WO2016121589A1 - Organic semiconductor material - Google Patents

Abstract

Provided are a polymer compound for providing an organic semiconductor material having excellent conversion efficiency, or a starting material compound having a high degree of freedom in material design, and a method for manufacturing the same. A polymer compound characterized by including repeating units of a benzobisthiazole structure represented by formula (1) and repeating units of a thiophene structure represented by formula (2). (In formula (1), T¹ and T² each independently represent a thiophene ring which may be substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group, a thiazole ring which may be substituted with a hydrocarbon group or an organosilyl group, or a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom, or a trifluoromethyl group.) (In formula (2), R¹ represents a hydrogen atom or a C1-3 hydrocarbon group.)

Description

Organic semiconductor materials

The present invention relates to a compound having a specific benzobisthiazole skeleton and a production method thereof.

Organic semiconductor materials are one of the most important materials in the field of organic electronics, and can be classified into electron-donating p-type organic semiconductor materials and electron-accepting n-type organic semiconductor materials. Various elements can be manufactured by appropriately combining p-type organic semiconductor materials and n-type organic semiconductor materials. For example, such elements are excitons formed by recombination of electrons and holes. It is applied to organic electroluminescence that emits light by the action of (exciton), an organic thin film solar cell that converts light into electric power, an organic thin film transistor that controls the amount of current and voltage, and the like.

Among these, organic thin-film solar cells are useful for environmental conservation because they do not release carbon dioxide into the atmosphere, and demand is increasing because they are easy to manufacture with a simple structure. However, the photoelectric conversion efficiency of the organic thin film solar cell is still not sufficient. The photoelectric conversion efficiency η is calculated by the product “η = open circuit voltage (Voc) × short circuit current density (Jsc) × curve factor (FF)” of the short circuit current density (Jsc), the open circuit voltage (Voc), and the fill factor (FF). In order to increase the photoelectric conversion efficiency, it is necessary to improve the short circuit current density (Jsc) and the fill factor (FF) in addition to the improvement of the open circuit voltage (Voc).

Since the open circuit voltage (Voc) is proportional to the energy difference between the HOMO (highest occupied orbital) level of the p-type organic semiconductor and the LUMO (lowest unoccupied orbital) level of the n-type organic semiconductor, the open circuit voltage (Voc) ) Needs to be deepened (reduced) in the HOMO level of the p-type organic semiconductor.

Further, the short circuit current density (Jsc) correlates with the amount of energy received by the organic semiconductor material. In order to improve the short circuit current density (Jsc) of the organic semiconductor material, from the visible region to the near infrared region. It is necessary to absorb light in a wide wavelength range. Of the light that can be absorbed by the organic semiconductor material, the wavelength of the light with the lowest energy (the longest wavelength) is the absorption edge wavelength, and the energy corresponding to this wavelength corresponds to the band gap energy. Therefore, in order to absorb light in a wider wavelength range, it is necessary to narrow the band gap (energy difference between the HOMO level and the LUMO level of the p-type organic semiconductor).
As one of such organic semiconductor materials, although a compound having a benzobisthiazole skeleton in a repeating unit has been proposed (Patent Document 1), performance as an organic semiconductor material such as photoelectric conversion efficiency is not specified.

Patent Document 1: JP 2007-238530 A

An object of the present invention is to provide an organic semiconductor material excellent in conversion efficiency. Another object of the present invention is to provide a raw material compound that can introduce more various skeletons and substituents because the organic semiconductor material is closely related to the chemical structure and the conversion efficiency. Furthermore, it is providing the manufacturing method of such an organic-semiconductor material and its raw material compound.

In order to improve the conversion efficiency, that is, to improve the short-circuit current density (Jsc) while improving the open circuit voltage (Voc), the present inventors have made the p-type organic semiconductor absorb light in a wide wavelength range and simultaneously perform HOMO. We found it useful to make the level moderately deep. And as a result of earnestly examining paying attention to the correlation between the conversion efficiency and the chemical structure in the p-type organic semiconductor material, by using an organic semiconductor polymer having a specific structure, the entire visible light region has a wide light absorption. At the same time, it was found that the short circuit current density (Jsc) can be improved while improving the open circuit voltage (Voc) because the HOMO level and the LUMO level can be adjusted to appropriate ranges. And when such an organic-semiconductor polymer was used, it discovered that a charge separation could be easily caused between a p-type organic semiconductor and an n-type organic semiconductor, and completed this invention.

That is, the polymer compound according to the present invention includes a repeating unit having a benzobisthiazole structure represented by the following formula (1) and a repeating unit having a thiophene structure represented by the following formula (2).

[In formula (1), T ¹ and T ² are each independently a thiophene ring, hydrocarbon group, or organosilyl optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group. Represents a thiazole ring which may be substituted with a group, or a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom or a trifluoromethyl group. ]

[In Formula (2), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. ]

The polymer compound according to the present invention preferably includes a repeating unit represented by the following formula (3).

[In Formula (3), T ¹ , T ² and R ¹ each represent the same group as described above, and p represents an integer of 1 to 10. ]

Moreover, it is preferable that the high molecular compound which concerns on this invention contains the repeating unit represented by following formula (6).

[In Formula (1), T ¹ , T ² , T ³ , T ⁴ are each independently a thiophene ring, carbonized, which may be substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group. A hydrogen group or a thiazole ring which may be substituted with an organosilyl group, or a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom or a trifluoromethyl group; To express.
R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
T ¹ , T ² , T ³ , and T ⁴ are all the same, and R ¹ , R ² , R ³ , and R ⁴ are not all the same. ]

In the formulas (1), (3) and (3), T ¹ , T ² , T ³ and T ⁴ are groups represented by any of the following formulas (t1) to (t5), respectively. It is preferable.

[In the formulas (t1) to (t5),
R ²¹ to R ²² each independently represents a hydrocarbon group having 6 to 30 carbon atoms.
R ²³ to R ²⁴ each independently represents a hydrocarbon group having 6 to 30 carbon atoms or a group represented by **-Si (R ²⁶ ) ₃ .
R ²⁵ each independently represents a hydrocarbon group having 6 to 30 carbon atoms, ** — O—R ²⁷ , ** — S—R ²⁸ , ** — Si (R ²⁶ ) ₃ , a halogen atom, or **. It represents a -CF _3.
R ²⁶ each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the plurality of R ²⁶ may be the same or different.
R ²⁷ to R ²⁸ each represents a hydrocarbon group having 6 to 30 carbon atoms.
* Represents a bond bonded to the thiazole ring of benzobisthiazole. ** represents a bond that binds to (t3) to (t5). ]

The technical scope of the present invention also includes an organic semiconductor material containing the compound of the present invention and that the organic semiconductor material is a p-type semiconductor or an n-type semiconductor. Furthermore, the technical scope of the present invention also includes an organic electronic device including the organic semiconductor material, and that the organic electronic device is a photoelectric conversion element or a solar cell.

A dihalogenobenzobisthiazole compound represented by the following formula (4) (hereinafter sometimes referred to as “compound (4)”);

[In Formula (4), T ¹ and T ² each represent the same group as described above, and X ¹ and X ² each represent a halogen atom. ]
A thiophene compound represented by the following formula (5) (hereinafter sometimes referred to as “compound (5)”),

[In Formula (5), R ¹ represents the same group as described above, and p represents the same integer as described above.
R ¹⁰ to R ¹³ each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.
M ¹ and M ² each independently represent a boron atom or a tin atom. R ¹⁰ and R ¹¹ may form a ring with M ¹ , and R ¹² and R ¹³ may form a ring with M ² .
m and n each represents an integer of 1 or 2. When m and n are 2, the plurality of R ¹⁰ and R ¹² may be the same or different. ]
A method for producing a polymer compound represented by formula (3), wherein a cross-coupling reaction is performed.

[In Formula (3), T ¹ , T ² and R ¹ each represent the same group as described above, and p represents the same integer as described above. ]

A dihalogenobenzobisthiazole compound represented by the following formula (7) (hereinafter sometimes referred to as “compound (7)”);

[In Formula (7), T ¹ and T ² are each independently a thiophene ring, hydrocarbon group, or organosilyl optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group. Represents a thiazole ring which may be substituted with a group, or a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom or a trifluoromethyl group.
R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
X ¹ and X ² represent a halogen atom. ]
A benzobisthiazole compound represented by the following formula (8) (hereinafter sometimes referred to as “compound (8)”),

[In formula (8), T ³ and T ⁴ are each independently a thiophene ring, hydrocarbon group, or organosilyl optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group. Represents a thiazole ring which may be substituted with a group, or a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom or a trifluoromethyl group.
R ³ and R ⁴ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
R ¹⁰ to R ¹³ each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.
M ¹ and M ² each independently represent a boron atom or a tin atom. R ¹⁰ and R ¹¹ may form a ring with M ¹ , and R ¹² and R ¹³ may form a ring with M ² .
m and n each represents an integer of 1 or 2. When m and n are 2, the plurality of R ¹⁰ and R ¹² may be the same or different. ]
A method for producing a polymer compound represented by formula (6), wherein a cross-coupling reaction is performed.

[In Formula (6), T ¹ , T ² , T ³ , T ⁴ , R ¹ , R ² , R ³ , R ⁴ each represents the same group as described above. ]

A dihalogenobenzobisthiazole compound represented by the following formula (7) (hereinafter sometimes referred to as “compound (7)”);

[In Formula (7), T ¹ and T ² are each independently a thiophene ring, hydrocarbon group, or organosilyl optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group. Represents a thiazole ring which may be substituted with a group, or a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom or a trifluoromethyl group.
R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
X ¹ and X ² represent a halogen atom. ]
A thiophene compound represented by the following formula (5) (hereinafter sometimes referred to as “compound (5)”),

[In Formula (5), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. p represents an integer of 1 to 10.
R ¹⁰ to R ¹³ each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.
M ¹ and M ² each independently represent a boron atom or a tin atom. R ¹⁰ and R ¹¹ may form a ring with M ¹ , and R ¹² and R ¹³ may form a ring with M ² .
m and n each represents an integer of 1 or 2. When m and n are 2, the plurality of R ¹⁰ and R ¹² may be the same or different. ]
A method for producing a polymer compound represented by formula (3), wherein a cross-coupling reaction is performed.

[In Formula (3), T ¹ , T ² and R ¹ each represent the same group as described above, and p represents the same integer as described above. ]

The benzobisthiazole compound of the present invention can form a planar cruciform skeleton by intramolecular SN interaction. As a result, π conjugation is extended to a planar cross-shaped skeleton, so that multiband light absorption derived from a plurality of π-π ^* transitions is exhibited, and the entire visible light region has wide light absorption. Furthermore, due to the high planarity of the planar cross-shaped skeleton, high charge transport characteristics can be achieved. Therefore, it is useful as an organic semiconductor material, particularly a solar cell material. Moreover, according to the production method of the present invention, benzobisthiazole compounds into which more various skeletons and substituents are introduced can be obtained.

FIG. 1 shows an ultraviolet-visible absorption spectrum (diluted chloroform solution) of the polymer compound of Example 1. FIG. 2 shows an ultraviolet-visible absorption spectrum (diluted chloroform solution) of the polymer compound of Example 2. FIG. 3 shows an ultraviolet-visible absorption spectrum (diluted chloroform solution) of the polymer compound of Example 3. FIG. 4 shows an ultraviolet-visible absorption spectrum (diluted chloroform solution) of the polymer compound of Example 4. FIG. 5 shows the UV-visible absorption spectrum (chloroform dilute solution) of the polymer compound of Example 5. FIG. 6 shows an ultraviolet-visible absorption spectrum (diluted chloroform solution) of the polymer compound of Example 6. FIG. 7 shows an ultraviolet-visible absorption spectrum (chloroform dilute solution) of the polymer compound of Example 7. FIG. 8 shows the UV-visible absorption spectrum (chloroform dilute solution) of the polymer compound of Example 8. FIG. 9 shows an ultraviolet-visible absorption spectrum (chloroform dilute solution) of the polymer compound of Example 9. FIG. 10 shows an ultraviolet-visible absorption spectrum (diluted chloroform solution) of the polymer compound of Example 10.

Hereinafter, embodiments of the present invention will be described in detail. The description of the constituent requirements described below is an example of the embodiment of the present invention, and the present invention is not specified by these contents unless it exceeds the gist.

1. Polymer Compound The polymer compound of the present invention has a repeating unit having a benzothiazole structure represented by the following formula (1) and a repeating unit having a thiophene structure represented by the formula (2).

[In Formula (1), T ¹ and T ² are each independently a thiophene ring, hydrocarbon group, or organosilyl group optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon, or an organosilyl group. Represents a thiazole ring which may be substituted with or a phenyl group which may be substituted with a hydrocarbon, alkoxy group or thioalkoxy group. ]

[In Formula (2), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. ]

Since the polymer compound of the present invention has a benzobisthiazole structural unit represented by the formula (1) and a thiazole structural unit represented by the formula (2), it has a high planar structure due to intramolecular SN interaction. However, the π-conjugated system spreads through the cruciform skeleton and exhibits multiband light absorption characteristics derived from a plurality of π-π ^* transitions. As a result, the entire visible light region has a wide absorption. Furthermore, the band gap can be narrowed while deepening the HOMO level, which is advantageous in increasing the photoelectric conversion efficiency.

The polymer compound of the present invention preferably contains a repeating unit having a benzobisthiazole structure represented by the following formula (3).

[In Formula (3), T ¹ , T ² and R ¹ each represent the same group as described above, and p represents an integer of 1 to 10. ]

The polymer compound of the present invention preferably has a repeating unit having a benzobisthiazole structure represented by the following formula (6).

[In Formula (1), T ¹ , T ² , T ³ , T ⁴ are each independently a thiophene ring, carbonized, which may be substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group. A hydrogen group or a thiazole ring which may be substituted with an organosilyl group, or a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom or a trifluoromethyl group; To express.
R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
T ¹ , T ² , T ³ , and T ⁴ are all the same, and R ¹ , R ² , R ³ , and R ⁴ are not all the same. ]

In the benzobisthiazole structural units represented by formula (1) and formula (3), T ¹ and T ² may be the same or different from each other, but are the same from the viewpoint of easy production. Preferably there is. In the benzobisthiazole structural unit represented by the formula (6), T ¹ , T ² , T ³ , and T ⁴ may be the same or different from each other, but at least one of them is different. It is preferable. Further, from the viewpoint of easy production, it is preferable that T ¹ and T ² are the same and T ³ and T ⁴ are the same.
T ¹ and T ² in the benzobisthiazole structural unit represented by formula (1) and formula (3), and T ¹ , T ² , T ³ and T in the benzobisthiazole structural unit represented by formula (6) Each of ⁴ is preferably a group represented by the following formulas (t1) to (t5). Specifically, the alkoxy group of T ¹ , T ² , T ³ , and T ⁴ is preferably a group represented by the following formula (t1), and the thioalkoxy group is represented by the following formula (t2). A thiophene ring optionally substituted with a hydrocarbon group or an organosilyl group is preferably a group represented by the following formula (t3), and a thiazole optionally substituted with a hydrocarbon group or an organosilyl group As the ring, a group represented by the following formula (t4) is preferable, and as a phenyl group optionally substituted by a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom, or a trifluoromethyl group Is preferably a group represented by the following formula (t5). When T ¹ , T ² , T ³ , and T ⁴ are groups represented by the following formulas (t1) to (t5), it is possible to absorb short-wavelength light and to have high planarity, thereby improving efficiency. Since π-π stacking is formed, the photoelectric conversion efficiency can be further increased.

[In the formulas (t1) to (t5),
R ²¹ to R ²² each independently represents a hydrocarbon group having 6 to 30 carbon atoms.
R ²³ to R ²⁴ each independently represents a hydrocarbon group having 6 to 30 carbon atoms or a group represented by **-Si (R ²⁶ ) ₃ .
R ²⁵ each independently represents a hydrocarbon group having 6 to 30 carbon atoms, ** — O—R ²⁷ , ** — S—R ²⁸ , ** — Si (R ²⁶ ) ₃ , a halogen atom, or * * Represents CF ₃ .
R ²⁶ each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the plurality of R ²⁶ may be the same or different.
R ²⁷ to R ²⁸ each represents a hydrocarbon group having 6 to 30 carbon atoms.
* Represents a bond bonded to the thiazole ring of benzobisthiazole. ** represents a bond that binds to (t3) to (t5). ]

In the above formulas (t1) to (t5), the hydrocarbon group having 6 to 30 carbon atoms of R ²¹ to R ²⁵ and R ²⁷ to R ²⁸ is preferably a branched hydrocarbon group, more preferably It is a branched chain saturated hydrocarbon group. Since the hydrocarbon groups of R ²¹ to R ²⁵ and R ²⁷ to R ²⁸ have a branch, the solubility in an organic solvent can be increased, and the polymer compound of the present invention can obtain appropriate crystallinity. . The larger the carbon number of the hydrocarbon group of R ²¹ to R ²⁵ and R ²⁷ to R ²⁸ , the more the solubility in an organic solvent can be improved. Therefore, the synthesis of the polymer compound becomes difficult. Therefore, the carbon number of the hydrocarbon group of R ²¹ to R ²⁵ and R ²⁷ to R ²⁸ is preferably 8 to 28, more preferably 8 to 26, and still more preferably 8 to 24.

Examples of the hydrocarbon group having 6 to 30 carbon atoms represented by R ²¹ to R ²⁵ and R ²⁷ to R ²⁸ include an n-hexyl group, an n-heptyl group, an n-octyl group, and 1-n-butylbutyl. Group, 1-n-propylpentyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 1-methylheptyl group, 2-methylheptyl group, 6-methylheptyl group, 2, C8 alkyl group such as 4,4-trimethylpentyl group, 2,5-dimethylhexyl group; n-nonyl group, 1-n-propylhexyl group, 2-n-propylhexyl group, 1-ethylheptyl group 2-ethylheptyl group, 1-methyloctyl group, 2-methyloctyl group, 6-methyloctyl group, 2,3,4,4-tetramethylpentyl group, 3,5,5- An alkyl group having 9 carbon atoms such as trimethylhexyl group; n-decyl group, 1-n-pentylpentyl group, 1-n-butylhexyl group, 2-n-butylhexyl group, 1-n-propylheptyl group, 1 An alkyl group having 10 carbon atoms such as -ethyloctyl group, 2-ethyloctyl group, 1-methylnonyl group, 2-methylnonyl group, 3,7-dimethyloctyl group; n-undecyl group, 1-n-butylheptyl group, An alkyl group having 11 carbon atoms such as 2-n-butylheptyl group, 1-n-propyloctyl group, 2-n-propyloctyl group, 1-ethylnonyl group, 2-ethylnonyl group; n-dodecyl group, 1-n -Pentylheptyl group, 2-n-pentylheptyl group, 1-n-butyloctyl group, 2-n-butyloctyl group, 1-n-propylnonyl group, 2-n-propylno group An alkyl group having 12 carbon atoms such as an alkyl group; n-tridecyl group, 1-n-pentyloctyl group, 2-n-pentyloctyl group, 1-n-butylnonyl group, 2-n-butylnonyl group, 1-methyldodecyl group Group, an alkyl group having 13 carbon atoms such as 2-methyldodecyl group; n-tetradecyl group, 1-n-heptylheptyl group, 1-n-hexyloctyl group, 2-n-hexyloctyl group, 1-n-pentyl C14 alkyl groups such as nonyl group and 2-n-pentylnonyl group; carbons such as n-pentadecyl group, 1-n-heptyloctyl group, 1-n-hexylnonyl group and 2-n-hexylnonyl group A number 15 alkyl group; carbon such as n-hexadecyl group, 2-n-hexyldecyl group, 1-n-octyloctyl group, 1-n-heptylnonyl group, 2-n-heptylnonyl group, etc. Alkyl group having 16 carbon atoms such as n-heptadecyl group and 1-n-octylnonyl group; alkyl group having 18 carbon atoms such as n-octadecyl group and 1-n-nonylnonyl group; n-nonadecyl group An alkyl group having 19 carbon atoms such as n-eicosyl group and 2-n-octyldodecyl group; an alkyl group having 21 carbon atoms such as n-heneicosyl group; a carbon such as n-docosyl group; An alkyl group having 22 carbon atoms; an alkyl group having 23 carbon atoms such as an n-tricosyl group; an alkyl group having 24 carbon atoms such as an n-tetracosyl group and a 2-n-decyltetradecyl group; An alkyl group having 8 to 28 carbon atoms is preferable, an alkyl group having 8 to 26 carbon atoms is more preferable, a branched alkyl group having 8 to 24 carbon atoms is further preferable, and 2-ethylhexyl is particularly preferable. A group, 3,7-dimethyloctyl group, 2-n-butyloctyl group, 2-n-hexyldecyl group, 2-n-octyldodecyl group and 2-n-decyltetradecyl group. When R ²¹ to R ²⁵ and R ²⁷ to R ²⁸ are the above groups, the polymer compound of the present invention has improved solubility in an organic solvent and has appropriate crystallinity.

In the above formulas (t1) to (t5), in the group represented by **-Si (R ²⁶ ) ₃ of R ²³ to R ²⁵ , the number of carbon atoms of the aliphatic hydrocarbon group of R ²⁶ is preferably 1 to 18, more preferably 1-8. Examples of the aliphatic hydrocarbon group for R ²⁶ include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an isobutyl group, an octyl group, and an octadecyl group. The number of carbon atoms of the aromatic hydrocarbon group for R ²⁶ is preferably 6 to 8, more preferably 6 to 7, and particularly preferably 6. Examples of the aromatic hydrocarbon group for R ²⁶ include a phenyl group. Among them, R ²⁶ is preferably an aliphatic hydrocarbon group, more preferably a branched aliphatic hydrocarbon group, and particularly preferably an isopropyl group. The plurality of R ²⁶ may be the same or different, but are preferably the same. When R ²³ to R ²⁵ are groups represented by **-Si (R ²⁶ ) ₃ , the polymer compound of the present invention has improved solubility in an organic solvent.

In the above formulas (t1) to (t5), the groups represented by **-Si (R ²⁶ ) ₃ in R ²³ to R ²⁵ are specifically a trimethylsilyl group, an ethyldimethylsilyl group, an isopropyldimethylsilyl group. Group, triisopropylsilyl group, tert-butyldimethylsilyl group, triethylsilyl group, triisobutylsilyl group, tripropylsilyl group, tributylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group and other alkylsilyl groups; Groups, arylsilyl groups such as tert-butylchlorodiphenylsilyl group; and the like. Among them, an alkylsilyl group is preferable, and a trimethylsilyl group and a triisopropylsilyl group are particularly preferable.

In the above formula (t5), when R ²⁵ is a halogen atom, any of fluorine, chlorine, bromine and iodine can be used.

T ¹ , T ² , T ³ , and T ⁴ are represented by the formulas (t1) to (t5) from the viewpoint of excellent planarity as the whole structural unit represented by the formula (1), the formula (3), or the formula (6). ) Is more preferred, a group represented by the formula (t3) is more preferred, and groups represented by the following formulas (t3-1) to (t3-12) are particularly preferred. In the formula, * represents a bond bonded to the thiazole ring of benzobisthiazole.

As the benzobisthiazole structural unit represented by the above formula (1), groups represented by the following formulas (1-1) to (1-6) are particularly preferable.

In the above formulas (2), (3) and (6), the larger the carbon number of the hydrocarbon group having 1 to 30 carbon atoms of R ¹ , R ² , R ³ and R ⁴ , The solubility can be improved, but if it becomes too large, the reactivity in the coupling reaction described later is lowered, and therefore, the synthesis of the polymer compound becomes difficult. Therefore, the carbon number of the hydrocarbon group of R ¹ , R ² , R ³ , R ⁴ is preferably 1-30, more preferably 1-16, and even more preferably 1-8.

Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ include a methyl group having 1 carbon atom; an ethyl group having 2 carbon atoms. An alkyl group having 3 carbon atoms such as n-propyl group; an alkyl group having 4 carbon atoms such as n-butyl group; an alkyl group having 5 carbon atoms such as n-pentyl group; a carbon atom having 6 carbon atoms such as n-hexyl group; Alkyl group; alkyl group having 7 carbon atoms such as n-heptyl group; n-octyl group, 1-n-butylbutyl group, 1-n-propylpentyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group Alkyl groups having 8 carbon atoms such as 4-ethylhexyl group, 1-methylheptyl group, 2-methylheptyl group, 6-methylheptyl group, 2,4,4-trimethylpentyl group, 2,5-dimethylhexyl group; n -Nonyl group, 1-n-propylhexyl group, 2-n-propylhexyl group, 1-ethylheptyl group, 2-ethylheptyl group, 1-methyloctyl group, 2-methyloctyl group, 6-methyloctyl group, C9 alkyl groups such as 2,3,3,4-tetramethylpentyl group and 3,5,5-trimethylhexyl group; n-decyl group, 1-n-pentylpentyl group, 1-n-butylhexyl Group, 2-n-butylhexyl group, 1-n-propylheptyl group, 1-ethyloctyl group, 2-ethyloctyl group, 1-methylnonyl group, 2-methylnonyl group, 3,7-dimethyloctyl group, etc. An alkyl group of several tens; n-undecyl group, 1-n-butylheptyl group, 2-n-butylheptyl group, 1-n-propyloctyl group, 2-n-propyloctyl group, 1- An alkyl group having 11 carbon atoms such as tilnonyl group, 2-ethylnonyl group; n-dodecyl group, 1-n-pentylheptyl group, 2-n-pentylheptyl group, 1-n-butyloctyl group, 2-n-butyl 12 alkyl groups such as octyl, 1-n-propylnonyl, 2-n-propylnonyl; n-tridecyl, 1-n-pentyloctyl, 2-n-pentyloctyl, 1- Alkyl groups having 13 carbon atoms such as n-butylnonyl group, 2-n-butylnonyl group, 1-methyldodecyl group, 2-methyldodecyl group; n-tetradecyl group, 1-n-heptylheptyl group, 1-n-hexyl C14 alkyl group such as octyl group, 2-n-hexyloctyl group, 1-n-pentylnonyl group, 2-n-pentylnonyl group; n-pentadecyl group, 1-n- C15 alkyl groups such as a ptyloctyl group, 1-n-hexylnonyl group, 2-n-hexylnonyl group; n-hexadecyl group, 2-n-hexyldecyl group, 1-n-octyloctyl group, 1 An alkyl group having 16 carbon atoms such as n-heptylnonyl group and 2-n-heptylnonyl group; an alkyl group having 17 carbon atoms such as n-heptadecyl group and 1-n-octylnonyl group; n-octadecyl group and 1-n An alkyl group having 18 carbon atoms such as nonylnonyl group; an alkyl group having 19 carbon atoms such as n-nonadecyl group; an alkyl group having 20 carbon atoms such as n-eicosyl group and 2-n-octyldodecyl group; n-heneicosyl group An alkyl group having 21 carbon atoms such as n-docosyl group; an alkyl group having 23 carbon atoms such as n-tricosyl group; an n-tetracosyl group, 2-n -C24 alkyl group such as decyltetradecyl group; and the like. Preferably, it is an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 16 carbon atoms, still more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group. Or a hydrogen atom is preferable. When R ¹ , R ² , R ³ , and R ⁴ are the above groups, the polymer compound of the present invention has improved solubility in an organic solvent and has appropriate solubility and crystallinity.

Further, as the thiophene structural unit represented by the above formula (2), groups represented by the following formulas (2-1) to (2-19) are particularly preferable.

In addition, T ¹ , T ² , and R ^{1 in} the structural unit of the polymer compound represented by the formula (3) are the same as described above. p is an integer of 1 to 10, but is preferably an alkyl group of 1 to 7, more preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 to 2.

As the structural unit of the polymer compound represented by the above formula (3), groups represented by the following formulas (3-1) to (3-18) are particularly preferable.

[Wherein, R ¹ represents the same group as described above. ]

As the benzobisthiazole structural unit represented by the above formula (6), groups represented by the following formulas (6-1) to (6-21) are particularly preferable.

[In the formula (6), R ¹ , R ² , R ³ and R ⁴ each represent the same group as described above. ]

The weight average molecular weight and number average molecular weight of the polymer compound of the present invention are generally 2,000 or more and 500,000 or less, more preferably 3,000 or more and 200,000 or less. The weight average molecular weight and number average molecular weight of the polymer compound of the present invention can be calculated based on a calibration curve prepared using polystyrene as a standard sample using gel permeation chromatography.

The ionization potential of the polymer compound of the present invention is preferably 4 eV or more, more preferably 4.5 eV or more, still more preferably 5 eV or more, and particularly preferably 5.1 eV or more. Although the upper limit of ionization potential is not specifically limited, For example, it is 7 eV or less, it is preferable that it is 6.5 eV or less, and it is preferable that it is 6 eV or less. When the ionization potential of the polymer compound of the present invention is in the above range, the HOMO level is appropriately deepened (lowered), so that both a high open-circuit voltage (Voc) and a short-circuit current density (Jsc) can be obtained. It becomes possible, and higher photoelectric conversion efficiency can be obtained.

2. Production Method The polymer compound represented by the formula (3) of the present invention is:

[In Formula (3), T ¹ , T ² and R ¹ each represent the same group as described above, and p represents the same integer as described above. ]
A dihalogenobenzobisthiazole compound represented by the following formula (4);

[In the formula (4), T ¹ , T ² , X ¹ and X ² each represent the same group as described above. ]
It can manufacture by carrying out a cross coupling reaction with the thiophene compound represented by following formula (5).

[In the formula (5), R ¹ , R ¹⁰ to R ¹³ , M ¹ , M ² and p each represent the same group as described above. ]

The polymer compound represented by the formula (6) of the present invention is

[In Formula (6), T ¹ , T ² , T ³ , T ⁴ , R ¹ , R ² , R ³ , R ⁴ each represents the same group as described above. ]
A dihalogenobenzobisthiazole compound represented by the following formula (7);

[In formula (7), T ¹ , T ² , R ¹ , R ² , X ¹ , X ² each represents the same group as described above. ]
It can manufacture by carrying out a cross coupling reaction with the benzobis thiazole compound represented by following formula (8).

[In the formula (8), T ³ , T ⁴ , R ³ , R ⁴ , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , M ¹ and M ² each represent the same group as described above. ]

Further, the polymer compound represented by the formula (3) of the present invention is obtained by cross-coupling a dihalogenobenzobisthiazole compound represented by the formula (7) and a thiophene compound represented by the formula (5). It can also be produced by reacting.

In formula (4) and formula (7), examples of the halogen atom for X ¹ and X ² include chlorine, bromine, and iodine. Any of them can be used, but bromine and iodine are particularly preferable from the viewpoint of a balance between reactivity and stability.

For example, 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d ′] bisthiazole (DI-DBTH-HDTH ) Can be synthesized from known 2,6-diiodobenzo [1,2-d; 4,5-d ′] bisthiazole (DBTH-DI) as shown in the following reaction formula.

In the formulas (2), (3), and (5) to (8), the hydrocarbon group having 1 to 30 carbon atoms represented by R ¹ , R ² , R ³ , and R ⁴ is a methyl group, An ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group are preferred. Or a hydrogen atom is preferable.

The compound (7) is preferably used as an intermediate compound of the polymer compound represented by the formulas (3) and (6) of the present invention. Since this compound (7) has the above-mentioned predetermined group, it has high temporal stability and can react efficiently to form the polymer compound of the present invention. As compound (7), the compound represented by a following formula can be illustrated, for example. In addition, a compound in which bromine is substituted with iodine in formulas (7-1) to (7-6) can also be preferably exemplified as compound (7).

In formula (5) and formula (8), the number of carbon atoms of the aliphatic hydrocarbon group of R ¹⁰ to R ¹³ is preferably 1 to 5, and more preferably 1 to 4. The aliphatic hydrocarbon group for R ¹⁰ to R ¹³ is preferably a methyl group, an ethyl group, a propyl group, or a butyl group, more preferably a methyl group or a butyl group. The number of carbon atoms of the alkoxy group of R ¹⁰ to R ¹³ is preferably 1 to 3, and more preferably 1 to 2. As the alkoxy group for R ¹⁰ to R ¹³ , a methoxy group, an ethoxy group, a propoxy group and the like are preferable, and a methoxy group and an ethoxy group are more preferable. The number of carbon atoms of the aryloxy group of R ¹⁰ to R ¹³ is preferably 6 to 9, and more preferably 6 to 8. Examples of the aryloxy group for R ¹⁰ to R ¹³ include a phenyloxy group, a benzyloxy group, and a phenylenebis (methyleneoxy) group. R ¹⁰ to R ¹³ may be the same or different from each other.

When M ¹ and M ² are boron atoms, R ¹⁰ to R ¹³ are preferably a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms, m, And n is preferably 1. ***-M ¹ (R ¹⁰ ) _m R ¹¹ , ***-M ² (R ¹² ) _n R ¹³ when M ¹ and M ² are boron atoms are represented by, for example, the following formulae: Group. However, *** represents a bond with a thiophene ring.

When M ¹ and M ² are tin atoms, R ¹⁰ to R ¹³ are preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and m and n are preferably 2. ***-M ¹ (R ¹⁰ ) _m R ¹¹ , ***-M ² (R ¹² ) _n R ¹³ in the case where M ¹ and M ² are tin atoms are represented by, for example, the following formulae: Group. However, *** represents a bond with a thiophene ring or a thiazole ring.

The compound (5) is an intermediate compound used for the synthesis of the polymer compound of the present invention. Since this compound (5) has the above-mentioned predetermined group, it has high temporal stability and can react efficiently to form the polymer compound of the present invention. As compound (5), the compound represented by a following formula can be illustrated, for example. In addition, compounds represented by formulas (5-1) to (5-10) in which the methyl group on the tin atom is substituted with a butyl group are also preferred as the compound (5).

In the production of the polymer compound represented by formula (3), the molar ratio of the dihalogenobenzobisthiazole compound represented by formula (4) or formula (7) and the thiophene compound represented by formula (5) is: Generally, it is about 1: 0.8 to 1:10, and is not particularly limited, but is preferably 1: 0.8 to 1: 8, more preferably 1: 0.9 to 1: 6 from the viewpoint of yield and reaction efficiency. More preferably, the ratio is 1: 1 to 1: 5.

The compound (8) is preferably used as an intermediate compound used for the synthesis of the polymer compound represented by the formula (6) of the present invention. Since this compound (8) has the above-mentioned predetermined group, it has high temporal stability and can react efficiently to form the polymer compound of the present invention. As compound (8), the compound represented by a following formula can be illustrated, for example. In addition, in the formulas (8-1) to (8-6), a compound in which the methyl group on the tin atom is substituted with a butyl group can also be preferably exemplified as the compound (8).

For example, 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-bis (5-trimethylstannylthiophen-2-yl) -benzo [1,2-d; , 5-d '] bisthiazole (DTH-DBTH-HDTH-DSM) and 4,8-bis (5-bromothiophen-2-yl) -2,6-bis [5- (2-hexyldecyl) thiophene- 2-yl] -benzo [1,2-d; 4,5-d ′] bisthiazole (DTH-DBTH-HDTH-DB) is a known 2,6-diiodobenzo [1,2-d; It can be synthesized from 5-d ′] bisthiazole (DBTH-DI) as shown in the following reaction formula.

In the production of the polymer compound represented by the formula (6), the molar ratio of the dihalogenobenzobisthiazole compound represented by the formula (7) and the benzobisthiazole compound represented by the formula (8) is generally 1: Although it is about 0.8 to 1:10 and is not particularly limited, it is preferably 1: 0.8 to 1: 8, more preferably 1: 0.9 to 1: 6, from the viewpoint of yield and reaction efficiency. 1 to 1: 5 is more preferable.

In the production of the polymer compound represented by the formula (3), the dihalogenobenzobisthiazole compound represented by the formula (4) or the formula (7) is reacted with the thiophene compound represented by the formula (5). Examples of the metal catalyst used include transition metal catalysts such as a palladium catalyst, a nickel catalyst, an iron catalyst, a copper catalyst, a rhodium catalyst, and a ruthenium catalyst. Among these, a palladium-based catalyst is preferable. Note that the valence of palladium is not particularly limited, and may be zero or divalent.

Metal catalyst used in the reaction of the dihalogenobenzobisthiazole compound represented by formula (7) and the benzobisthiazole compound represented by formula (8) in the production of the polymer compound represented by formula (6) Examples thereof include transition metal catalysts such as palladium catalysts, nickel catalysts, iron catalysts, copper catalysts, rhodium catalysts, and ruthenium catalysts. Among these, a palladium-based catalyst is preferable. Note that the valence of palladium is not particularly limited, and may be zero or divalent.

Examples of the palladium-based catalyst include palladium (II) chloride, palladium (II) bromide, palladium (II) iodide, palladium (II) oxide, palladium (II) sulfide, palladium (II) telluride, palladium hydroxide ( II), palladium selenide (II), palladium cyanide (II), palladium acetate (II), palladium trifluoroacetate (II), palladium acetylacetonate (II), diacetate bis (triphenylphosphine) palladium (II) ), Tetrakis (triphenylphosphine) palladium (0), dichlorobis (triphenylphosphine) palladium (II), dichlorobis (acetonitrile) palladium (II), dichlorobis (benzonitrile) palladium (II), dichloro [1,2 Bis (diphenylphosphino) ethane] palladium (II), dichloro [1,3-bis (diphenylphosphino) propane] palladium (II), dichloro [1,4-bis (diphenylphosphino) butane] palladium (II) Dichloro [1,1-bis (diphenylphosphinoferrocene)] palladium (II), dichloro [1,1-bis (diphenylphosphino) ferrocene] palladium (II) dichloromethane adduct, bis (dibenzylideneacetone) palladium ( 0), tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium (0) chloroform adduct, dichloro [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene ] (3-chloropyridyl) paradi (II), bis (tri-tert-butylphosphine) palladium (0), dichloro [2,5-norbornadiene] palladium (II), dichlorobis (ethylenediamine) palladium (II), dichloro (1,5-cyclooctadiene ) Palladium (II), dichlorobis (methyldiphenylphosphine) palladium (II). These catalysts may be used individually by 1 type, and may mix and use 2 or more types. Of these, dichlorobis (triphenylphosphine) palladium (II), tris (dibenzylideneacetone) dipalladium (0), and tris (dibenzylideneacetone) dipalladium (0) chloroform adduct are particularly preferred.

In the production of the polymer compound represented by formula (3), the molar ratio of the dihalogenobenzobisthiazole compound represented by formula (4) or formula (7) to the metal catalyst (dihalogenobenzobisthiazole compound: metal The catalyst) is generally about 1: 0.0001 to 1: 0.5 and is not particularly limited, but is preferably 1: 0.001 to 1: 0.4 from the viewpoint of yield and reaction efficiency. 005 to 1: 0.3 is more preferable, and 1: 0.01 to 1: 0.2 is more preferable.

In the production of the polymer compound represented by formula (6), the molar ratio of the dihalogenobenzobisthiazole compound represented by formula (7) to the metal catalyst (dihalogenobenzobisthiazole compound: metal catalyst) is generally Although it is about 1: 0.0001 to 1: 0.5 and is not particularly limited, it is preferably 1: 0.001 to 1: 0.4 from the viewpoint of yield and reaction efficiency, and 1: 0.005 to 1: 0. .3 is more preferable, and 1: 0.01 to 1: 0.2 is more preferable.

In the production of the polymer compound represented by Formula (3) or Formula (6), a specific ligand may be coordinated to a metal catalyst such as a palladium-based catalyst. The ligands include trimethylphosphine, triethylphosphine, tri (n-butyl) phosphine, tri (isopropyl) phosphine, tri (tert-butyl) phosphine, tri-tert-butylphosphonium tetrafluoroborate, bis (tert-butyl) ) Methylphosphine, tricyclohexylphosphine, diphenyl (methyl) phosphine, triphenisphosphine, tris (o-tolyl) phosphine, tris (m-tolyl) phosphine, tris (p-tolyl) phosphine, tris (2-methoxyphenyl) phosphine , Tris (3-methoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (2-furyl) phosphine, 2-dicyclohexylphosphinobiphenyl, 2-dicyclohexylphosphine No-2′-methylbiphenyl, 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropyl-1,1′-biphenyl, 2-dicyclohexylphosphino-2 ′, 6′-dimethoxy-1,1 '-Biphenyl, 2-dicyclohexylphosphino-2'-(N, N'-dimethylamino) biphenyl, 2-diphenylphosphino-2 '-(N, N'-dimethylamino) biphenyl, 2- (di-tert -Butyl) phosphino-2 '-(N, N'-dimethylamino) biphenyl, 2- (di-tert-butyl) phosphinobiphenyl, 2- (di-tert-butyl) phosphino-2'-methylbiphenyl, 1 , 2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphine) Dino) butane, 1,2-bis (dicyclohexylphosphino) ethane, 1,3-bis (dicyclohexylphosphino) propane, 1,4-bis (dicyclohexylphosphino) butane, 1,2-bisdiphenylphosphinoethylene 1,1′-bis (diphenylphosphino) ferrocene, 1,2-ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, 2,2′-bipyridyl, 1,3-diphenyldihydroimidazolylidene 1,3-dimethyldihydroimidazolidene, diethyldihydroimidazolylidene, 1,3-bis (2,4,6-trimethylphenyl) dihydroimidazolidene, 1,3-bis (2,6-diisopropylphenyl) Dihydroimidazolidene, 1,10-phenanthroline, 5,6-dimethyl- Examples include 1,10-phenanthroline and butophenanthroline. Only 1 type may be used for a ligand and 2 or more types may be used for it. Of these, triphenylphosphine, tris (o-tolyl) phosphine, and tris (2-methoxyphenyl) phosphine are particularly preferable.

In the production of a polymer compound represented by formula (3) or formula (6), when a ligand is coordinated to a metal catalyst, the molar ratio of the metal catalyst to the ligand (metal catalyst: ligand) Is generally about 1: 0.5 to 1:10 and is not particularly limited, but is preferably 1: 1 to 1: 8, more preferably 1: 1 to 1: 7, from the viewpoint of yield and reaction efficiency. 1 to 1: 5 is more preferable.

In the production of the polymer compound represented by formula (3), the dihalogenobenzobisthiazole compound represented by formula (4) or formula (7) is represented by formula (5) in the presence of a metal catalyst. When reacting the thiophene compound, a base may coexist. In the production of the polymer compound represented by formula (6), the dihalogenobenzobisthiazole compound represented by formula (7) is added to the benzobisthiazole represented by formula (8) in the presence of a metal catalyst. When reacting the compound, a base may coexist. For example, when M ¹ and M ² are boron atoms, it is preferable to coexist with a base, and when M ¹ and M ² are tin atoms, it is not necessary to coexist with a base.

Examples of the base include lithium metal hydride, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate and other alkali metal salt compounds; magnesium hydroxide, calcium hydroxide, barium hydroxide, Alkaline earth metal salt compounds such as magnesium carbonate, calcium carbonate, barium carbonate; lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide, lithium isopropoxide, sodium isopropoxide Potassium isopropoxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, lithium tert-amyl alkoxide, sodium tert-amyl alkoxide Alkoxymethyl alkali metal compounds such as potassium tert- amyl alkoxide; lithium hydride, sodium hydride, metal hydride compounds such as potassium hydride. Among them, as the base, an alkoxyalkali metal compound is preferable, and lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, sodium carbonate, potassium carbonate, and cesium carbonate are more preferable.

In the production of the polymer compound represented by formula (3), the molar ratio of the dihalogenobenzobisthiazole compound represented by formula (4) or formula (7) to the base (dihalogenobenzobisthiazole compound: base) Is generally about 1: 1 to 1:10 and is not particularly limited, but is preferably 1: 1.5 to 1: 8, more preferably 1: 1.8 to 1: 6, from the viewpoint of yield and reaction efficiency. 1: 2 to 1: 5 is more preferable.

In the production of the polymer compound represented by formula (6), the molar ratio of the dihalogenobenzobisthiazole compound represented by formula (7) to the base (dihalogenobenzobisthiazole compound: base) is generally 1: Although it is about 1 to 1:10 and is not particularly limited, it is preferably 1: 1.5 to 1: 8, more preferably 1: 1.8 to 1: 6, and more preferably 1: 2 to 1: 8 from the viewpoint of yield and reaction efficiency. 1: 5 is more preferable.

In the production of the polymer compound represented by formula (3), the dihalogenobenzobisthiazole compound represented by formula (4) or formula (7) is represented by formula (5) in the presence of a metal catalyst. The solvent for reacting the thiophene compound is not particularly limited as long as it does not affect the reaction, ether solvent, aromatic solvent, ester solvent, hydrocarbon solvent, halogen solvent, ketone solvent, An amide solvent or the like can be used. Examples of the ether solvent include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, methyltetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, t-butyl methyl ether, and dioxane. Examples of the aromatic solvent include benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, and tetralin. Examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, and butyl acetate. Examples of the hydrocarbon solvent include pentane, hexane, heptane, octane, and decalin. Examples of the halogen solvent include dichloromethane, chloroform, dichloroethane, and dichloropropane. Examples of the ketone solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro- ( 1H) -pyrimidine. A nitrile solvent such as acetonitrile, a sulfoxide solvent such as dimethyl sulfoxide, and a sulfone solvent such as sulfolane can be used.
Among these, tetrahydrofuran, toluene, chlorobenzene, and N, N-dimethylformamide are particularly preferable.

In the production of the polymer compound represented by the formula (6), the benzobisthiazole compound represented by the formula (8) is added to the dihalogenobenzobisthiazole compound represented by the formula (7) in the presence of a metal catalyst. The said solvent can be used also about the solvent made to react.

The amount of the solvent used in the production of the polymer compound represented by formula (3) is generally 1 mL or more with respect to 1 g of the dihalogenobenzobisthiazole compound represented by formula (4) or formula (7), Although it is about 150 mL or less and it is not specifically limited, From a viewpoint of a yield or reaction efficiency, 5 mL or more and 100 mL or less are preferable, 8 mL or more and 90 mL or less are more preferable, 10 mL or more and 80 mL or less are more preferable.

The amount of the solvent used in the production of the polymer compound represented by formula (6) is the sum of the dihalogenobenzobisthiazole compound represented by formula (7) and the benzobisthiazole compound represented by formula (8). Although it is generally 1 mL or more and about 150 mL or less with respect to 1 g, it is preferably 5 mL or more and 100 mL or less from the viewpoint of yield or reaction efficiency, more preferably 8 mL or more and 90 mL or less, more preferably 10 mL or more and 80 mL or less. Further preferred.

In the production of the polymer compound represented by the formula (3) or the formula (6), the reaction temperature is not particularly limited, but is preferably 0 ° C. or higher and 200 ° C. or lower from the viewpoint of increasing the reaction yield, 30 ° C. As mentioned above, it is more preferable that it is 180 degrees C or less, and it is still more preferable that it is 40 degrees C or more and 150 degrees C or less.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention. In the following, “part” means “part by mass” and “%” means “mass%” unless otherwise specified.

The measurement method used in the examples is as follows.

(NMR spectrum measurement)
Regarding the benzobisthiazole compound, an NMR spectrum measuring apparatus (manufactured by Agilent (formerly Varian), “400MR”, and Bruker, “AVANCE”)
500 ") and NMR spectra were measured.

(Gel permeation chromatography (GPC))
The molecular weight of the benzobisthiazole compound was measured using gel permeation chromatography (GPC). In the measurement, the benzobisthiazole compound was dissolved in a mobile phase solvent (chloroform) so as to have a concentration of 0.5 g / L, measured under the following conditions, and based on a calibration curve prepared using polystyrene as a standard sample. By converting, the weight average molecular weight of the benzobisthiazole compound was calculated. The GPC conditions in the measurement are as follows.
Mobile phase: Chloroform flow rate: 0.6 ml / min
Apparatus: HLC-8320GPC (manufactured by Tosoh Corporation)
Column: TSKgel (registered trademark) SuperHM-H´2 + TSKgel (registered trademark) SuperH2000 (manufactured by Tosoh Corporation)

(UV-visible absorption spectrum)
The obtained benzobisthiazole compound was dissolved in chloroform so as to have a concentration of 0.03 g / L, and an ultraviolet / visible spectroscopic device (manufactured by Shimadzu Corporation, “UV-2450”, “UV-3150”), and The UV-visible absorption spectrum was measured using a cell having an optical path length of 1 cm.

(Ionization potential measurement)
A benzobisthiazole compound was formed on a glass substrate so as to have a thickness of 50 nm to 100 nm. The ionization potential of this membrane was measured with an ultraviolet photoelectron analyzer (“AC-3” manufactured by Riken Keiki Co., Ltd.) at room temperature and normal pressure.

(Reference Example 1)
Synthesis of 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] benzo [1,2-d; 4,5-d ′] bisthiazole (DBTH-HDTH)

In a 300 mL flask, 2,6-diiodobenzo [1,2-d; 4,5-d ′] bisthiazole (DBTH-DI, 5.2 g, 11.7 mmol), tributyl [5- (2-hexyldecyl) thiophene- 2-yl] stannane (HDT-Sn, 23.2 g, 38.6 mmol), tris (2-furyl) phosphine (443 mg, 1.87 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct ( 490 mg, 0.47 mol) and N, N-dimethylformamide (115 mL) were added and reacted at 120 ° C. for 23 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, water was added, and the mixture was extracted twice with chloroform. The organic layer was washed with water and then dried over anhydrous magnesium sulfate. Next, the crude product obtained by filtration and concentration was purified by column chromatography (silica gel, chloroform / hexane = 1/1) to obtain 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl. ] 5.62 g of benzo [1,2-d; 4,5-d ′] bisthiazole (DBTH-HDTH) was obtained as a light yellow solid (yield 60%).
It was confirmed by ¹ H-NMR measurement that the target compound was produced.

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.39 (s, 2H), 7.53 (d, J = 3.6 Hz, 2H), 6.81 (d, J = 3.6 Hz, 2H), 2.81 (m, 4H), 1.66 (m, 2H), 1.37-1.24 (m, 48H), 0.90 (t, J = 6.4 Hz, 6H), 0.88 (t, J = 6.4 Hz, 6H).

(Reference Example 2)
2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d '] bisthiazole (DI-DBTH-HDTH) Composition

In a 100 mL flask was 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] benzo [1,2-d; 4,5-d ′] bisthiazole (DBTH-HDTH, 4 g, 4.97 mmol). ) And tetrahydrofuran (80 mL) were added and the mixture was cooled to −40 ° C., and then lithium diisopropylamide (2M solution, 5.5 mL, 10.9 mmol) was added dropwise and stirred for 30 minutes. Next, iodine (3.8 g, 14.9 mol) was added, followed by reaction at room temperature for 2 hours. After completion of the reaction, 10% sodium bisulfite was added and the mixture was extracted with chloroform. The obtained organic layer was washed with saturated aqueous sodium hydrogen carbonate and then with saturated brine and dried over anhydrous magnesium sulfate. Next, the crude product obtained by filtration and concentration was purified by column chromatography (silica gel, chloroform / hexane = 1/1) to obtain 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl. ] -4,8-diiodobenzo [1,2-d; 4,5-d '] bisthiazole (DI-DBTH-HDTH) was obtained as a yellow solid (yield 51%).
It was confirmed by ¹ H-NMR measurement that the target compound was produced.

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.53 (d, J = 3.6 Hz, 2H), 6.81 (d, J = 3.6 Hz, 2H), 2.80 (m, 4H), 1.70 (m, 2H), 1.36-1.24 (m, 48H), 0.89 (t, J = 6.4 Hz, 6H), 0.86 (t, J = 6.4 Hz, 6H).

(Reference Example 3)
Synthesis of 2,6-bis [5- (2-butyloctyl) thiophen-2-yl] benzo [1,2-d; 4,5-d ′] bisthiazole (DBTH-BOTH)

In a 50 mL flask, 2,6-diiodobenzo [1,2-d; 4,5-d ′] bisthiazole (DBTH-DI, 0.86 g, 1.93 mmol), tributyl [5- (2-butyloctyl) thiophene- 2-yl] stannane (BOT-Sn, 3.4 g, 6.37 mmol), tris (2-furyl) phosphine (72 mg, 0.31 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct ( 8 mg, 0.08 mol) and N, N-dimethylformamide (20 mL) were added and reacted at 120 ° C. for 24 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, water was added, and the mixture was extracted twice with chloroform. The organic layer was washed with water and then dried over anhydrous magnesium sulfate. Next, the crude product obtained by filtration and concentration was purified by column chromatography (silica gel, chloroform / hexane = 1/1) to give 2,6-bis [5- (2-butyloctyl) thiophen-2-yl. ] 0.68 g of benzo [1,2-d; 4,5-d ′] bisthiazole (DBTH-BOTH) was obtained as a pale yellow solid (yield 51%).
It was confirmed by ¹ H-NMR measurement that the target compound was produced.

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.42 (s, 2H), 7.59 (d, J = 3.8 Hz, 2H), 6.82 (d, J = 3.8 Hz, 2H), 2.81 (m, 4H), 1.66 (m, 2H), 1.37-1.24 (m, 32H), 0.91 (t, J = 6.4 Hz,
6H), 0.88 (t, J = 6.4 Hz, 6H).

(Reference Example 4)
Of 2,6-bis [5- (2-butyloctyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d ′] bisthiazole (DI-DBTH-BOTH) Composition

In a 100 mL flask, 2,6-bis [5- (2-butyloctyl) thiophen-2-yl] benzo [1,2-d; 4,5-d ′] bisthiazole (DBTH-BOTH, 1.5 g, 2 .16 mmol) and tetrahydrofuran (30 mL) were added and cooled to −40 ° C., then lithium diisopropylamide (2M solution, 2.4 mL, 4.75 mmol) was added dropwise and stirred for 30 minutes. Next, iodine (1.7 g, 6.48 mmol) was added, followed by reaction at room temperature for 2 hours. After completion of the reaction, 10% sodium bisulfite was added and the mixture was extracted with chloroform. The obtained organic layer was washed with saturated aqueous sodium hydrogen carbonate and then with saturated brine and dried over anhydrous magnesium sulfate. Next, the crude product obtained by filtration and concentration was purified by column chromatography (silica gel, chloroform / hexane = 1/1) to give 2,6-bis [5- (2-butyloctyl) thiophen-2-yl. ] -4,8-diiodobenzo [1,2-d; 4,5-d '] bisthiazole (DI-DBTH-BOTH) was obtained as a yellow solid (yield 56%).
It was confirmed by ¹ H-NMR measurement that the target compound was produced.

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.52 (d, J = 3.6 Hz, 2H), 6.80 (d, J = 3.6 Hz, 2H), 2.80 (m, 4H), 1.69 (m, 2H), 1.34-1.23 (m, 32H), 0.89 (t, J = 6.4 Hz, 6H), 0.86 (t, J = 6.4 Hz, 6H).

(Reference Example 5)
2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-dithiophen-2-yl-benzo [1,2-d; 4,5-d ′] bisthiazole (DTH -DBTH-HDTH)

In a 50 mL flask, 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d ′] bisthiazole (DI-DBTH— HDTH, 1.1 g, 1.04 mmol), tributylthiophen-2-yl-stannane (830 μL, 2.60 mmol), tris (2-furyl) phosphine (40 mg, 0.17 mmol), tris (dibenzylideneacetone) dipalladium (0) -Chloroform adduct (45 mg, 0.04 mmol) and N, N-dimethylformamide (22 mL) were added and reacted at 80 ° C. for 19 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, water was added, and the mixture was extracted twice with chloroform. The organic layer was washed with water and then dried over anhydrous magnesium sulfate. Subsequently, the crude product obtained by filtration and concentration is purified by column chromatography (silica gel, chloroform / hexane = 1/1 to chloroform) to obtain 2,6-bis [5- (2-hexyldecyl) thiophene-2. -Il] -4,8-dithiophen-2-yl-benzo [1,2-d; 4,5-d ′] bisthiazole (DTH-DBTH-HDTH) was obtained as a yellow solid (1.01 g). Yield 100%).
It was confirmed by ¹ H-NMR measurement that the target compound was produced.

¹ H NMR (400 MHz, CDCl ₃ ): δ8.00 (dd, J = 4.0, 0.8 Hz, 2H), 7.58 (dd, J = 5.2, 0.8 Hz, 2H), 7.55 (d, J = 4.0 Hz, 2H), 7.27 (dd, J = 5.2, 4.0 Hz, 2H), 6.81 (d, J =
4.0 Hz, 2H), 2.81 (m, 4H), 1.72 (m, 2H), 1.34-1.25 (m, 48H), 0.89 (t J = 6.4 Hz, 6H), 0.87 (t, J = 6.4 Hz, 12H ).

(Reference Example 6)
2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-bis (5-trimethylstannylthiophen-2-yl) -benzo [1,2-d; -D '] Synthesis of bisthiazole (DTH-DBTH-HDTH-DSM)

Add 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-dithiophen-2-yl-benzo [1,2-d; 4,5-d ′] bis in a 30 mL flask. Add thiazole (DTH-DBTH-HDTH, 700 mg, 0.72 mmol) and tetrahydrofuran (14 mL), cool to −50 ° C., add lithium diisopropylamide (2M solution, 0.79 mL, 1.58 mmol) dropwise, and stir for 30 minutes. did. Thereafter, trimethyltin chloride (1M solution, 16 mL, 1.58 mmol) was added, and the mixture was warmed to room temperature and stirred for 2 hours. After completion of the reaction, water was added and extracted twice with toluene. The organic layer was washed with water and then dried over anhydrous magnesium sulfate. Next, the crude product obtained by filtration and concentration is purified by GPC-HPLC (JAIGEL-1H, 2H, chloroform) to give 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl]- 518 mg of 4,8-bis (5-trimethylstannylthiophen-2-yl) -benzo [1,2-d; 4,5-d '] bisthiazole (DTH-DBTH-HDTH-DSM) as a yellow solid Obtained (yield 55%). It was confirmed by ¹ H-NMR measurement that the target compound was produced.

¹ H NMR (400 MHz, CDCl ₃ ): δ8.16 (d, J = 3.6 Hz, 2H), 7.56 (d, J = 3.6 Hz, 2H), 7.37 (d, J = 3.6 Hz, 2H), 6.82 (d, J = 3.6 Hz, 2H), 2.82 (m, 4H), 1.71 (m, 2H), 1.35-1.25 (m, 48H), 0.88 (t J = 6.4 Hz, 6H), 0.87 (t, J = 6.4 Hz, 6H), 0.47 (s, 18H).

Reference Example 7 4,8-bis (5-bromothiophen-2-yl) -2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -benzo [1,2-d; Synthesis of 4,5-d ′] bisthiazole (DTH-DBTH-HDTH-DB)

2,6-Bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-dithiophen-2-yl-benzo [1,2-d; 4,5-d ′] bis in a 20 mL flask Thiazole (DTH-DBTH-HDTH, 300 mg, 0.31 mmol), NBS (N-bromosuccinimide, 122 mg, 0.70 mmol) and chloroform (6 mL) were added and reacted at room temperature for 43 hours. After completion of the reaction, it was washed with water (twice) and then dried over anhydrous magnesium sulfate. Next, the crude product obtained by filtration and concentration is purified by column chromatography (silica gel, toluene) to give 4,8-bis (5-bromothiophen-2-yl) -2,6-bis [5- ( 273 mg of 2-hexyldecyl) thiophen-2-yl] -benzo [1,2-d; 4,5-d ′] bisthiazole (DTH-DBTH-HDTH-DB) was obtained as a yellow solid (yield) 79%).
It was confirmed by ¹ H-NMR measurement that the target compound was produced.

¹ H NMR (400 MHz, CDCl ₃ ): δ7.68 (d, J = 4.0 Hz, 2H), 7.65 (d, J = 4.0 Hz, 2H), 7.20 (d, J = 4.0 Hz, 2H), 6.82 (d, J = 4.0 Hz, 2H), 2.82 (m, 4H), 1.72 (m, 2H), 1.35-1.26 (m, 48H), 0.89 (t J = 6.4 Hz, 6H), 0.87 (t, J = 6.4 Hz, 12H).

(Reference Example 8)
2,6-bis [5- (2-butyloctyl) thiophen-2-yl] -4,8-dithiophen-2-yl-benzo [1,2-d; 4,5-d ′] bisthiazole (DTH -DBTH-BOTH)

In a 50 mL flask, 2,6-bis [5- (2-butyloctyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d ′] bisthiazole (DI-DBTH— BOTH, 1.1 g, 1.16 mmol), tributylthiophen-2-yl-stannane (930 μL, 2.90 mmol), tris (2-furyl) phosphine (33 mg, 0.14 mmol), tris (dibenzylideneacetone) dipalladium (0) -Chloroform adduct (36 mg, 0.03 mmol) and N, N-dimethylformamide (22 mL) were added and reacted at 80 ° C. for 22 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, water was added, and the mixture was extracted twice with chloroform. The organic layer was washed with water and then dried over anhydrous magnesium sulfate. Next, the crude product obtained by filtration and concentration is purified by column chromatography (silica gel, chloroform / hexane = 1/1 to chloroform) to give 2,6-bis [5- (2-butyloctyl) thiophene-2. -Il] -4,8-dithiophen-2-yl-benzo [1,2-d; 4,5-d ′] bisthiazole (DTH-DBTH-BOTH) was obtained as a yellow solid (DTH-DBTH-BOTH). Yield 99%).
It was confirmed by ¹ H-NMR measurement that the target compound was produced.

¹ H NMR (400 MHz, CDCl ₃ ): δ8.00 (dd, J = 4.0, 0.8 Hz, 2H), 7.58 (dd, J = 5.2, 0.8 Hz, 2H), 7.55 (d, J = 4.0 Hz, 2H), 7.27 (dd, J = 5.2, 4.0 Hz, 2H), 6.81 (d, J =
4.0 Hz, 2H), 2.81 (m, 4H), 1.71 (m, 2H), 1.35-1.24 (m, 32H), 0.90 (t J = 6.4 Hz, 6H), 0.88 (t, J = 6.4 Hz, 12H ).

(Reference Example 9)
4,8-bis (5-bromothiophen-2-yl) -2,6-bis [5- (2-butyloctyl) thiophen-2-yl] -benzo [1,2-d; 4,5-d '] Synthesis of bisthiazole (DTH-DBTH-BOTH-DB)

2,6-bis [5- (2-butyloctyl) thiophen-2-yl] -4,8-dithiophen-2-yl-benzo [1,2-d; 4,5-d ′] bis in a 20 mL flask Thiazole (DTH-DBTH-BOTH, 200 mg, 0.23 mmol), NBS (N-bromosuccinimide, 92 mg, 0.51 mmol) and chloroform (4 mL) were added and reacted at room temperature for 19 hours. After completion of the reaction, it was washed with water (twice) and then dried over anhydrous magnesium sulfate. Next, the crude product obtained by filtration and concentration is purified by column chromatography (silica gel, toluene) to give 4,8-bis (5-bromothiophen-2-yl) -2,6-bis [5- ( 165 mg of 2-butyloctyl) thiophen-2-yl] -benzo [1,2-d; 4,5-d ′] bisthiazole (DTH-DBTH-BOTH-DB) was obtained as a yellow solid (yield) 70%).
It was confirmed by ¹ H-NMR measurement that the target compound was produced.

¹ H NMR (400 MHz, CDCl ₃ ): δ7.68 (d, J = 4.0 Hz, 2H), 7.65 (d, J = 4.0 Hz, 2H), 7.20 (d, J = 4.0 Hz, 2H), 6.82 (d, J = 4.0 Hz, 2H), 2.83 (m, 4H), 1.74 (m, 2H), 1.35-1.26 (m, 32H), 0.90 (t J = 6.4 Hz, 6H), 0.89 (t, J = 6.4 Hz, 12H).

(Reference Example 10) DBTH-DMOTH
Synthesis of 2,6-bis [5- (3,7-dimethyloctyl) thiophen-2-yl] benzo [1,2-d; 4,5-d ′] bisthiazole (DBTH-DMOTH)

In a 100 mL flask, 2,6-diiodobenzo [1,2-d; 4,5-d ′] bisthiazole (DBTH-DI, 3 g, 6.76 mmol), tributyl [5- (3,7-dimethyloctyl) thiophene- 2-yl] stannane (DMOT-Sn, 12.1 g, 22.6 mmol), tris (2-furyl) phosphine (188 mg, 0.81 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct ( 420 mg, 0.41 mmol) and N, N-dimethylformamide (60 mL) were added, and the mixture was reacted at 120 ° C. for 21 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, water was added, and the mixture was extracted twice with chloroform. The organic layer was washed with water and then dried over anhydrous magnesium sulfate. Subsequently, the crude product obtained by filtration and concentration was purified by column chromatography (silica gel, chloroform / hexane = 1/1) to obtain 2,6-bis [5- (3,7-dimethyloctyl) thiophene-2. -Il] benzo [1,2-d; 4,5-d ′] bisthiazole (DBTH-DMOTH) was obtained as a yellow solid (yield 46%).
It was confirmed by ¹ H-NMR measurement that the target compound was produced.

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.38 (s, 2H), 7.50 (d, J = 3.8 Hz, 2H), 6.84 (d, J = 3.8 Hz, 2H), 2.89 (m, 4H), 1.76 (m, 2H), 1.54 (m, 6H), 1.33 (m, 6H), 1.15 (m, 6H), 0.92 (d, J = 5.6 Hz, 6H), 0.87 (d, J = 6.4 Hz, 12H ).

(Reference Example 11) DI-DBTH-DMOTH
2,6-bis [5- (3,7-dimethyloctyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d ′] bisthiazole (DI-DBTH-DMOTH ) Synthesis

In a 50 mL flask, 2,6-bis [5- (3,7-dimethyloctyl) thiophen-2-yl] benzo [1,2-d; 4,5-d ′] bisthiazole (DBTH-DMOTH, 1.4 g) 2.12 mmol) and tetrahydrofuran (27 mL) were added, and the mixture was cooled to −40 ° C., and then lithium diisopropylamide (2M solution, 2.3 mL, 4.66 mmol) was added dropwise and stirred for 30 minutes. Then, iodine (1.6 g, 6.36 mmol) was added and reacted at room temperature for 2 hours. After completion of the reaction, 10% sodium bisulfite was added and the mixture was extracted with chloroform. The obtained organic layer was washed with saturated aqueous sodium hydrogen carbonate and then with saturated brine and dried over anhydrous magnesium sulfate. Subsequently, the crude product obtained by filtration and concentration was purified by column chromatography (silica gel, chloroform / hexane = 1/1) to obtain 2,6-bis [5- (3,7-dimethyloctyl) thiophene-2. -Il] -4,8-diiodobenzo [1,2-d; 4,5-d ′] bisthiazole (DI-DBTH-DMOTH) was obtained as a yellow solid (yield 70%).
It was confirmed by ¹ H-NMR measurement that the target compound was produced.

¹ H NMR (400 MHz, CDCl ₃ ): δ7.51 (d, J = 3.8 Hz, 2H), 6.83 (d, J = 3.8 Hz, 2H), 2.88 (m, 4H), 1.76 (m, 2H) , 1.56 (m, 6H), 1.33 (m, 6H), 1.15 (m, 6H), 0.93 (d, J =
5.6 Hz, 6H), 0.87 (d, J = 6.4 Hz, 12H).

(Reference Example 12) DBTH-TDTH
Synthesis of 2,6-bis [5- (2-decyltetradecyl) thiophen-2-yl] benzo [1,2-d; 4,5-d ′] bisthiazole (DBTH-TDTH)

In a 200 mL flask, 2,6-diiodobenzo [1,2-d; 4,5-d '] bisthiazole (DBTH-DI, 5.2 g, 11.6 mmol), tributyl [5- (2-decyltetradecyl) thiophene -2-yl] stannane (TDT-Sn, 60.8 g, 38.0 mmol), tris (2-furyl) phosphine (448 mg, 2.09 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (493 mg, 0.46 mol) and N, N-dimethylformamide (112 mL) were added and reacted at 120 ° C. for 23 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, water was added, and the mixture was extracted twice with chloroform. The organic layer was washed with water and then dried over anhydrous magnesium sulfate. Next, the crude product obtained by filtration and concentration is purified by column chromatography (silica gel, chloroform / hexane = 1/1) to give 2,6-bis [5- (2-decyltetradecyl) thiophene-2- Yl] benzo [1,2-d; 4,5-d ′] bisthiazole (DBTH-TDTH) was obtained as a pale yellow solid (yield 51%).
It was confirmed by ¹ H-NMR measurement that the target compound was produced.

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.40 (s, 2H), 7.56 (d, J = 3.6 Hz, 2H), 6.81 (d, J = 3.6 Hz, 2H), 2.80 (m, 4H), 1.69 (m, 2H), 1.35-1.20 (m, 80H), 0.87 (t, J = 6.4 Hz, 6H), 0.86 (t, J = 6.4 Hz, 6H).

(Reference Example 13) DI-DBTH-TDTH
2,6-bis [5- (2-decyltetradecyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d ′] bisthiazole (DI-DBTH-TDTH) Synthesis of

In a 200 mL flask, 2,6-bis [5- (2-decyltetradecyl) thiophen-2-yl] benzo [1,2-d; 4,5-d ′] bisthiazole (DBTH-TDTH, 4.1 g, 3.97 mmol) and tetrahydrofuran (80 mL) were added and cooled to −40 ° C., and then lithium diisopropylamide (2M solution, 4.4 mL, 8.8 mmol) was added dropwise and stirred for 30 minutes. Next, iodine (3.1 g, 24.0 mol) was added, and the mixture was reacted at room temperature for 2 hours. After completion of the reaction, 10% sodium bisulfite was added and the mixture was extracted with chloroform. The obtained organic layer was washed with saturated aqueous sodium hydrogen carbonate and then with saturated brine and dried over anhydrous magnesium sulfate. Subsequently, the crude product obtained by filtration and concentration was purified by column chromatography (silica gel, ethyl acetate / hexane = 5/95) to obtain 2,6-bis [5- (2-decyltetradecyl) thiophene-2. -Yl] -4,8-diiodobenzo [1,2-d; 4,5-d ′] bisthiazole (DI-DBTH-TDTH) was obtained as a yellow solid (yield 69%).
It was confirmed by ¹ H-NMR measurement that the target compound was produced.

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.53 (d, J = 3.6 Hz, 2H), 6.80 (d, J = 3.6 Hz, 2H), 2.80 (m, 4H), 1.70 (m, 2H), 1.38-1.20 (m, 80H), 0.89 (t, J = 6.4 Hz, 6H), 0.86 (t, J = 6.4 Hz, 6H).

(Reference Example 14) DTH-DBTH-TDTH
2,6-bis [5- (2-decyltetradecyl) thiophen-2-yl] -4,8-dithiophen-2-yl-benzo [1,2-d; 4,5-d ′] bisthiazole ( DTH-DBTH-TDTH)

In a 100 mL flask, 2,6-bis [5- (2-decyltetradecyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d ′] bisthiazole (DI-DBTH -TDTH, 2.5 g, 1.95 mmol), tributylthiophen-2-yl-stannane (1.6 mL, 4.88 mmol), tris (2-furyl) phosphine (55 mg, 0.23 mmol), tris (dibenzylideneacetone) ) Dipalladium (0) -chloroform adduct (62 mg, 0.06 mmol) and N, N-dimethylformamide (50 mL) were added and reacted at 100 ° C. for 23 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, water was added, and the mixture was extracted twice with chloroform. The organic layer was washed with water and then dried over anhydrous magnesium sulfate. Subsequently, the crude product obtained by filtration and concentration was purified by column chromatography (silica gel, ethyl acetate / hexane = 1/9) to obtain 2,6-bis [5- (2-decyltetradecyl) thiophene-2. -Il] -4,8-dithiophen-2-yl-benzo [1,2-d; 4,5-d ′] bisthiazole (DTH-DBTH-TDTH) was obtained as a yellow solid (2.21 g). Yield 95%).
It was confirmed by ¹ H-NMR measurement that the target compound was produced.
¹ H NMR (400 MHz, CDCl ₃ ): δ8.00 (dd, J = 4.0, 0.8 Hz, 2H), 7.58 (dd, J = 5.2, 0.8 Hz, 2H), 7.55 (d, J = 4.0 Hz, 2H), 7.27 (dd, J = 5.2, 4.0 Hz, 2H), 6.81 (d, J =
4.0 Hz, 2H), 2.82 (m, 4H), 1.71 (m, 2H), 1.39-1.20 (m, 80H), 0.88 (t J = 6.4 Hz, 6H), 0.87 (t, J = 6.4 Hz, 12H ).

Reference Example 15 DTH-DBTH-TDTH-DSM
2,6-bis [5- (2-decyltetradecyl) thiophen-2-yl] -4,8-bis (5-trimethylstannylthiophen-2-yl) -benzo [1,2-d; 5-d ′] bisthiazole (DTH-DBTH-TDTH-DSM)

In a 30 mL flask, 2,6-bis [5- (2-decyltetradecyl) thiophen-2-yl] -4,8-dithiophen-2-yl-benzo [1,2-d; 4,5-d ′] Bisthiazole (DTH-DBTH-TDTH, 1.5 g, 1.26 mmol) and tetrahydrofuran (50 mL) were added, cooled to −30 ° C., and lithium diisopropylamide (2M solution, 1.38 mL, 2.77 mmol) was added dropwise. Stir for 30 minutes. Thereafter, trimethyltin chloride (1M solution, 3.0 mL, 3.02 mmol) was added, and the mixture was warmed to room temperature and stirred for 2 hours. After completion of the reaction, water was added and extracted twice with toluene. The organic layer was washed with water and then dried over anhydrous magnesium sulfate. Next, the crude product obtained by filtration and concentration is purified by GPC-HPLC (JAIGEL-1H, 2H, chloroform) to give 2,6-bis [5- (2-decyltetradecyl) thiophen-2-yl]. 1.28 g of -4,8-bis (5-trimethylstannylthiophen-2-yl) -benzo [1,2-d; 4,5-d '] bisthiazole (DTH-DBTH-TDTH-DSM), Obtained as a yellow solid (67% yield). It was confirmed by ¹ H-NMR measurement that the target compound was produced.

¹ H NMR (400 MHz, CDCl ₃ ): δ8.15 (d, J = 3.6 Hz, 2H), 7.56 (d, J = 3.6 Hz, 2H), 7.35 (d, J = 3.6 Hz, 2H), 6.84 (d, J = 3.6 Hz, 2H), 2.82 (m, 4H), 1.71 (m, 2H), 1.39-1.20 (m, 80H), 0.88 (t J = 6.4 Hz, 6H), 0.86 (t, J = 6.4 Hz, 12H), 0.47 (s, 18H).

Reference Example 16 4,8-bis (5-bromothiophen-2-yl) -2,6-bis [5- (2-decyltetradecyl) thiophen-2-yl] -benzo [1,2-d Synthesis of 4,5-d ′] bisthiazole (DTH-DBTH-TDTH-DB)

In a 20 mL flask, 2,6-bis [5- (2-decyltetradecyl) thiophen-2-yl] -4,8-dithiophen-2-yl-benzo [1,2-d; 4,5-d ′] Bisthiazole (DTH-DBTH-TDTH, 300 mg, 0.25 mmol), NBS (N-bromosuccinimide, 99 mg, 0.55 mmol) and chloroform (6 mL) were added and reacted at room temperature for 19 hours. After completion of the reaction, it was washed with water (twice) and then dried over anhydrous magnesium sulfate. Next, the crude product obtained by filtration and concentration is purified by column chromatography (silica gel, toluene) to give 4,8-bis (5-bromothiophen-2-yl) -2,6-bis [5- ( 2-decyltetradecyl) thiophen-2-yl] -benzo [1,2-d; 4,5-d ′] bisthiazole (DTH-DBTH-TDTH-DB) was obtained as a yellow solid (yield). 80%).
It was confirmed by ¹ H-NMR measurement that the target compound was produced.

¹ H NMR (400 MHz, CDCl ₃ ): δ7.68 (d, J = 4.0 Hz, 2H), 7.65 (d, J = 4.0 Hz, 2H), 7.20 (d, J = 4.0 Hz, 2H), 6.82 (d, J = 4.0 Hz, 2H), 2.82 (m, 4H), 1.72 (m, 2H), 1.39-1.22 (m, 80H), 0.89 (t J = 6.4 Hz, 6H), 0.86 (t, J = 6.4 Hz, 12H).

Example 1 Synthesis of P-TDMOT-DBTH-T

In a 20 mL flask, 2,6-bis [5- (3,7-dimethyloctyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d ′] bisthiazole (DI -DBTH-DMOTH, 110 mg, 0.12 mmol), 1,1 '-(2.5-thiophenediyl) bis [1,1,1-trimethyl] stannane (52 mg, 0.12), dipalladium (0)- Chloroform adduct (4 mg, 4.8 μmol), tris (2-methylphenyl) phosphine (6 mg, 19.2 μmol) and chlorobenzene (6 mL) were added and reacted at 130 ° C. for 24 hours. After completion of the reaction, the reaction solution was added to methanol (40 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequent extraction with Soxhlet (chloroform) gave 53 mg (60%) of P-TDMOT-DBTH-T as a black solid.

Ionization potential: 5.17 eV (HOMO-5.17 eV)
GPC measurement results Mw (weight average molecular weight): 2800, Mn (number average molecular weight): 1800

Example 2 Synthesis of P-THDT-DBTH-T

To a 20 mL flask, add 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d ′] bisthiazole (DI-DBTH). -HDTH, 100 mg, 0.09 mmol), 1,1 ′-(2.5-thiophenediyl) bis [1,1,1-trimethyl] stannane (39 mg, 0.09), dipalladium (0) -chloroform addition (4 mg, 3.8 μmol), tris (2-methoxyphenyl) phosphine (5 mg, 15.1 μmol) and chlorobenzene (8 mL) were added and reacted at 130 ° C. for 24 hours. After completion of the reaction, the reaction solution was added to methanol (40 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequent extraction with Soxhlet (chloroform) gave 52 mg (62%) of P-THDT-DBTH-T as a black solid.

Ionization potential: 5.20 eV (HOMO -5.20 eV)
GPC measurement results Mw (weight average molecular weight): 4400, Mn (number average molecular weight): 3400

Production / Evaluation of Photoelectric Conversion Element Using P-THDT-DBTH-T obtained as described above as a donor material and PCBM (C61) (phenyl C61-butyric acid methyl ester) as an acceptor material, donor material: acceptor material = 1: 2 (weight) (total concentration 30 mg / mL) and 1,8-diiodooctane (0.03 mL / mL) were dissolved in chlorobenzene and passed through a 0.45 μm filter to obtain a mixed solution.
A glass substrate on which ITO is formed is subjected to surface treatment by ozone UV treatment, and then a PEDOT-PSS ([poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)) aqueous dispersion is spun. It was applied and annealed with a coater. Next, the mixed solution of the above donor material and acceptor material was formed into a film with a spin coater and dried under reduced pressure at room temperature. On top of that, an ethanol solution of tetraisopropyl orthotitanate (about 0.3 v%) was spin-coated, and a film converted into titanium oxide by moisture in the atmosphere was prepared. Then, aluminum which is an electrode was vapor-deposited to make a device.
The obtained device was subjected to characteristic evaluation using a solar simulator (CEP2000, AM1.5G filter, radiation intensity 100 mW / cm ² , manufactured by Spectrometer). As a result, it was confirmed that the conversion efficiency was 1.35% when Jsc (short-circuit current density) = 3.27 mA / cm ² , Voc (open-circuit voltage) = 0.75 V, and FF (fill factor) = 0.55.

Example 3 Synthesis of P-TBOT-DBTH-DT

In a 20 mL flask, add 2,6-bis [5- (2-butyloctyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d ′] bisthiazole (DI-DBTH). -BOTH, 100 mg, 0.11 mmol), 5,5′-bis (trimethylstannyl) -2,2′-bithiophene (52 mg, 0.11 mmol), dipalladium (0) -chloroform adduct (4 mg, 4. 2 μmol), tris (2-methoxyphenyl) phosphine (5 mg, 16.8 μmol) and chlorobenzene (8 mL) were added and reacted at 130 ° C. for 24 hours. After completion of the reaction, the reaction solution was added to methanol (40 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequent Soxhlet extraction (chloroform) gave 35 mg (39%) of P-TBOT-DBTH-DT as a black solid.

Ionization potential: 5.14 eV (HOMO-5.14 eV)

Example 4 P-THDT-DBTH-DT

To a 20 mL flask, add 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d ′] bisthiazole (DI-DBTH). -HDTH, 100 mg, 0.09 mmol), 5,5′-bis (trimethylstannyl) -2,2′-bithiophene (47 mg, 0.09), dipalladium (0) -chloroform adduct (3 mg, 3. 6 μmol), tris (2-methylphenyl) phosphine (4 mg, 14.4 μmol) and chlorobenzene (4 mL) were added and reacted at 130 ° C. for 27 hours. After completion of the reaction, the reaction solution was added to methanol (40 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequent extraction with Soxhlet (chloroform) gave 22 mg (24%) of P-THDT-DBTH-DT as a black solid.

Ionization potential: 5.36 eV (HOMO -5.36 eV)

Example 5 Synthesis of P-TODDT-DBTH-DT

In a 20 mL flask, 2,6-bis [2-octyldodecyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d ′] bisthiazole (DI-DBTH-ODDTH, 178 mg, 0.10 mmol), 5,5′-bis (trimethylstannyl) -2,2′-bithiophene (50 mg, 0.10), dipalladium (0) -chloroform adduct (4 mg, 4.0 μmol), Tris (2-methylphenyl) phosphine (5 mg, 16.0 μmol) and chlorobenzene (5 mL) were added and reacted at 130 ° C. for 24 hours. After completion of the reaction, the reaction solution was added to methanol (40 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequent Soxhlet extraction (chloroform) yielded 48 mg (44%) of P-TODDT-DBTH-DT as a black solid.

Ionization potential: 5.34 eV (HOMO -5.34 eV)
GPC measurement results Mw (weight average molecular weight): 9600, Mn (number average molecular weight): 6800

Preparation / Evaluation of Photoelectric Conversion Element Using P-TODDT-DBTH-DT obtained as described above as a donor material and PCBM (C61) (phenyl C61-butyric acid methyl ester) as an acceptor material, donor material: acceptor material = 1: 2 (weight) (total concentration 24 mg / mL) and 1,8-diiodooctane (0.03 mL / mL) were dissolved in chlorobenzene and passed through a 0.45 μm filter to obtain a mixed solution.
A glass substrate on which ITO is formed is subjected to surface treatment by ozone UV treatment, and then a PEDOT-PSS ([poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)) aqueous dispersion is spun. It was applied and annealed with a coater. Next, the mixed solution of the above donor material and acceptor material was formed into a film with a spin coater and dried under reduced pressure at room temperature. On top of that, an ethanol solution of tetraisopropyl orthotitanate (about 0.3 v%) was spin-coated, and a film converted into titanium oxide by moisture in the atmosphere was prepared. Then, aluminum which is an electrode was vapor-deposited to make a device.
The obtained device was subjected to characteristic evaluation using a solar simulator (CEP2000, AM1.5G filter, radiation intensity 100 mW / cm ² , manufactured by Spectrometer). As a result, it was confirmed that the conversion efficiency was 2.82% when Jsc (short-circuit current density) = 5.78 mA / cm ² , Voc (open-circuit voltage) = 0.80 V, FF (fill factor) = 0.61.

(Example 6) P-TTDT-DBTH-DT

In a 20 mL flask, 4,8-bis (5-bromothiophen-2-yl) -2,6-bis [5- (2-decyltetradecyl) thiophen-2-yl] -benzo [1,2-d; 4,5-d ′] bisthiazole (DTH-DBTH-TDTH-DB, 40 mg, 0.03 mmol), 2,6-bis [5- (2-decyltetradecyl) thiophen-2-yl] -4,8 -Bis (5-trimethylstannylthiophen-2-yl) -benzo [1,2-d; 4,5-d '] bisthiazole (DTH-DBTH-TDTH-DSM, 45 mg, 0.03 mmol), dipalladium Add (0) -chloroform adduct (1 mg, 1.2 μmol), tris (2-methoxyphenyl) phosphine (2 mg, 4.8 μmol) and chlorobenzene (2 mL) at It was time reaction. After completion of the reaction, the reaction solution was added to methanol (20 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequent Soxhlet extraction (chloroform) yielded 34 mg (48%) of P-TTDT-DBTH-DT as a black solid.

Ionization potential: 5.29 eV (HOMO -5.29 eV)
GPC measurement results Mw (weight average molecular weight): 12300, Mn (number average molecular weight): 8800

(Example 7) P-TBOT-DBTH-HTD

In a 20 mL flask, add 2,6-bis [5- (2-butyloctyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d ′] bisthiazole (DI-DBTH). -BOTH, 100 mg, 0.11 mmol), 3,3′-dihexyl-5,5′-bistributylstannyl [2,2 ′] bithiophenyl (97 mg, 0.11 mmol), dipalladium (0) -chloroform adduct (4 mg, 4.2 μmol), tris (2-methoxyphenyl) phosphine (5 mg, 16.8 μmol) and chlorobenzene (8 mL) were added and reacted at 130 ° C. for 24 hours. After completion of the reaction, the reaction solution was added to methanol (40 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequent Soxhlet extraction (chloroform) yielded 92 mg (86%) of P-TBOT-DBTH-HTD as a black solid.

Ionization potential: 5.25 eV (HOMO -5.25 eV)
GPC measurement results Mw (weight average molecular weight): 9100, Mn (number average molecular weight): 3800

(Example 8)
Synthesis of P-THDBOT-DBTH-DT

In a 20 mL flask, 4,8-bis (5-bromothiophen-2-yl) -2,6-bis [5- (2-butyloctyl) thiophen-2-yl] -benzo [1,2-d; , 5-d ′] bisthiazole (DTH-DBTH-BOTH-DB, 48 mg, 0.05 mmol), 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-bis (5-Trimethylstannylthiophen-2-yl) -benzo [1,2-d; 4,5-d ′] bisthiazole (DTH-DBTH-HDTH-DSM, 60 mg, 0.05 mmol), dipalladium (0 ) -Chloroform adduct (2 mg, 1.9 μmol), tris (2-methoxyphenyl) phosphine (3 mg, 7.5 μmol) and chlorobenzene (7 mL) were added, and the mixture was reacted at 130 ° C. for 24 hours. It was. After completion of the reaction, the reaction solution was added to methanol (40 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequent extraction with Soxhlet (chloroform) gave 26 mg (31%) of P-THDBOT-DBTH-DT as a black solid.

Ionization potential: 5.23 eV (HOMO -5.23 eV)
GPC measurement results Mw (weight average molecular weight): 6100, Mn (number average molecular weight): 3800

(Example 9) P-TTDHDT-DBTH-DT

In a 20 mL flask, 4,8-bis (5-bromothiophen-2-yl) -2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -benzo [1,2-d; , 5-d ′] bisthiazole (DTH-DBTH-HDTH-DB, 45 mg, 0.04 mmol), 2,6-bis [5- (2-decyltetradecyl) thiophen-2-yl] -4,8- Bis (5-trimethylstannylthiophen-2-yl) -benzo [1,2-d; 4,5-d ′] bisthiazole (DTH-DBTH-TDTH-DSM, 60 mg, 0.04 mmol), dipalladium ( 0) -chloroform adduct (3 mg, 1.6 μmol), tris (2-methoxyphenyl) phosphine (3 mg, 6.4 μmol) and chlorobenzene (3 mL) were added, and the mixture was stirred at 130 ° C. for 24 hours. I reacted. After completion of the reaction, the reaction mixture was added to methanol (30 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequent Soxhlet extraction (chloroform) yielded 22 mg (26%) of P-TTDHDT-DBTH-DT as a black solid.

Ionization potential: 5.36 eV (HOMO -5.36 eV)
GPC measurement results Mw (weight average molecular weight): 6300, Mn (number average molecular weight): 4900

Production / Evaluation of Photoelectric Conversion Element Using P-TTDHDT-DBTH-DT obtained as described above as a donor material and PCBM (C61) (phenyl C61-butyric acid methyl ester) as an acceptor material, donor material: acceptor material = 1: 2 (weight) (total concentration 24 mg / mL) and 1,8-diiodooctane (0.03 mL / mL) were dissolved in chlorobenzene and passed through a 0.45 μm filter to obtain a mixed solution.
A glass substrate on which ITO is formed is subjected to surface treatment by ozone UV treatment, and then a PEDOT-PSS ([poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)) aqueous dispersion is spun. It was applied and annealed with a coater. Next, the mixed solution of the above donor material and acceptor material was formed into a film with a spin coater and dried under reduced pressure at room temperature. On top of that, an ethanol solution of tetraisopropyl orthotitanate (about 0.3 v%) was spin-coated, and a film converted into titanium oxide by moisture in the atmosphere was prepared. Then, aluminum which is an electrode was vapor-deposited to make a device.
The obtained device was subjected to characteristic evaluation using a solar simulator (CEP2000, AM1.5G filter, radiation intensity 100 mW / cm ² , manufactured by Spectrometer). As a result, it was confirmed that Jsc (short-circuit current density) = 4.24 mA / cm ² , Voc (open-circuit voltage) = 0.79 V, FF (fill factor) = 1.94, and a conversion efficiency of 0.77%.

(Example 10) P-TTDT-DBTH-TT

In a 20 mL flask, 4,8-bis (5-bromothiophen-2-yl) -2,6-bis [5- (2-decyltetradecyl) thiophen-2-yl] -benzo [1,2-d; 4,5-d ′] bisthiazole (DTH-DBTH-TDTH-DB, 100 mg, 0.09 mmol), 1,1 ′-(2.5-thiophendiyl) bis [1,1,1-trimethyl] stannane ( 36 mg, 0.09 mmol), dipalladium (0) -chloroform adduct (3 mg, 3.6 μmol), tris (2-methylphenyl) phosphine (3 mg, 14.4 μmol) and chlorobenzene (5 mL) were added, and the mixture was added at 130 ° C. Reacted for hours. After completion of the reaction, the reaction solution was added to methanol (40 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequent Soxhlet extraction (chloroform) gave 94 mg (83%) of P-TTDT-DBTH-TT as a black solid.
Ionization potential: 5.21 eV (HOMO -5.21 eV)
GPC measurement results Mw (weight average molecular weight): 27200, Mn (number average molecular weight): 13000

Production / Evaluation of Photoelectric Conversion Element Using P-TTDT-DBTH-TT obtained as described above as a donor material and PCBM (C61) (phenyl C61-butyric acid methyl ester) as an acceptor material, donor material: acceptor material = 1: 2 (weight) (total concentration 24 mg / mL) and 1,8-diiodooctane (0.03 mL / mL) were dissolved in chlorobenzene and passed through a 0.45 μm filter to obtain a mixed solution.
A glass substrate on which ITO is formed is subjected to surface treatment by ozone UV treatment, and then a PEDOT-PSS ([poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)) aqueous dispersion is spun. It was applied and annealed with a coater. Next, the mixed solution of the above donor material and acceptor material was formed into a film with a spin coater and dried under reduced pressure at room temperature. On top of that, an ethanol solution of tetraisopropyl orthotitanate (about 0.3 v%) was spin-coated, and a film converted into titanium oxide by moisture in the atmosphere was prepared. Then, aluminum which is an electrode was vapor-deposited to make a device.
The obtained device was subjected to characteristic evaluation using a solar simulator (CEP2000, AM1.5G filter, radiation intensity 100 mW / cm ² , manufactured by Spectrometer). As a result, Jsc (short-circuit current density) = 7.25 mA / cm ² , Voc (open-circuit voltage) = 0.68 V, FF (curve factor) = 0.62, and a conversion efficiency of 3.06% was confirmed.

Since the polymer compound of the present invention has high photoelectric conversion efficiency, it is useful for organic electro devices such as organic electroluminescence elements and organic thin film transistor elements.

Claims (12)

1. A polymer compound comprising a repeating unit having a benzobisthiazole structure represented by the following formula (1) and a repeating unit having a thiophene structure represented by the following formula (2).
   

   

   
   [In formula (1), T ¹ and T ² are each independently a thiophene ring, hydrocarbon group, or organosilyl optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group. Represents a thiazole ring which may be substituted with a group, or a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom or a trifluoromethyl group. ]
   

   

   
   [In Formula (2), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. ]
2. The polymer compound according to claim 1, comprising a repeating unit represented by the following formula (3).
   

   

   
   [In Formula (3), T ¹ , T ² and R ¹ each represent the same group as described above, and p represents an integer of 1 to 10. ]
3. The polymer compound according to claim 1, comprising a repeating unit represented by the following formula (6).
   

   

   
   [In Formula (1), T ¹ , T ² , T ³ , T ⁴ are each independently a thiophene ring, carbonized, which may be substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group. A hydrogen group or a thiazole ring which may be substituted with an organosilyl group, or a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom or a trifluoromethyl group; To express.
   R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
   T ¹ , T ² , T ³ , and T ⁴ are all the same, and R ¹ , R ² , R ³ , and R ⁴ are not all the same. ]
4. The polymer compound according to claim 1 or 2, wherein T ¹ and T ² are each a group represented by any of the following formulas (t1) to (t5).
   

   

   
   [In the formulas (t1) to (t5),
   R ²¹ to R ²² each independently represents a hydrocarbon group having 6 to 30 carbon atoms.
   R ²³ to R ²⁴ each independently represents a hydrocarbon group having 6 to 30 carbon atoms or a group represented by **-Si (R ²⁶ ) ₃ .
   R ²⁵ each independently represents a hydrocarbon group having 6 to 30 carbon atoms, ** — O—R ²⁷ , ** — S—R ²⁸ , ** — Si (R ²⁶ ) ₃ , a halogen atom, or **. It represents a -CF _3.
   R ²⁶ each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the plurality of R ²⁶ may be the same or different.
   R ²⁷ to R ²⁸ each represents a hydrocarbon group having 6 to 30 carbon atoms.
   * Represents a bond bonded to the thiazole ring of benzobisthiazole. ** represents a bond that binds to (t3) to (t5). ]
5. ^4. The polymer compound according to claim 3, wherein T ¹ , T ² , T ³ , and T ⁴ are each a group represented by any of the following formulas (t1) to (t5).
   

   

   
   [In the formulas (t1) to (t5),
   R ²¹ to R ²² each independently represents a hydrocarbon group having 6 to 30 carbon atoms.
   R ²³ to R ²⁴ each independently represents a hydrocarbon group having 6 to 30 carbon atoms or a group represented by **-Si (R ²⁶ ) ₃ .
   R ²⁵ each independently represents a hydrocarbon group having 6 to 30 carbon atoms, ** — O—R ²⁷ , ** — S—R ²⁸ , ** — Si (R ²⁶ ) ₃ , a halogen atom, or **. It represents a -CF _3.
   R ²⁶ each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the plurality of R ²⁶ may be the same or different.
   R ²⁷ to R ²⁸ each represents a hydrocarbon group having 6 to 30 carbon atoms.
   * Represents a bond bonded to the thiazole ring of benzobisthiazole. ** represents a bond that binds to (t3) to (t5). ]
6. An organic semiconductor material comprising the polymer compound according to any one of claims 1 to 5.
7. The organic semiconductor material according to claim 6, wherein the organic semiconductor material is a p-type semiconductor or an n-type semiconductor.
8. An organic electronic device comprising the organic semiconductor material according to claim 7.
9. The organic electronic device according to claim 8, wherein the organic electronic device is a photoelectric conversion element or a solar battery.
10. A dihalogenobenzobisthiazole compound represented by the following formula (4);
    

    

    
    [In Formula (4), T ¹ and T ² are each independently a thiophene ring, hydrocarbon group, or organosilyl optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group. Represents a thiazole ring which may be substituted with a group, or a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom or a trifluoromethyl group. X ¹ and X ² represent a halogen atom. ]
    A thiophene compound represented by the following formula (5):
    

    

    
    [In Formula (5), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. p represents an integer of 1 to 10.
    R ¹⁰ to R ¹³ each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.
    M ¹ and M ² each independently represent a boron atom or a tin atom. R ¹⁰ and R ¹¹ may form a ring with M ¹ , and R ¹² and R ¹³ may form a ring with M ² .
    m and n each represents an integer of 1 or 2. When m and n are 2, the plurality of R ¹⁰ and R ¹² may be the same or different. ]
    A method for producing a polymer compound represented by formula (3), wherein a cross-coupling reaction is performed.
    

    

    
    [In Formula (3), T ¹ , T ² and R ¹ each represent the same group as described above, and p represents the same integer as described above. ]
11. A dihalogenobenzobisthiazole compound represented by the following formula (7);
    

    

    
    [In Formula (7), T ¹ and T ² are each independently a thiophene ring, hydrocarbon group, or organosilyl optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group. Represents a thiazole ring which may be substituted with a group, or a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom or a trifluoromethyl group.
    R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
    X ¹ and X ² represent a halogen atom. ]
    A benzobisthiazole compound represented by the following formula (8):
    

    

    
    [In formula (8), T ³ and T ⁴ are each independently a thiophene ring, hydrocarbon group, or organosilyl optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group. Represents a thiazole ring which may be substituted with a group, or a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom or a trifluoromethyl group.
    R ³ and R ⁴ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
    R ¹⁰ to R ¹³ each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.
    M ¹ and M ² each independently represent a boron atom or a tin atom. R ¹⁰ and R ¹¹ may form a ring with M ¹ , and R ¹² and R ¹³ may form a ring with M ² .
    m and n each represents an integer of 1 or 2. When m and n are 2, the plurality of R ¹⁰ and R ¹² may be the same or different. ]
    A method for producing a polymer compound represented by formula (6), wherein a cross-coupling reaction is performed.
    

    

    
    [In Formula (6), T ¹ , T ² , T ³ , T ⁴ , R ¹ , R ² , R ³ , R ⁴ each represents the same group as described above. ]
12. A dihalogenobenzobisthiazole compound represented by the following formula (7);
    

    

    
    [In Formula (7), T ¹ and T ² are each independently a thiophene ring, hydrocarbon group, or organosilyl optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group. Represents a thiazole ring which may be substituted with a group, or a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom or a trifluoromethyl group.
    R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
    X ¹ and X ² represent a halogen atom. ]
    A thiophene compound represented by the following formula (5):
    

    

    
    [In Formula (5), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. p represents an integer of 1 to 10.
    R ¹⁰ to R ¹³ each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.
    M ¹ and M ² each independently represent a boron atom or a tin atom. R ¹⁰ and R ¹¹ may form a ring with M ¹ , and R ¹² and R ¹³ may form a ring with M ² .
    m and n each represents an integer of 1 or 2. When m and n are 2, the plurality of R ¹⁰ and R ¹² may be the same or different. ]
    A method for producing a polymer compound represented by formula (3), wherein a cross-coupling reaction is performed.
    

    

    
    [In Formula (3), T ¹ , T ² and R ¹ each represent the same group as described above, and p represents the same integer as described above. ]

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