JP6688453B2 - Organic semiconductor material - Google Patents

Description

  The present invention relates to a compound having a specific benzobisthiazole skeleton and a method for producing the same.

  The organic semiconductor material is one of the most important materials in the field of organic electronics, and can be classified into an electron-donating p-type organic semiconductor material and an electron-accepting n-type organic semiconductor material. Various devices can be manufactured by appropriately combining p-type organic semiconductor materials and n-type organic semiconductor materials, and such devices include, for example, 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 the amount of voltage, and the like.

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

  Since the open circuit voltage (Voc) is proportional to the energy difference between the HOMO (highest occupied molecular orbital) level of the p-type organic semiconductor and the LUMO (lowest unoccupied molecular orbital) level of the n-type organic semiconductor, the open circuit voltage (Voc) is ), It is necessary to deepen (lower) the HOMO level of the p-type organic semiconductor.

The short-circuit current density (Jsc) correlates with the amount of energy received by the organic semiconductor material, and in order to improve the short-circuit current density (Jsc) of the organic semiconductor material, the visible region to the near-infrared region is increased. 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 light with the lowest energy (longest wavelength) is the absorption edge wavelength, and the energy corresponding to this wavelength corresponds to the bandgap 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).
Although a compound having a benzobisthiazole skeleton as a repeating unit has been proposed as one of such organic semiconductor materials (Patent Document 1), performance as an organic semiconductor material such as photoelectric conversion efficiency is not specified.

Patent Document 1: Japanese Patent Laid-Open No. 2007-238530

  An object of the present invention is to provide an organic semiconductor material having excellent conversion efficiency. In addition, since the chemical structure and the conversion efficiency of organic semiconductor materials are closely related to each other, it is also an object of the present invention to provide a raw material compound into which more diverse skeletons and substituents can be introduced. Further, it is to provide a method for producing such an organic semiconductor material or a raw material compound thereof.

  In order to improve the conversion efficiency, that is, the open-circuit voltage (Voc) and the short-circuit current density (Jsc), the p-type organic semiconductor absorbs light in a wide wavelength range and at the same time, HOMO. It was found that it is useful to make the level moderately deep. Then, as a result of intensive investigations focusing on 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, it has a wide light absorption in the entire visible light region. At the same time, it was found that the HOMO level and the LUMO level can be adjusted within an appropriate range, so that the short circuit current density (Jsc) can be improved while improving the open circuit voltage (Voc). Then, the inventors have found that the use of such an organic semiconductor polymer facilitates charge separation between a p-type organic semiconductor and an n-type organic semiconductor, and completed the present invention.

That is, the polymer compound according to the present invention is characterized by containing 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 an thiophene ring optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group, a hydrocarbon group, or an organosilyl group. It 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 the 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 contains 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. ]

Further, the polymer compound according to the present invention preferably contains a repeating unit represented by the following formula (6).

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

Further, 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). It is preferable.

[In formulas (t1) to (t5),
R ^{21 to} R ²² each independently represent a hydrocarbon group having 6 to 30 carbon atoms.
R ^{23 to} R ²⁴ each independently represent a hydrocarbon group having 6 to 30 carbon atoms or a group represented by **-Si (R ²⁶ ) ₃ .
R ²⁵ is independently 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's each independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and a plurality of R ^26's may be the same or different.
R ^{27 to} R ²⁸ represent a hydrocarbon group having 6 to 30 carbon atoms.
* Represents a bond that bonds to the thiazole ring of benzobisthiazole. ** represents a bond that bonds to (t3) to (t5). ]

  It is also within the technical scope of the present invention that the 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, it is within the technical scope of the present invention that the organic electronic device containing the organic semiconductor material and the organic electronic device being 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 the 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 the formula (5), R ¹ represents a group similar to the above, and p represents an integer similar to the above.
R ^{10 to} R ¹³ each independently represent 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 together with M ¹ , and R ¹² and R ¹³ may form a ring together with M ² .
m and n each represent an integer of 1 or 2. Further, when m and n are 2, a plurality of R ¹⁰ and R ¹² may be the same or different. ]
A method for producing a polymer compound represented by formula (3), which comprises a cross-coupling reaction.

[In the formula (3), T ¹ , T ² , and R ¹ each represent the same group as described above, and p represents an integer similar to the 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 an thiophene ring optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group, a hydrocarbon group, or an organosilyl group. It 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 represent 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 the formula (8), T ³ and T ⁴ are each independently an thiophene ring optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group, a hydrocarbon group, or an organosilyl group. It 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 represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
R ^{10 to} R ¹³ each independently represent 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 together with M ¹ , and R ¹² and R ¹³ may form a ring together with M ² .
m and n each represent an integer of 1 or 2. Further, when m and n are 2, a plurality of R ¹⁰ and R ¹² may be the same or different. ]
A method for producing a polymer compound represented by formula (6), which comprises a cross-coupling reaction.

[In the formula (6), T ¹ , T ² , T ³ , T ⁴ , R ¹ , R ² , R ³ , and R ⁴ each represent 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 an thiophene ring optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group, a hydrocarbon group, or an organosilyl group. It 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 represent 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 the 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 represent 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 together with M ¹ , and R ¹² and R ¹³ may form a ring together with M ² .
m and n each represent an integer of 1 or 2. Further, when m and n are 2, a plurality of R ¹⁰ and R ¹² may be the same or different. ]
A method for producing a polymer compound represented by formula (3), which comprises a cross-coupling reaction.

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

The benzobisthiazole compound of the present invention can form a plane cruciform skeleton by intramolecular S-N interaction. As a result, the π-conjugation is extended to the planar cruciform skeleton, so that the multi-band light absorption derived from a plurality of π-π ^* transitions is exhibited, and the light absorption is wide in the entire visible light region. Furthermore, the high planarity of the planar cruciform skeleton makes it possible to achieve high charge transport properties. Therefore, it is useful as an organic semiconductor material, particularly as a solar cell material. Further, according to the production method of the present invention, it is possible to obtain a benzobisthiazole compound into which various skeletons and substituents are introduced.

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

  Embodiments of the present invention will be described in detail below. The description of the constituent elements described below is an example of the embodiment of the present invention, and the present invention is not limited to these contents unless the gist thereof is exceeded.

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 an thiophene ring optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon, or an organosilyl group, a hydrocarbon group, or an organosilyl group. Represents a thiazole ring optionally substituted with or a phenyl group optionally substituted with a hydrocarbon, an alkoxy group or a thioalkoxy group. ]

[In the 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 the benzobisthiazole structural unit represented by the formula (1) and the thiazole structural unit represented by the formula (2), it has a high planar structure due to intramolecular SN interaction. Then, as a result of the π-conjugated system extending through the cross-shaped skeleton and exhibiting multi-band light absorption characteristics derived from a plurality of π-π ^* transitions, it has wide absorption in the entire visible light region. Further, the band gap can be narrowed while the HOMO level is deepened, which is advantageous for 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 the formula (1), T ¹ , T ² , T ³ , and T ⁴ are each independently an thiophene ring optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group, or a carbon atom. A hydrogen group, or a thiazole ring which may be substituted with an organosilyl group, or a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a phenyl group which may be substituted with a halogen atom or a trifluoromethyl group, Represent
R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
T ¹ , T ² , T ³ , and T ⁴ are not 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 the formulas (1) and (3), T ¹ and T ² may be the same or different from each other, but from the viewpoint of easy production, they are the same. 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, but at least one of them is different. It is preferable. 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 units represented by the formulas (1) and (3), and T ¹ , T ² , T ³ and T in the benzobisthiazole structural units represented by the formula (6). ⁴ is preferably a group represented by each of 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). The thiophene ring which may be substituted with a hydrocarbon group or an organosilyl group is preferably a group represented by the following formula (t3), and thiazole which may be substituted with a hydrocarbon group or an organosilyl group. The ring is preferably a group represented by the following formula (t4), and as 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. 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), light having a short wavelength can be absorbed, and high planarity can be obtained. Since π-π stacking is formed, the photoelectric conversion efficiency can be further increased.

[In formulas (t1) to (t5),
R ^{21 to} R ²² each independently represent a hydrocarbon group having 6 to 30 carbon atoms.
R ^{23 to} R ²⁴ each independently represent a hydrocarbon group having 6 to 30 carbon atoms or a group represented by **-Si (R ²⁶ ) ₃ .
R ²⁵ is independently a hydrocarbon group having 6 to 30 carbon atoms, **-O-R ²⁷ , **-S-R ²⁸ , **-Si (R ²⁶ ) ₃ , a halogen atom, or *. * represents a -CF _3.
R ^26's each independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and a plurality of R ^26's may be the same or different.
R ^{27 to} R ²⁸ represent a hydrocarbon group having 6 to 30 carbon atoms.
* Represents a bond that bonds to the thiazole ring of benzobisthiazole. ** represents a bond that bonds 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, and more preferably It is a branched chain saturated hydrocarbon group. The hydrocarbon groups of R ^{21 to} R ²⁵ and R ^{27 to} R ²⁸ have branching, whereby 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 the organic solvent can be improved, but if it is too large, the reactivity in the coupling reaction described below decreases. Therefore, it becomes difficult to synthesize a polymer compound. 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 further 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 n-hexyl group, n-heptyl group, and n-octyl group, 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, C4-C8 alkyl group such as 4,4-trimethylpentyl group and 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, 2,3,3,4-tetramethylpentyl group, 3,5,5- C9 alkyl group 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 an ethyloctyl group, a 2-ethyloctyl group, a 1-methylnonyl group, a 2-methylnonyl group, and a 3,7-dimethyloctyl group; an n-undecyl group, a 1-n-butylheptyl group, 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-propylnoyl group Alkyl group having 12 carbon atoms, such as a vinyl group; n-tridecyl group, 1-n-pentyloctyl group, 2-n-pentyloctyl group, 1-n-butylnonyl group, 2-n-butylnonyl group, 1-methyldodecyl group Group, 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 group C14 alkyl group such as nonyl group and 2-n-pentylnonyl group; carbon such as n-pentadecyl group, 1-n-heptyloctyl group, 1-n-hexylnonyl group and 2-n-hexylnonyl group Alkyl group of formula 15; carbon such as n-hexadecyl group, 2-n-hexyldecyl group, 1-n-octyloctyl group, 1-n-heptylnonyl group, 2-n-heptylnonyl group 16 alkyl groups; C17 alkyl groups such as n-heptadecyl group and 1-n-octylnonyl group; C18 alkyl groups such as n-octadecyl group and 1-n-nonylnonyl group; n-nonadecyl group An alkyl group having 19 carbon atoms such as; an alkyl group having 20 carbon atoms such as an n-eicosyl group and a 2-n-octyldodecyl group; an alkyl group having 21 carbon atoms such as an n-heneicosyl group; Examples include an alkyl group having a number of 22; an alkyl group having a carbon number of 23 such as an n-tricosyl group; an alkyl group having a carbon number of 24 such as an n-tetracosyl group and a 2-n-decyltetradecyl group; It is preferably an alkyl group having 8 to 28 carbon atoms, more preferably an alkyl group having 8 to 26 carbon atoms, further preferably a branched chain alkyl group having 8 to 24 carbon atoms, particularly preferably 2-ethylhexyl. Group, 3,7-dimethyloctyl group, 2-n-butyloctyl group, 2-n-hexyldecyl group, 2-n-octyldodecyl group, 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 appropriate crystallinity.

The formula (t1) in ~ ^(t5), ** of R 23 ^{to R 25} - In Si group represented by ^{(R 26) _3,} the number of carbon atoms of the aliphatic hydrocarbon group ^{R 26} is preferably 1 to It is 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 aromatic hydrocarbon group of R ²⁶ preferably has 6 to 8 carbon atoms, more preferably 6 to 7 carbon atoms, and particularly preferably 6 carbon atoms. 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. A plurality of R ^{26 s} may be the same or different, but are preferably the same. R ²³ to R ²⁵ is ** - a group represented by Si ^{(R 26)} _3, the polymer compound of the present invention improves the solubility in organic solvents.

In the above formulas (t1) to (t5), the groups represented by **-Si (R ²⁶ ) ₃ of R ^{23 to} R ²⁵ are, specifically, trimethylsilyl group, ethyldimethylsilyl group, isopropyldimethylsilyl group. Group, triisopropylsilyl group, tert-butyldimethylsilyl group, triethylsilyl group, triisobutylsilyl group, tripropylsilyl group, tributylsilyl group, dimethylphenylsilyl group, alkyldisilyl group such as methyldiphenylsilyl group; triphenylsilyl Group, an arylsilyl group such as a tert-butylchlorodiphenylsilyl group; and the like. Of these, an alkylsilyl group is preferable, and a trimethylsilyl group and a triisopropylsilyl group are particularly preferable.

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

Further, 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.

Further, 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 more the organic solvent is added. Although it is possible to improve the solubility, if it becomes too large, the reactivity in the coupling reaction described below decreases, making it difficult to synthesize a polymer compound. Therefore, the number of carbon atoms of the hydrocarbon group represented by R ¹ , R ² , R ³ , and R ⁴ is preferably 1 to 30, more preferably 1 to 16, and further preferably 1 to 8.

Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ¹ , R ² , R ³ , and R ⁴ include, for example, 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; an alkyl group having 6 carbon atoms such as n-hexyl group Alkyl group; C7 alkyl group 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 An alkyl group 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, C3 alkyl group 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 Group, carbon such as 2-n-butylhexyl group, 1-n-propylheptyl group, 1-ethyloctyl group, 2-ethyloctyl group, 1-methylnonyl group, 2-methylnonyl group, 3,7-dimethyloctyl group Number 10 alkyl group; n-undecyl group, 1-n-butylheptyl group, 2-n-butylheptyl group, 1-n-propyloctyl group, 2-n-propyloctyl group, 1- C11 alkyl group such as tylnonyl group and 2-ethylnonyl group; n-dodecyl group, 1-n-pentylheptyl group, 2-n-pentylheptyl group, 1-n-butyloctyl group, 2-n-butyl C12 alkyl group such as octyl group, 1-n-propylnonyl group, 2-n-propylnonyl group; n-tridecyl group, 1-n-pentyloctyl group, 2-n-pentyloctyl group, 1- C13 alkyl group 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 group C14 alkyl group such as octyl group, 2-n-hexyloctyl group, 1-n-pentylnonyl group, 2-n-pentylnonyl group; n-pentadecyl group, 1-n- An alkyl group having 15 carbon atoms such as a pentyloctyl group, a 1-n-hexylnonyl group and a 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, 1-n An alkyl group having 18 carbon atoms such as nonyl nonyl 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 a carbon number of 21, such as an n-docosyl group; an alkyl group having a carbon number of 22 such as an n-docosyl group; an alkyl group having a carbon number of 23, such as an n-tricosyl group; an n-tetracosyl group, 2-n An alkyl group having 24 carbon atoms such as a decyltetradecyl group; and the like. It is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 16 carbon atoms, further preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably a methyl group, an ethyl group, and n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group. Alternatively, 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.

  In addition, 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.

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

Further, 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.


[In formula, R < ¹ > represents group similar to the 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, and more preferably 3,000 or more and 200,000 or less. The weight average molecular weight and the number average molecular weight of the polymer compound of the present invention can be calculated using gel permeation chromatography based on a calibration curve prepared using polystyrene as a standard sample.

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

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

[In the formula (3), T ¹ , T ² , and R ¹ each represent the same group as described above, and p represents an integer similar to the 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 be produced by a cross coupling reaction with a thiophene compound represented by the 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. ]

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

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

[In the formula (7), T ¹ , T ² , R ¹ , R ² , X ¹ and X ² each represent the same group as described above. ]
It can be produced by a cross coupling reaction with a benzobisthiazole compound represented by the following formula (8).

Wherein (8) ^represents the ^{T 3, T 4, R 3} , R 4, R 13, R 14, R 15, R 16, M 1, M 2 are each the same groups. ]

  Further, the polymer compound represented by the formula (3) of the present invention comprises a cross-coupling of 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 these can be used, but bromine and iodine are particularly preferable from the viewpoint of the 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 the known 2,6-diiodobenzo [1,2-d; 4,5-d '] bisthiazole (DBTH-DI) as shown in the following reaction formula.

In formula (2), formula (3), formula (5) to formula (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, 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. Alternatively, a hydrogen atom is preferable.

The compound (7) is preferably used as an intermediate compound of the polymer compounds represented by the formulas (3) and (6) of the present invention. Since this compound (7) has the above-mentioned predetermined group, it has high stability over time and can react efficiently to form the polymer compound of the present invention. Examples of compound (7) include compounds represented by the following formulas. Further, in the formulas (7-1) to (7-6), compounds in which bromine is replaced with iodine can be preferably exemplified as the compound (7).

In formulas (5) and (8), the number of carbon atoms of the aliphatic hydrocarbon group represented by R ^{10 to} R ¹³ is preferably 1 to 5, 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 alkoxy group of R ^{10 to} R ¹³ preferably has 1 to 3 carbon atoms, and more preferably 1 to 2 carbon atoms. The alkoxy group for R ^{10 to} R ¹³ is preferably a methoxy group, an ethoxy group, a propoxy group or the like, more preferably a methoxy group or an ethoxy group. The aryloxy group of R ^{10 to} R ¹³ preferably has 6 to 9 carbon atoms, and more preferably 6 to 8 carbon atoms. Examples of the aryloxy group of R ^{10 to} R ¹³ include a phenyloxy group, a benzyloxy group, a phenylenebis (methyleneoxy) group and the like. R ^{10 to} R ¹³ may be the same or different.

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, and m, And n is preferably 1. Examples of ***-M ¹ (R ¹⁰ ) _m R ¹¹ and ***-M ² (R ¹² ) _n R ¹³ in the case where M ¹ and M ² are boron atoms are represented by the following formulas, for example. Group. However, *** represents a bond with the thiophene ring.

When M ¹ and M ² are tin atoms, R ^{10 to} R ¹³ are preferably aliphatic hydrocarbon groups having 1 to 6 carbon atoms, and m and n are preferably 2. Examples of ***-M ¹ (R ¹⁰ ) _m R ¹¹ and ***-M ² (R ¹² ) _n R ¹³ in the case where M ¹ and M ² are tin atoms are represented by the following formulas. Group. However, *** represents a bond with a thiophene ring or a thiazole ring.

  The compound (5) is an intermediate compound used in the synthesis of the polymer compound of the present invention. Since this compound (5) has the above-mentioned predetermined group, it has high stability over time and can react efficiently to form the polymer compound of the present invention. Examples of compound (5) include compounds represented by the following formulas. Further, in the formulas (5-1) to (5-10), compounds in which a methyl group on a tin atom is substituted with a butyl group can also be preferably exemplified as the compound (5).

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

  The compound (8) is preferably used as an intermediate compound used in 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 stability over time and can react efficiently to form the polymer compound of the present invention. Examples of compound (8) include compounds represented by the following formulas. Further, in the formulas (8-1) to (8-6), compounds in which a methyl group on a tin atom is replaced 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; 4 , 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; 4, respectively. 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: It is about 0.8 to 1:10 and not particularly limited, but from the viewpoint of yield and reaction efficiency, 1: 0.8 to 1: 8 is preferable, 1: 0.9 to 1: 6 is more preferable, and 1: 1 to 1: 5 is more preferable.

  In the production of the polymer compound represented by the formula (3), when 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 palladium-based catalysts, nickel-based catalysts, iron-based catalysts, copper-based catalysts, rhodium-based catalysts, and ruthenium-based catalysts. Of these, a palladium-based catalyst is preferable. The valence of palladium is not particularly limited, and may be zero or divalent.

  Metal catalyst used when reacting the dihalogenobenzobisthiazole compound represented by formula (7) with 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-based catalysts, nickel-based catalysts, iron-based catalysts, copper-based catalysts, rhodium-based catalysts and ruthenium-based catalysts. Of these, a palladium-based catalyst is preferable. 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, and 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- Su (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) imidazole-2-ylidene ] (3-Chloropyridyl) paradiu (II), bis (tri-tert-butylphosphine) palladium (0), dichloro [2,5-norbornadiene] palladium (II), dichlorobis (ethylenediamine) palladium (II), dichloro (1,5-cyclooctadiene). Examples thereof include palladium (II) and dichlorobis (methyldiphenylphosphine) palladium (II). These catalysts may be used alone or in combination of two or more. Of these, dichlorobis (triphenylphosphine) palladium (II), tris (dibenzylideneacetone) dipalladium (0) and tris (dibenzylideneacetone) dipalladium (0) chloroform adducts are particularly preferable.

  In the production of the polymer compound represented by the formula (3), the molar ratio of the dihalogenobenzobisthiazole compound represented by the formula (4) or (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, and 1: 0. 005 to 1: 0.3 is more preferable, and 1: 0.01 to 1: 0.2 is further preferable.

  In the production of the polymer compound represented by the formula (6), the molar ratio of the dihalogenobenzobisthiazole compound represented by the formula (7) to the metal catalyst (dihalogenobenzobisthiazole compound: metal catalyst) is generally Although it is about 1: 0.0001 to 1: 0.5 and 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. 0.3 is more preferable, and 1: 0.01 to 1: 0.2 is still more preferable.

  In the production of the polymer compound represented by formula (3) or formula (6), a specific ligand may be coordinated with a metal catalyst such as a palladium catalyst. Examples of the ligand include trimethylphosphine, triethylphosphine, tri (n-butyl) phosphine, tri (isopropyl) phosphine, tri (tert-butyl) phosphine, tri-tert-butylphosphonium tetrafluoroborate, and 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 (diphenylphos) Ino) 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-dimethyldihydroimidazolylidene, diethyldihydroimidazolylidene, 1,3-bis (2,4,6-trimethylphenyl) dihydroimidazolylidene, 1,3-bis (2,6-diisopropylphenyl) Dihydroimidazolylidene, 1,10-phenanthroline, 5,6-dimethyl- Examples include 1,10-phenanthroline and butophenanthroline. As the ligand, only one kind may be used, or two or more kinds may be used. Among these, triphenylphosphine, tris (o-tolyl) phosphine and tris (2-methoxyphenyl) phosphine are particularly preferable.

  In the production of the polymer compound represented by formula (3) or formula (6), when the ligand is coordinated to the metal catalyst, the molar ratio of the metal catalyst and the ligand (metal catalyst: ligand) Is generally about 1: 0.5 to 1:10 and is not particularly limited, but from the viewpoint of yield and reaction efficiency, 1: 1 to 1: 8 is preferable, 1: 1 to 1: 7 is more preferable, and 1 is : 1 to 1: 5 are 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 represented by the formula (5) in the presence of a metal catalyst. A base may coexist when the thiophene compound is reacted. Further, in the production of the polymer compound represented by the formula (6), the benzobisthiazole represented by the formula (8) is added to the dihalogenobenzobisthiazole compound represented by the formula (7) 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 allow a base to coexist, and when M ¹ and M ² are tin atoms, a base does not have to coexist.

  As the base, alkali metal salt compounds such as lithium hydride, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate; 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, Alkoxy alkali metal compounds such as potassium tert- amyl alkoxide; lithium hydride, sodium hydride, metal hydride compounds such as potassium hydride. Among them, the alkali alkali metal compound is preferable as the base, 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 the formula (3), the molar ratio of the dihalogenobenzobisthiazole compound represented by the formula (4) or (7) to the base (dihalogenobenzobisthiazole compound: base) Is generally about 1: 1 to 1:10 and is not particularly limited, but from the viewpoint of yield and reaction efficiency, 1: 1.5 to 1: 8 is preferable, and 1: 1.8 to 1: 6 is more preferable. , 1: 2 to 1: 5 are more preferable.

  In the production of the polymer compound represented by the formula (6), the molar ratio of the dihalogenobenzobisthiazole compound represented by the formula (7) to the base (dihalogenobenzobisthiazole compound: base) is generally 1: It is about 1 to 1:10 and is not particularly limited, but from the viewpoint of yield and reaction efficiency, 1: 1.5 to 1: 8 is preferable, 1: 1.8 to 1: 6 is more preferable, and 1: 2 to 2. 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 represented by the 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, an ether solvent, an aromatic solvent, an ester solvent, a hydrocarbon solvent, a halogen solvent, a 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-based 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. Further, 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. As the solvent to be reacted, the above solvent can be used.

  The amount of the solvent used in the production of the polymer compound represented by the formula (3) is generally 1 mL or more with respect to 1 g of the dihalogenobenzobisthiazole compound represented by the formula (4) or the formula (7). Although it is about 150 mL or less and not particularly limited, from the viewpoint of yield and 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, and 10 mL or more and 80 mL or less are further preferable.

  The amount of the solvent used in the production of the polymer compound represented by the formula (6) is the sum of the dihalogenobenzobisthiazole compound represented by the formula (7) and the benzobisthiazole compound represented by the formula (8). It is generally 1 mL or more and 150 mL or less per 1 g and is not particularly limited, but from the viewpoint of yield and 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, and 10 mL or more and 80 mL or less are More preferable.

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

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples as well as the present invention, and may be appropriately modified within a range compatible with the gist of the preceding and the following. Of course, it is possible to carry out, and all of them are included in the technical scope of the present invention. In the following, "parts" means "parts by mass" and "%" means "% by mass" unless otherwise specified.

  The measuring method used in the examples is as follows.

(NMR spectrum measurement)
Regarding the benzobisthiazole compound, an NMR spectrum measuring device ("400MR" manufactured by Agilent (formerly Varian) and "AVANCE" manufactured by Bruker
500 ") was used for NMR spectrum measurement.

(Gel Permeation Chromatography (GPC))
The molecular weight of the benzobisthiazole compound was measured using gel permeation chromatography (GPC). At the time of measurement, the benzobisthiazole compound was dissolved in a mobile phase solvent (chloroform) to a concentration of 0.5 g / L, the measurement was performed 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
Device: 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 that the concentration became 0.03 g / L, and an ultraviolet / visible spectrophotometer (manufactured by Shimadzu Corporation, "UV-2450", "UV-3150"), and The UV-visible absorption spectrum was measured using a cell with 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 film was measured at room temperature and atmospheric pressure with an ultraviolet photoelectron analyzer ("AC-3" manufactured by Riken Keiki Co., Ltd.).

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

2,6-diiodobenzo [1,2-d; 4,5-d '] bisthiazole (DBTH-DI, 5.2 g, 11.7 mmol), tributyl [5- (2-hexyldecyl) thiophene-in a 300 mL flask. 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 the mixture was reacted at 120 ° C for 23 hours. After completion of the reaction, the mixture was cooled to room temperature, water was added, the mixture was extracted twice with chloroform, the organic layer was washed with water and then dried over anhydrous magnesium sulfate. Then, 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-hexyldecyl) thiophen-2-yl. ] Benzo [1,2-d; 4,5-d '] bisthiazole (DBTH-HDTH) (5.62 g) was obtained as a pale yellow solid (yield 60%).
It was confirmed by ¹ H-NMR measurement that the desired 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)
Of 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d '] bisthiazole (DI-DBTH-HDTH) Synthesis

2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] benzo [1,2-d; 4,5-d '] bisthiazole (DBTH-HDTH, 4 g, 4.97 mmol) in a 100 mL flask. ) And tetrahydrofuran (80 mL) were added and the mixture was cooled to −40 ° C., lithium diisopropylamide (2M solution, 5.5 mL, 10.9 mmol) was added dropwise, and the mixture was stirred for 30 minutes. Then, after adding iodine (3.8 g, 14.9 mol), the reaction was carried out at room temperature for 2 hours. After completion of the reaction, 10% sodium hydrogen sulfite was added and the mixture was extracted with chloroform. The obtained organic layer was washed with saturated aqueous sodium hydrogen carbonate and then saturated brine, and dried over anhydrous magnesium sulfate. Then, 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-hexyldecyl) thiophen-2-yl. ] -4,8-Diiodobenzo [1,2-d; 4,5-d '] bisthiazole (DI-DBTH-HDTH) was obtained in an amount of 2.66 g as a yellow solid (yield 51%).
It was confirmed by ¹ H-NMR measurement that the desired 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)

2,6-diiodobenzo [1,2-d; 4,5-d '] bisthiazole (DBTH-DI, 0.86 g, 1.93 mmol), tributyl [5- (2-butyloctyl) thiophene-in a 50 mL flask. 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 mixture was cooled to room temperature, water was added, the mixture was extracted twice with chloroform, the organic layer was washed with water and then dried over anhydrous magnesium sulfate. Then, 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-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 (51% yield).
It was confirmed by ¹ H-NMR measurement that the desired 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) Synthesis

2,6-bis [5- (2-butyloctyl) thiophen-2-yl] benzo [1,2-d; 4,5-d '] bisthiazole (DBTH-BOTH, 1.5 g, 2 in a 100 mL flask) 0.16 mmol) and tetrahydrofuran (30 mL) were added and the mixture was cooled to −40 ° C., and then lithium diisopropylamide (2M solution, 2.4 mL, 4.75 mmol) was added dropwise and stirred for 30 minutes. Then, after adding iodine (1.7 g, 6.48 mmol), the reaction was carried out at room temperature for 2 hours. After completion of the reaction, 10% sodium hydrogen sulfite was added and the mixture was extracted with chloroform. The obtained organic layer was washed with saturated aqueous sodium hydrogen carbonate and then saturated brine, and dried over anhydrous magnesium sulfate. Then, 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-butyloctyl) thiophen-2-yl. ] -4,8-Diiodobenzo [1,2-d; 4,5-d '] bisthiazole (DI-DBTH-BOTH) was obtained as 1.15 g as a yellow solid (yield 56%).
It was confirmed by ¹ H-NMR measurement that the desired 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)

2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d '] bisthiazole (DI-DBTH- in a 50 mL flask. 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 mixture was cooled to room temperature, water was added, the mixture was extracted twice with chloroform, the organic layer was washed with water and then dried over anhydrous magnesium sulfate. Then, 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-hexyldecyl) thiophene-2. -Yl] -4,8-dithiophen-2-yl-benzo [1,2-d; 4,5-d '] bisthiazole (DTH-DBTH-HDTH) was obtained as 1.01 g as a yellow solid ( Yield 100%).
It was confirmed by ¹ H-NMR measurement that the desired 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; 4,5 Synthesis of -d '] bisthiazole (DTH-DBTH-HDTH-DSM)

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. Then, trimethyltin chloride (1M solution, 16 mL, 1.58 mmol) was added, the temperature was raised to room temperature, and the mixture was stirred for 2 hours. After completion of the reaction, water was added and the mixture was extracted twice with toluene. The organic layer was washed with water and dried over anhydrous magnesium sulfate. Then, 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 desired 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 the mixture was reacted at room temperature for 43 hours. After the reaction was completed, it was washed with water (twice) and then dried over anhydrous magnesium sulfate. Then, 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 desired compound was produced.

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.68 (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)

2,6-bis [5- (2-butyloctyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d '] bisthiazole (DI-DBTH- in a 50 mL flask. 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 the mixture was reacted at 80 ° C for 22 hours. After completion of the reaction, the mixture was cooled to room temperature, water was added, the mixture was extracted twice with chloroform, the organic layer was washed with water and then dried over anhydrous magnesium sulfate. Then, 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. -Yl] -4,8-dithiophen-2-yl-benzo [1,2-d; 4,5-d '] bisthiazole (DTH-DBTH-BOTH) was obtained as a yellow solid (0.99 g) ( Yield 99%).
It was confirmed by ¹ H-NMR measurement that the desired 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 '] Bisthiazole (DTH-DBTH-BOTH-DB) synthesis
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 the mixture was reacted at room temperature for 19 hours. After the reaction was completed, it was washed with water (twice) and then dried over anhydrous magnesium sulfate. Then, 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 desired compound was produced.

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.68 (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)

2,6-diiodobenzo [1,2-d; 4,5-d '] bisthiazole (DBTH-DI, 3 g, 6.76 mmol), tributyl [5- (3,7-dimethyloctyl) thiophene-in a 100 mL flask. 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 mixture was cooled to room temperature, water was added, the mixture was extracted twice with chloroform, the organic layer was washed with water and then dried over anhydrous magnesium sulfate. Then, 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- (3,7-dimethyloctyl) thiophene-2. 2.0 g of -yl] 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 desired 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

2,6-bis [5- (3,7-dimethyloctyl) thiophen-2-yl] benzo [1,2-d; 4,5-d '] bisthiazole (DBTH-DMOTH, 1.4 g in a 50 mL flask) , 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, after adding iodine (1.6 g, 6.36 mmol), the mixture was reacted at room temperature for 2 hours. After completion of the reaction, 10% sodium hydrogen sulfite was added and the mixture was extracted with chloroform. The obtained organic layer was washed with saturated aqueous sodium hydrogen carbonate and then saturated brine, and dried over anhydrous magnesium sulfate. Then, 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- (3,7-dimethyloctyl) thiophene-2. 1.32 g of -yl] -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 desired 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)

2,6-diiodobenzo [1,2-d; 4,5-d '] bisthiazole (DBTH-DI, 5.2 g, 11.6 mmol), tributyl [5- (2-decyltetradecyl) thiophene in a 200 mL flask. -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 the mixture was reacted at 120 ° C for 23 hours. After completion of the reaction, the mixture was cooled to room temperature, water was added, the mixture was extracted twice with chloroform, the organic layer was washed with water and then dried over anhydrous magnesium sulfate. Then, 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-. Yield] benzo [1,2-d; 4,5-d '] bisthiazole (DBTH-TDTH) was obtained as 6.12 g as a pale yellow solid (yield 51%).
It was confirmed by ¹ H-NMR measurement that the desired 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

2,6-bis [5- (2-decyltetradecyl) thiophen-2-yl] benzo [1,2-d; 4,5-d '] bisthiazole (DBTH-TDTH, 4.1 g) in a 200 mL flask. After adding 3.97 mmol) and tetrahydrofuran (80 mL) and cooling to -40 degreeC, lithium diisopropylamide (2M solution, 4.4 mL, 8.8 mmol) was dripped and stirred for 30 minutes. Then, 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 hydrogen sulfite was added and the mixture was extracted with chloroform. The obtained organic layer was washed with saturated aqueous sodium hydrogen carbonate and then saturated brine, and dried over anhydrous magnesium sulfate. Then, the crude product obtained by filtration and concentration is purified by column chromatography (silica gel, ethyl acetate / hexane = 5/95) to give 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 3.98 g as a yellow solid (yield 69%).
It was confirmed by ¹ H-NMR measurement that the desired 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 ( Synthesis of DTH-DBTH-TDTH)

2,6-bis [5- (2-decyltetradecyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d '] bisthiazole (DI-DBTH) in a 100 mL flask. -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 the mixture was reacted at 100 ° C for 23 hours. After completion of the reaction, the mixture was cooled to room temperature, water was added, the mixture was extracted twice with chloroform, the organic layer was washed with water and then dried over anhydrous magnesium sulfate. Then, the crude product obtained by filtration and concentration is purified by column chromatography (silica gel, ethyl acetate / hexane = 1/9) to give 2,6-bis [5- (2-decyltetradecyl) thiophene-2. 2.21 g of -yl] -4,8-dithiophen-2-yl-benzo [1,2-d; 4,5-d '] bisthiazole (DTH-DBTH-TDTH) was obtained as a yellow solid ( Yield 95%).
It was confirmed by ¹ H-NMR measurement that the desired 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; 4 5-d '] bisthiazole (DTH-DBTH-TDTH-DSM)

2,6-bis [5- (2-decyltetradecyl) thiophen-2-yl] -4,8-dithiophen-2-yl-benzo [1,2-d; 4,5-d '] in a 30 mL flask. 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. Then, trimethyltin chloride (1M solution, 3.0 mL, 3.02 mmol) was added, the temperature was raised to room temperature, and the mixture was stirred for 2 hours. After completion of the reaction, water was added and the mixture was extracted twice with toluene. The organic layer was washed with water and dried over anhydrous magnesium sulfate. Then, 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 desired 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)
2,6-bis [5- (2-decyltetradecyl) thiophen-2-yl] -4,8-dithiophen-2-yl-benzo [1,2-d; 4,5-d '] in a 20 mL flask. Bisthiazole (DTH-DBTH-TDTH, 300 mg, 0.25 mmol), NBS (N-bromosuccinimide, 99 mg, 0.55 mmol) and chloroform (6 mL) were added, and the mixture was reacted at room temperature for 19 hours. After the reaction was completed, it was washed with water (twice) and then dried over anhydrous magnesium sulfate. Then, 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- ( 300 mg of 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 desired compound was produced.

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.68 (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-thiophendiyl) 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 the mixture was reacted at 130 ° C. for 24 hours. After the reaction was completed, the reaction solution was added to methanol (40 mL), and the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Then, Soxhlet extraction (chloroform) was performed to obtain 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

In a 20 mL flask, 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d '] bisthiazole (DI-DBTH) was added. -HDTH, 100 mg, 0.09 mmol), 1,1 '-(2.5-thiophendiyl) bis [1,1,1-trimethyl] stannane (39 mg, 0.09), addition of dipalladium (0) -chloroform The body (4 mg, 3.8 μmol), tris (2-methoxyphenyl) phosphine (5 mg, 15.1 μmol) and chlorobenzene (8 mL) were added, and the mixture was reacted at 130 ° C. for 24 hours. After the reaction was completed, the reaction solution was added to methanol (40 mL), and the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Then, Soxhlet extraction (chloroform) was performed to obtain 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

Preparation / 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, a donor material: an 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 give a mixed solution.
The glass substrate on which the ITO film was formed was subjected to ozone UV treatment and surface treatment, and then a PEDOT-PSS ([poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)) aqueous dispersion was spun. It was applied and annealed with a coater. Next, the mixed solution of the donor material and the acceptor material was formed into a film by a spin coater and dried under reduced pressure at room temperature. An ethanol solution of tetraisopropyl orthotitanate (about 0.3 v%) was spin-coated thereon to form a film converted into titanium oxide by water in the atmosphere. Then, aluminum which is an electrode was vapor-deposited to obtain a device.
The device thus obtained was characterized by using a solar simulator (CEP2000, AM1.5G filter, radiant intensity 100 mW / cm ² , manufactured by Spectrometer). As a result, it was confirmed that the conversion efficiency was 1.35% at Jsc (short circuit current density) = 3.27 mA / cm ² , Voc (open end voltage) = 0.75 V, and FF (fill factor) = 0.55.

(Example 3) Synthesis of P-TBOT-DBTH-DT
In a 20 mL flask, 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 the mixture was reacted at 130 ° C. for 24 hours. After the reaction was completed, the reaction solution was added to methanol (40 mL), and the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Then, Soxhlet extraction (chloroform) was performed to obtain 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
In a 20 mL flask, 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d '] bisthiazole (DI-DBTH) was added. -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 the mixture was reacted at 130 ° C. for 27 hours. After the reaction was completed, the reaction solution was added to methanol (40 mL), and the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Then, Soxhlet extraction (chloroform) was performed to obtain 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 the mixture was reacted at 130 ° C. for 24 hours. After the reaction was completed, the reaction solution was added to methanol (40 mL), and the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Then, Soxhlet extraction (chloroform) was performed to obtain 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 give a mixed solution.
The glass substrate on which the ITO film was formed was subjected to ozone UV treatment and surface treatment, and then a PEDOT-PSS ([poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)) aqueous dispersion was spun. It was applied and annealed with a coater. Next, the mixed solution of the donor material and the acceptor material was formed into a film by a spin coater and dried under reduced pressure at room temperature. An ethanol solution of tetraisopropyl orthotitanate (about 0.3 v%) was spin-coated thereon to form a film converted into titanium oxide by water in the atmosphere. Then, aluminum which is an electrode was vapor-deposited to obtain a device.
The device thus obtained was characterized by using a solar simulator (CEP2000, AM1.5G filter, radiant intensity 100 mW / cm ² , manufactured by Spectrometer). As a result, it was confirmed that the conversion efficiency was 2.82% at 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 (0) -Chloroform adduct (1 mg, 1.2 μmol), tris (2-methoxyphenyl) phosphine (2 mg, 4.8 μmol) and chlorobenzene (2 mL) were added, and the mixture was added at 130 ° C. for 2 hours. It was time reaction. After completion of the reaction, the reaction solution was added to methanol (20 mL), and the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Then, Soxhlet extraction (chloroform) was performed to obtain 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, 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 the mixture was reacted at 130 ° C. for 24 hours. After the reaction was completed, the reaction solution was added to methanol (40 mL), and the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Then, Soxhlet extraction (chloroform) was performed to obtain P-TBOT-DBTH-HTD as a black solid in an amount of 92 mg (86%).

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; 4. , 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 the reaction was completed, the reaction solution was added to methanol (40 mL), and the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Then, Soxhlet extraction (chloroform) was performed to obtain 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; 4. , 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 added at 130 ° C. for 24 hours. I reacted. After completion of the reaction, the reaction liquid was added to methanol (30 mL), and the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Then, Soxhlet extraction (chloroform) was performed to obtain 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 Device 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 give a mixed solution.
The glass substrate on which the ITO film was formed was subjected to ozone UV treatment and surface treatment, and then a PEDOT-PSS ([poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)) aqueous dispersion was spun. It was applied and annealed with a coater. Next, the mixed solution of the donor material and the acceptor material was formed into a film by a spin coater and dried under reduced pressure at room temperature. An ethanol solution of tetraisopropyl orthotitanate (about 0.3 v%) was spin-coated thereon to form a film converted into titanium oxide by water in the atmosphere. Then, aluminum which is an electrode was vapor-deposited to obtain a device.
The device thus obtained was characterized by using a solar simulator (CEP2000, AM1.5G filter, radiant intensity 100 mW / cm ² , manufactured by Spectrometer). As a result, it was confirmed that the conversion efficiency was 0.77% at Jsc (short circuit current density) = 4.24 mA / cm ² , Voc (open end voltage) = 0.79 V, and FF (fill factor) = 1.94.

(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-thiophenediyl) bis [1,1,1-trimethyl] stannane ( 36 mg, 0.09 mmol), a 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 heated to 27 ° C. at 27 ° C. Reacted for hours. After the reaction was completed, the reaction solution was added to methanol (40 mL), and the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Then, Soxhlet extraction (chloroform) was performed to obtain 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 using 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 give a mixed solution.
The glass substrate on which the ITO film was formed was subjected to ozone UV treatment and surface treatment, and then a PEDOT-PSS ([poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)) aqueous dispersion was spun. It was applied and annealed with a coater. Next, the mixed solution of the donor material and the acceptor material was formed into a film by a spin coater and dried under reduced pressure at room temperature. An ethanol solution of tetraisopropyl orthotitanate (about 0.3 v%) was spin-coated thereon to form a film converted into titanium oxide by water in the atmosphere. Then, aluminum which is an electrode was vapor-deposited to obtain a device.
The device thus obtained was characterized by using a solar simulator (CEP2000, AM1.5G filter, radiant intensity 100 mW / cm ² , manufactured by Spectrometer). As a result, it was confirmed that the conversion efficiency was 3.06% at Jsc (short circuit current density) = 7.25 mA / cm ² , Voc (open circuit voltage) = 0.68 V, and FF (fill factor) = 0.62.

  INDUSTRIAL APPLICABILITY The polymer compound of the present invention has high photoelectric conversion efficiency, and thus is useful in organic electrodevices such as organic electroluminescence elements and organic thin film transistor elements.

Claims (12)

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 Expression ^{(1), T 1, T} 2 each independently represents an thiophene ring optionally substituted with charcoal hydrocarbon group or an organosilyl group. ]
[In the formula (2), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. ] 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. ] The polymer compound according to claim 1 or 2, which comprises a repeating unit represented by the following formula (6).
In Expression ^{(1), T 1, T} 2, T 3, T 4 each independently represent an thiophene ring optionally substituted with charcoal hydrocarbon group or an organosilyl group.
R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
T ¹ , T ² , T ³ , and T ⁴ are not all the same, and R ¹ , R ² , R ³ , and R ⁴ are not all the same. ] The polymer compound according to claim ¹ , wherein T ¹ and T ² are each a group represented by the following formula (t3) .
[In formula (t3) ,
R ²³ are each independently a hydrocarbon group having 6 to 30 carbon atoms, or ** - represents a group represented by Si ^{(R 26)} _3.
R ^26's each independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and a plurality of R ^26's may be the same or different .
* Represents a bond that bonds to the thiazole ring of benzobisthiazole. ** represents a bond that bonds to (t3) . ] The polymer compound according to claim 3, wherein each of T ¹ , T ² , T ³ , and T ⁴ is a group represented by the following formula (t3) .
[In formula (t3) ,
R ²³ are each independently a hydrocarbon group having 6 to 30 carbon atoms, or ** - represents a group represented by Si ^{(R 26)} _3.
R ^26's each independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and a plurality of R ^26's may be the same or different .
* Represents a bond that bonds to the thiazole ring of benzobisthiazole. ** represents a bond that bonds to (t3) . ]   An organic semiconductor material comprising the polymer compound according to claim 1.   The organic semiconductor material according to claim 6, which is a p-type semiconductor or an n-type semiconductor.   An organic electronic device comprising the organic semiconductor material according to claim 7.   It is a photoelectric conversion element or a solar cell, The organic electronic device of Claim 8 characterized by the above-mentioned. A dihalogenobenzobisthiazole compound represented by the following formula (4),
Wherein ^{(4), T 1, T} 2 each independently represents an thiophene ring optionally substituted with charcoal hydrocarbon group or an organosilyl group. X ¹ and X ² represent a halogen atom. ]
A thiophene compound represented by the following formula (5):
[In the 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 represent 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 together with M ¹ , and R ¹² and R ¹³ may form a ring together with M ² .
m and n each represent an integer of 1 or 2. Further, when m and n are 2, a plurality of R ¹⁰ and R ¹² may be the same or different. ]
A method for producing a polymer compound represented by formula (3), which comprises a cross-coupling reaction.
[In the formula (3), T ¹ , T ² , and R ¹ each represent the same group as described above, and p represents an integer similar to the above. ] A dihalogenobenzobisthiazole compound represented by the following formula (7),
Wherein ^{(7), T 1, T} 2 each independently represents an thiophene ring optionally substituted with charcoal hydrocarbon group or an organosilyl group.
R ¹ and R ² each independently represent 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):
Wherein ^{(8), T 3, T} 4 each independently represent an thiophene ring optionally substituted with charcoal hydrocarbon group or an organosilyl group.
R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
R ^{10 to} R ¹³ each independently represent 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 together with M ¹ , and R ¹² and R ¹³ may form a ring together with M ² .
m and n each represent an integer of 1 or 2. Further, when m and n are 2, a plurality of R ¹⁰ and R ¹² may be the same or different. ]
A method for producing a polymer compound represented by formula (6), which comprises a cross-coupling reaction.
[In the formula (6), T ¹ , T ² , T ³ , T ⁴ , R ¹ , R ² , R ³ , and R ⁴ each represent the same group as described above. ] A dihalogenobenzobisthiazole compound represented by the following formula (7),
Wherein ^{(7), T 1, T} 2 each independently represents an thiophene ring optionally substituted with charcoal hydrocarbon group or an organosilyl group.
R ¹ and R ² each independently represent 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 the 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 represent 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 together with M ¹ , and R ¹² and R ¹³ may form a ring together with M ² .
m and n each represent an integer of 1 or 2. Further, when m and n are 2, a plurality of R ¹⁰ and R ¹² may be the same or different. ]
A method for producing a polymer compound represented by formula (3), which comprises a cross-coupling reaction.
[In the formula (3), T ¹ , T ² , and R ¹ each represent the same group as described above, and p represents an integer similar to the above. ]