz, CDCl ₃ ) δ 8.30 (s, 1H), 3.52 (d, 2H), 1.88-1.91 (m, 1H), 1.24-1.47 (m, 40H), 0.85-0.89 (t, overlapped , 6H).

Synthesis Example 3-5 (Compound 13)

The compound 11 (2.80 g, 5.0 mmol) obtained in Synthesis Example 3-3 and iron (III) chloride hexahydrate (0.811 g, 3 mmol) were added to the two-necked flask, and deaeration and Ar substitution were performed. Bromine (12 mL, 233 mmol) was added, protected from light, and stirred at 50 ° C. for 17 hours. Cool to room temperature, add CH ₂ Cl ₂ (50 mL), add the solution to saturated aqueous NaHSO ₃ (250 mL), extract the aqueous layer with CH ₂ Cl ₂ (200 mL x 2) and extract the organic layer. Extracted with saturated brine (200 mL). The organic layer was dried over Na ₂ SO ₄ and filtered. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, toluene / hexane = 1: 1, Rf = 0.6 (toluene / hexane = 1: 1)) to give compound 13 (1.90 g, 2.63 mmol) as a yellow oil Obtained as a liquid in 53% yield.
¹ H NMR (500 MHz, CDCl ₃ ) δ 3.50 (d, 2H), 1.88-1.90 (m, 1H), 1.24-1.46 (m, 40H), 0.85-0.89 (t, overlapped, 6H).

Synthesis Example 3-6 (Compound 14)

In Schlenk, Compound 12 (0.52 g, 0.82 mmol) obtained in Synthesis Example 3-4, 2,6-bis (trimethyltin) -4,8-bis (5- (2-ethylhexyl) thiophen-2-yl) benzo [1,2-b: 4,5-b '] bithiophene (0.37 g, 0.41 mmol), o-tolylphosphine (24.9 mg, 82 μmol), tris (dibenzylideneacetone) dipalladium (0) chloroform adduct (21.2 mg , 20 μmol), and deaeration and Ar substitution were performed. Dehydrated toluene (10 mL) was added, and the mixture was stirred at 110 ° C. under reflux for 18 hours. After cooling to room temperature, the solvent was distilled off under reduced pressure. Purification by column chromatography (silica gel, toluene / hexane = 1: 2, Rf = 0.13 (toluene / hexane = 1: 2)) gave compound 14 (0.38 g, 0.22 mmol) as a purple solid in a yield of 54%. It was.
¹ H NMR (500 MHz, CDCl ₃ ) δ 9.64 (s, 2H), 8.21 (s, 2H), 7.57 (d, 2H), 6.97 (d, 2H), 3.71 (d, 4H), 2.92-2.95 ( m, 4H), 1.77-1.90 (m, 4H), 1.15-1.60 (m, 96H), 1.00-1.03 (t, 6H), 0.90-0.93 (t, 6H), 0.79-0.85 (t, overlapped, 12H ).

Synthesis Example 3-7 (Compound 15)

Compound 14 (0.38 g, 0.22 mmol) obtained in Synthesis Example 3-6 was added to the two-necked flask, and deaeration and Ar substitution were performed. Dehydrated CH ₂ Cl ₂ (3 mL) and N-bromosuccinimide (NBS; 88.8 mg, 0.50 mmol) were added, protected from light, and stirred at room temperature for 19 hours. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, toluene / hexane = 1: 2, Rf = 0.45 (toluene / hexane = 1: 2)) to obtain compound 15 (0.35 g, 0.19 mmol) as a dark purple solid As a yield of 85%.
¹ H NMR (500 MHz, CDCl ₃ ) δ 9.37 (s, 2H), 7.58 (d, 2H), 6.96 (d, 2H), 3.74 (d, 4H), 2.94-2.99 (m, 4H), 1.82- 1.87 (m, 4H), 1.14-1.70 (m, 96H), 1.05-1.08 (t, 6H), 0.94-0.97 (t, 6H), 0.78-0.83 (t, overlapped, 12H).

Synthesis Example 3-8 (Polymer 16)

In a microwave reaction vessel, compound 15 (120 mg, 63 μmol) obtained in Synthesis Example 3-7, 2,6-bis (trimethyltin) -4,8-bis (5- (2-ethylhexyl) thiophen-2-yl ) Benzo [1,2-b: 4,5-b '] bithiophene (57 mg, 63 μmol), o-tolylphosphine (1.58 mg, 5.2 μmol), tris (dibenzylideneacetone) dipalladium (0) chloroform adduct ( 1.31 mg, 1.3 μmol) was added to perform deaeration and Ar replacement. Dehydrated toluene (5 mL) was added, and the mixture was stirred at 150 ° C. for 1 hour in a microwave reactor. After cooling to room temperature, the reaction solution was dispersed in methanol (30 mL), and the solution was transferred to Soxhlet filter paper. Soxhlet extraction was performed sequentially with methanol, acetone, and hexane to remove impurities and short molecules, followed by Soxhlet extraction with chloroform. The chloroform extract solution was concentrated, dispersed in methanol, and collected by filtration to obtain polymer 16 (109 mg) as a dark blue solid in a yield of 75%.
GPC (o-dichlorobenzene) Mn = 14,000, Mw = 25,000.

Synthesis Example 3-9 (Compound 17)

In Schlenk, Compound 12 (0.41 g, 0.65 mmol) obtained in Synthesis Example 3-4, 2,6-bis (trimethyltin) -4,8-bis (2-ethylhexyloxy) benzo [1,2-b: 4 , 5-b '] bithiophene (0.25 g, 0.32 mmol), o-tolylphosphine (19.7 mg, 65 μmol), tris (dibenzylideneacetone) dipalladium (0) chloroform adduct (16.8 mg, 16 μmol), and deaerated And Ar substitution was performed. Dehydrated toluene (10 mL) was added, and the mixture was stirred at 110 ° C. under reflux for 21 hours. After cooling to room temperature, the solvent was distilled off under reduced pressure. Purification by column chromatography (silica gel, toluene / hexane = 1: 1, Rf = 0.5 (toluene / hexane = 1: 1)) gave compound 17 (0.35 g, 0.23 mmol) as a purple solid in a yield of 70%. It was.
¹ H NMR (500 MHz, CDCl ₃ ) δ 9.48 (s, 2H), 8.25 (s, 2H), 4.38-4.43 (m, 4H), 3.80 (d, 4H), 1.95-1.97 (m, 4H), 1.13-1.90 (m, 102H), 0.96-0.97 (t, 6H), 0.81-0.85 (t, overlapped, 12H).

Synthesis Example 3-10 (Compound 18)

Compound 17 (0.28 g, 0.18 mmol) obtained in Synthesis Example 3-9 was added to the two-necked flask, and deaeration and Ar substitution were performed. Dehydrated CH ₂ Cl ₂ (3 mL) and N-bromosuccinimide (NBS; 68.8 mg, 0.39 mmol) were added, protected from light, and stirred at room temperature for 17 hours. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, toluene / hexane = 1: 2, Rf = 0.3 (toluene / hexane = 1: 2)) to obtain compound 18 (0.11 g, 0.063 mmol) as a dark purple solid As a yield of 34%.
¹ H NMR (500 MHz, CDCl ₃ ) δ 9.41 (s, 2H), 4.36-4.41 (m, 4H), 3.77 (d, 4H), 1.93-1.96 (m, 4H), 1.10-1.89 (m, 102H ), 0.92-0.95 (t, 6H), 0.79-0.85 (t, overlapped, 12H).

Synthesis Example 3-11 (Compound 19)

In Schlenk, compound 18 (0.11 g, 0.063 mmol) obtained in Synthesis Example 3-10, 2,6-bis (trimethyltin) -4,8-bis (2-ethylhexyloxy) benzo [1,2-b: 4 , 5-b '] bithiophene (0.048 g, 0.63 mmol), o-tolylphosphine (3.8 mg, 12.5 μmol), tris (dibenzylideneacetone) dipalladium (0) chloroform adduct (3.2 mg, 3.1 μmol), Degassing and Ar replacement were performed. Dehydrated toluene (1 mL) was added, and the mixture was stirred at 110 ° C. under reflux for 20 hours. After cooling to room temperature, the reaction solution was dispersed in methanol (5 mL), and the solution was transferred to Soxhlet filter paper. Soxhlet extraction was performed sequentially with methanol and acetone to remove impurities, followed by Soxhlet extraction with hexane. The hexane extract solution was concentrated, dispersed in methanol and collected by filtration to obtain polymer 19 (119 mg) as a dark blue solid in a yield of 93%.
GPC (o-dichlorobenzene) Mn = 6,000, Mw = 13,000.

Synthesis Example 3-12 (Polymer 20)

In a microwave reaction vessel, compound 13 (59.9 mg, 81.6 μmol) obtained in Synthesis Example 3-5, 2,6-bis (trimethyltin) -4,8-bis (2-ethylhexyloxy) benzo [1,2- b: 4,5-b '] bithiophene (64.8 mg, 83.9 μmol), o-tolylphosphine (1.94 mg, 6.4 μmol), tris (dibenzylideneacetone) dipalladium (0) chloroform adduct (2.14 mg, 2.1 μmol) Was added, and deaeration and Ar substitution were performed. Dehydrated toluene (3 mL) was added, and the mixture was stirred at 150 ° C. for 1 hour in a microwave reactor. After cooling to room temperature, the reaction solution was dispersed in methanol (50 mL), and the solution was transferred to Soxhlet filter paper. Soxhlet extraction was performed sequentially with methanol, acetone, and hexane to remove impurities and short molecules, followed by Soxhlet extraction with chloroform. The chloroform extract solution was concentrated, dispersed in methanol, and collected by filtration to obtain polymer 20 (12.5 mg) as a dark blue solid in a yield of 15%.
GPC (o-dichlorobenzene) Mn = 11,000, Mw = 16,000.

Synthesis Example 3-13 (Polymer 21)

Compound 13 (0.1 g, 0.14 mmol) obtained in Synthesis Example 3-5, 5,5 ′ ″-bis (trimethyltin) -3,3 ′ ″-bis (2-octyldodecyl) in a microwave reaction vessel -2,2 ': 5', 2 '': 5 '', 2 '''benzoquaterthiophene (0.17 g, 0.14 mmol), o-tolylphosphine (3.38 mg, 11.1 μmol), tris (dibenzylideneacetone) Di-palladium (0) chloroform adduct (2.88 mg, 2.8 μmol) was added to perform deaeration and Ar substitution. Dehydrated toluene (5 mL) was added, and the mixture was stirred with a microwave reactor at 160 ° C. for 1 hour. After cooling to room temperature, the reaction solution was dispersed in methanol (50 mL), and the solution was transferred to Soxhlet filter paper. Soxhlet extraction with methanol and acetone in order to remove impurities and short molecules, hexane extraction solution extracted with Soxhlet extraction with hexane is concentrated, then dispersed in methanol and collected by filtration to collect polymer 21 (0.15 g) as a black solid. Obtained at a rate of 75%.
GPC (o-dichlorobenzene) Mn = 8,924, Mw = 16,283.

  The light absorption characteristics of the obtained spin coat film of polymer 21 are shown in FIG. As shown in FIG. 1, the polymer 21 has absorption peaks at three locations of 712 mm, 662 mm, and 445 mm, and it can be understood that the polymer 21 has absorption peaks at long wavelengths.

Synthesis Example 3-14 (Compound 22)

Compound 13 (0.22 g, 0.30 mmol) obtained in Synthesis Example 3-5 was added to the two-necked flask, and deaeration and Ar substitution were performed. Dehydrated CH ₂ Cl ₂ (3 mL) was added, and after cooling to 0 ° C., metachlorobenzoic acid (0.15 g, 0.6 mmol) was added, and the mixture was warmed to room temperature and stirred for 21 hours. Add 10% aqueous sodium thiosulfate solution (20 mL), extract with CH ₂ Cl ₂ solvent (20 mL × 2), and extract the organic layer with saturated aqueous NaHCO ₃ solution (20 mL) and saturated brine (20 mL). did. The organic layer was dried over Na ₂ SO ₄ and filtered. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, toluene / hexane = 2: 1), Rf = 0.45 (toluene / hexane = 2: 1)), and compound 22 (0.20 g, 0.27 mmol) was diluted. Obtained as a yellow solid in 89% yield.
¹ H NMR (500 MHz, CDCl ₃ ) δ 3.61 (d, 2H), 2.18-2.21 (m, 1H), 1.21-1.57 (m, 40H), 0.86-0.89 (t, overlapped, 12H).

Synthesis Example 3-15 (Polymer 23)

Compound 22 (0.08 g, 0.11 mmol) obtained in Synthesis Example 3-14, 5,5 ′ ″-bis (trimethyltin) -3,3 ′ ″-bis (2-octyldodecyl) in a microwave reaction vessel -2,2 ': 5', 2 '': 5 '', 2 '''benzoquaterthiophene (0.13 g, 0.11 mmol), o-tolylphosphine (2.61 mg, 8.6 μmol), tris (dibenzylideneacetone) Di-palladium (0) chloroform adduct (2.22 mg, 2.6 μmol) was added to perform deaeration and Ar substitution. Dehydrated toluene (5 mL) was added, and the mixture was stirred in a microwave reactor at 160 ° C. for 1 hour. After cooling to room temperature, the reaction solution was dispersed in methanol (50 mL), and the solution was transferred to Soxhlet filter paper. Soxhlet extraction with methanol and acetone in order to remove impurities and short molecules, hexane extraction solution extracted with Soxhlet extraction with hexane is concentrated, then dispersed in methanol and collected by filtration to collect polymer 23 (0.14 g) as a black solid. Obtained at a rate of 87%.
GPC (o-dichlorobenzene) Mn = 12,905, Mw = 24,631.

  The light absorption characteristic of the spin coat film of the obtained polymer 23 is shown in FIG. As shown in FIG. 2, it can be understood that the polymer 23 has absorption peaks at two locations of 777 mm and 458 mm, and has an absorption peak at a long wavelength.

Example 1 (Polymer 16)
PEDOT-PSS (Nagase Chemtech PT-100) used as a hole transport layer was spin-coated (5000 rpm) on a glass-ITO substrate subjected to cleaning and UV-ozone treatment, and heated at 200 ° C. for 10 minutes. A mixture of 10 mg of polymer 16 and 10 mg of PCBM [60] was dissolved in 1 mL of chlorobenzene containing 3% by weight of 1,8-diiodooctane. The solution was applied onto the PEDOT-PSS layer by spin coating (1000 rpm, 40 seconds) and dried to prepare a photoelectric conversion layer. After applying an ethanol solution of titanium (IV) tetraisopropoxide (concentration 3.3 μL / mL) on the photoelectric conversion layer at 4000 rpm, aluminum was evaporated to form the upper electrode, and an element (organic thin film solar cell) was obtained. It was. The evaluation results are shown in Table 1 and FIGS.

Example 2 (Polymer 19)
A mixture of 8 mg of Polymer 19 and 16 mg of PCBM [60] was dissolved in 1 mL of chlorobenzene containing 3% by weight of 1,8-diiodooctane, and the solution was spin-coated on the PEDOT-PSS layer. An element (organic thin film solar cell) was obtained in the same manner as in Example 1 except that coating was performed at (800 rpm, 40 seconds). The evaluation results are shown in Table 2 and FIG.

Claims (11)

General formula (1):
[Wherein R ¹ represents O, S, Se or Te. R ² represents a group represented by —SR ³ (R ³ is an alkyl group) or a group represented by —SO ₂ R ⁴ (R ⁴ is an alkyl group). * Indicates a binding position. ]
The polymer which has a structural unit represented by these. General formula (2):
[Wherein, R ¹ and R ² are the same as defined above. D represents a donor linking group. * Indicates a binding position. ]
The polymer which has a structural unit represented by these. The polymer according to claim 1 or 2, which is a regioregular polymer. General formula (3):
[Wherein, R ¹ and R ² are the same or different and the same as above. D is the same or different and represents a donor linking group. * Indicates a binding position. ]
The polymer in any one of Claims 1-3 which has a repeating unit represented by these. The polymer according to claim 1, wherein R ¹ is S. A charge transport material comprising the polymer according to claim 1. The organic thin-film solar cell material which consists of a polymer in any one of Claims 1-5. An organic thin-film solar cell using the polymer according to claim 1, the charge transport material according to claim 6, or the organic solar cell material according to claim 7. General formula (4):
[Wherein R ¹ represents O, S, Se or Te. R ² represents a group represented by —SR ³ (R ³ is an alkyl group) or a group represented by —SO ₂ R ⁴ (R ⁴ is an alkyl group). X ¹ and X ² are the same or different and represent H or a halogen atom. ]
A compound represented by The compound according to claim 9, wherein R ¹ is S. The compound according to claim 9 or 10, wherein X ² is a halogen atom.