JP7565564B2 - Compounds, organic semiconductor materials, and organic electronic devices - Google Patents

Description

The present invention relates to a compound having a donor unit containing specific units and an acceptor unit, an organic semiconductor material containing the compound, and an organic electronic device containing the organic semiconductor material.

Organic semiconductor materials are important materials in the field of organic electronics, and monomeric compounds and polymeric compounds are used as organic semiconductor materials. Organic semiconductor materials can be classified into p-type organic semiconductor materials, which are electron-donating, and n-type organic semiconductor materials, which are electron-accepting, and various organic electronic devices can be manufactured by appropriately combining p-type and n-type organic semiconductor materials. Examples of organic electronic devices include organic electroluminescence elements that emit light due to the action of excitons formed by the recombination of electrons and holes, organic thin-film transistor elements that control the amount of current or voltage, organic photoelectric conversion elements, and organic thin-film solar cell modules that convert light into electricity.

As an example of an organic semiconductor material, a polymer used as an n-type organic semiconductor material is proposed in Patent Document 1. The polymer proposed in Patent Document 1 is a nitrogen-containing fused ring polymer having at least one repeating unit represented by the following general formula (II) and at least one repeating unit represented by the following general formula (III). In formula (II), ^Z1 and ^Z2 are exemplified by S (sulfur atom), and in formula (III), ^Ar1 is exemplified by a divalent aromatic hydrocarbon group or a divalent heterocyclic group.

JP 2009-215278 A

Organic electronic devices are manufactured, for example, by forming an organic semiconductor material into an organic thin film by a vacuum deposition method, or by forming an organic semiconductor material dissolved in a solvent or the like into an organic thin film by a predetermined film-forming method. If the organic semiconductor material is soluble in a solvent (particularly an organic solvent), it is possible to form a film by a printing process, for example, so that the area of the organic thin film can be increased and the manufacturing cost can be reduced. For this reason, it is desirable for the organic semiconductor material to have good solubility in the solvent. However, in the examples of the above-mentioned Patent Document 1, a nitrogen-containing fused ring compound is used as the organic semiconductor material, and an organic semiconductor element is manufactured by a vacuum deposition method. The reason why the vacuum deposition method is adopted is thought to be that the nitrogen-containing fused ring compound is difficult to dissolve in a solvent, and the solubility of the nitrogen-containing fused ring compound in a solvent is not examined in Patent Document 1. When the present inventors examined the solubility of the organic semiconductor material, they found that there was room for improvement.

An object of the present invention is to provide a compound that can be preferably used as an organic semiconductor material and has good solubility in a solvent. Another object of the present invention is to provide an organic semiconductor material containing such a compound. Another object of the present invention is to provide an organic electronic device containing such an organic semiconductor material.

［２］ 前記アクセプター性ユニットが、（１）縮環構造を有し、かつ環の少なくとも１つが芳香族環であり、環を構成する元素が炭素原子とヘテロ原子である、ヘテロ芳香族縮環型ユニット、（２）縮環構造を有し、かつ環の少なくとも１つが芳香族環であり、環を構成する元素が炭素原子である、芳香族縮環型ユニット、及び（３）芳香族環を有し、縮環構造を有さない、単環型ユニット、からなる群より選ばれる少なくとも１種を含む［１］に記載の化合物。
［３］ 前記ドナー性ユニットと、前記アクセプター性ユニットとを繰り返し単位として有する［１］または［２］に記載の高分子型化合物。
［４］ 前記ドナー性ユニットと前記アクセプター性ユニットとが交互に配置されている［３］に記載の高分子型化合物。
［５］ 重量平均分子量（Ｍｗ）が１５００以上である［３］または［４］に記載の高分子型化合物。
［６］ 前記高分子型化合物に含まれる複数のドナー性ユニットが、更に下記式（Ｄｏ－Ｋ）で表される単位を含む［３］～［５］のいずれかに記載の高分子型化合物。下記式（Ｄｏ－Ｋ）中、＊は、結合手を表す。

［７］ 前記ドナー性ユニットおよび前記アクセプター性ユニットを合計で２つまたは３つ有する［１］に記載の低分子型化合物。
［８］ 前記ドナー性ユニットに２つの前記アクセプター性ユニットが連結されている［１］に記載の三量体型化合物。
［９］ ［１］～［８］のいずれかに記載の化合物を含む有機半導体材料。
［１０］ ［９］に記載の有機半導体材料を含む有機電子デバイス。 The present invention includes the following inventions.
[1] A compound having at least one donor unit and at least one acceptor unit each containing a unit represented by the following formula (Do-A), in which the donor unit and the acceptor unit are linked to each other, wherein R ^a represents an alkylene group having 2 to 10 carbon atoms, and * represents a bond.

[2] The compound according to [1], wherein the acceptor unit includes at least one unit selected from the group consisting of: (1) a heteroaromatic fused ring unit having a fused ring structure, at least one of the rings being an aromatic ring, and the elements constituting the ring being a carbon atom and a heteroatom; (2) an aromatic fused ring unit having a fused ring structure, at least one of the rings being an aromatic ring, and the elements constituting the ring being a carbon atom; and (3) a monocyclic unit having an aromatic ring and no fused ring structure.
[3] The polymer compound according to [1] or [2], which has the donor unit and the acceptor unit as repeating units.
[4] The polymer compound according to [3], in which the donor units and the acceptor units are arranged alternately.
[5] The polymeric compound according to [3] or [4], having a weight average molecular weight (Mw) of 1,500 or more.
[6] The polymer compound according to any one of [3] to [5], wherein the donor units contained in the polymer compound further include a unit represented by the following formula (Do-K): In the following formula (Do-K), * represents a bond.

[7] The low molecular weight compound according to [1], having a total of two or three of the donor units and the acceptor units.
[8] The trimer compound according to [1], wherein the donor unit is linked to two of the acceptor units.
[9] An organic semiconductor material comprising the compound according to any one of [1] to [8].
[10] An organic electronic device comprising the organic semiconductor material according to [9].

According to the present invention, it is possible to provide a compound that can be preferably used as an organic semiconductor material and has good solubility in a solvent. Furthermore, according to the present invention, it is possible to provide an organic semiconductor material containing such a compound, and an organic electronic device containing such an organic semiconductor material.

FIG. 1 shows the ultraviolet-visible absorption spectrum of polymer compound 1. FIG. 2 shows the ultraviolet-visible absorption spectrum of polymer compound 2. FIG. 3 shows the ultraviolet-visible absorption spectrum of polymer compound 3. FIG. 4 shows the ultraviolet-visible absorption spectrum of polymer compound 4. FIG. 5 shows the ultraviolet-visible absorption spectrum of polymer compound 5. FIG. 6 shows the ultraviolet-visible absorption spectrum of polymer compound 6. FIG. 7 shows the ultraviolet-visible absorption spectrum of polymer compound 7. FIG. 8 shows the ultraviolet-visible absorption spectrum of polymer compound 8. FIG. 9 shows the ultraviolet-visible absorption spectrum of polymer compound 9. FIG. 10 shows the ultraviolet-visible absorption spectrum of the polymer compound 10. FIG. 11 shows the ultraviolet-visible absorption spectrum of the polymer compound 11. FIG. 12 shows the ultraviolet-visible absorption spectrum of the polymer compound 12. FIG. 13 shows the ultraviolet-visible absorption spectrum of the polymer compound 13. FIG. 14 is a schematic diagram for explaining a method for calculating the band gap, in which auxiliary lines are drawn on the ultraviolet-visible absorption spectrum obtained by performing UV measurement on a thin film containing polymer-type compound 9. FIG. 15 shows the ultraviolet-visible absorption spectrum of the low molecular weight compound 1. FIG. 16 shows the ultraviolet-visible absorption spectrum of the low molecular weight compound 3. FIG. 17 shows the ultraviolet-visible absorption spectrum of low molecular weight compound 4. FIG. 18 shows the ultraviolet-visible absorption spectrum of the low molecular weight compound 5. FIG. 19 shows the ultraviolet-visible absorption spectrum of the low molecular weight compound 6. FIG. 20 shows the ultraviolet-visible absorption spectrum of the low molecular weight compound 7.

The compound of the present invention has one or more donor units each containing a unit represented by the following formula (Do-A) and one or more acceptor units, and the donor units and the acceptor units are linked to each other. In the following formula (Do-A), R ^a represents an alkylene group having 2 to 10 carbon atoms, and * represents a bond. When the donor unit containing a unit represented by the following formula (Do-A) is at the end of the compound, * may be a hydrogen atom.

A donor unit constituting a compound means an electron-donating structural unit. An acceptor unit constituting a compound means an electron-accepting structural unit.

The unit represented by formula (Do-A) has excellent electron donating properties. The unit represented by formula (Do-A) also has a spiro skeleton including an acetal structure, and therefore has good solubility in a solvent. Therefore, if a compound that combines a donor unit containing a unit represented by formula (Do-A) and an acceptor unit is used, the compound has good solubility in a solvent. Therefore, the film quality of the film coated with the compound on a substrate is good, and the electron mobility of the film is good. In addition, if a compound that combines a donor unit containing a unit represented by formula (Do-A) and an acceptor unit is used, the band gap between the ionization energy value (HOMO value) and the LUMO value is small, and electrons are easily moved. Furthermore, the electrostatic interaction between the molecules improves the orientation, and an improvement in electron mobility can be expected. In addition, the LUMO value is, for example, -3.5 eV or less, and the compound has atmospheric stability. Therefore, a compound having one or more donor units each containing a unit represented by formula (Do-A) and one or more acceptor units, in which the donor units and the acceptor units are linked to each other, can be suitably used, for example, as an organic semiconductor material.

The compound of the present invention has one or more donor units and one or more acceptor units each containing a unit represented by the above formula (Do-A), and the donor units and the acceptor units are linked to each other. Among such compounds, compounds having a total of two or three donor units and acceptor units may be referred to as low molecular weight compounds hereinafter. In addition, compounds having donor units and acceptor units each containing a unit represented by the above formula (Do-A) as repeating units may be referred to as polymer compounds hereinafter. In other words, polymer compounds are compounds having two or more donor units and acceptor units each containing a unit represented by the above formula (Do-A), and the donor units and the acceptor units are linked to each other. Among low molecular weight compounds, compounds having a total of two donor units and acceptor units (i.e., compounds in which one donor unit and one acceptor unit are linked to each other) are called dimeric compounds. Among low molecular weight compounds, compounds having a total of three donor units and acceptor units in which the donor units and the acceptor units are linked to each other are hereinafter sometimes called trimer compounds or simply trimers. The trimer compounds may be compounds in which two donor units are linked to one acceptor unit, but are preferably compounds in which two acceptor units are linked to one donor unit. In the case of low molecular weight compounds, the solubility in a solvent is better than that of polymeric compounds. As a result, by using low molecular weight compounds, for example, a homogeneous thin film can be produced by spin coating, resulting in good electron mobility.

In formula (Do-A), the carbon number of R ^a is preferably 2 to 8, more preferably 2 to 6, and even more preferably 2 to 4. The alkylene group may be a linear alkylene group or a branched alkylene group, but is preferably a linear alkylene group. Examples of ^{R a} include an ethylene group, an n-propylene group, a 1-methyl-ethane-1,2-yl group, a 1,2-dimethyl-ethane-1,2-yl group, and a 1-methyl-propan-1,3-yl group, and among these, an ethylene group and an n-propylene group are preferred.

In the unit represented by formula (Do-A), when R ^a is an ethylene group having 2 carbon atoms, the unit represented by formula (Do-A) is represented by the following formula (Do-a).

The donor units constituting the compound of the present invention may contain units represented by the above formula (Do-A), and may contain other donor units such as known donor units or units represented by the formula (Do-K) described below. When the entire donor units are taken as 100 mol%, the proportion of units represented by the above formula (Do-A) is, for example, preferably 40 mol% or more, more preferably 50 mol% or more, and even more preferably 80 mol% or more. The entire donor units (100 mol%) may be units represented by the above formula (Do-A).

The acceptor unit to be combined with the donor unit constituting the compound may be a known acceptor unit. The acceptor unit preferably contains at least one type selected from the group consisting of the following (1) to (3):
(1) A heteroaromatic fused ring type unit having a fused ring structure, in which at least one of the rings is an aromatic ring, and the elements constituting the ring are carbon atoms and heteroatoms.
(2) An aromatic fused ring type unit having a fused ring structure, in which at least one of the rings is an aromatic ring, and the elements constituting the ring are carbon atoms.
(3) A monocyclic unit having an aromatic ring and no condensed ring structure.

The following explains units (1) to (3).

(1) Heteroaromatic fused ring unit Heteroaromatic fused ring unit is a structural unit having a fused ring structure, at least one of the rings being an aromatic ring, and the elements constituting the ring being carbon atoms and heteroatoms. A heteroatom is an atom other than a carbon atom. In other words, a heteroaromatic fused ring unit is a fused ring unit containing an aromatic ring, and at least one of the rings constituting the fused ring of the fused ring unit is a heterocycle composed of carbon atoms and heteroatoms. That is, a fused ring unit having a fused ring structure has at least one heterocycle. Each heteroatom is, for example, a nitrogen atom, a sulfur atom, or an oxygen atom.

The number of rings constituting the condensed ring structure is not particularly limited, but is preferably, for example, 2 or more and 10 or less. The number of rings may be 3 or more and 8 or less.

The aromatic ring may be an aromatic hydrocarbon ring or a heteroaromatic ring (sometimes called a heteroaromatic ring).

The elements constituting the ring are carbon atoms and heteroatoms, and the ring contains at least one heteroatom, with the remainder being carbon atoms. The number of heteroatoms may be two or more, or may be three or more. The upper limit of the number of heteroatoms depends on the number of atoms constituting the condensed ring structure, but is preferably, for example, 10 or less, more preferably 8 or less, and even more preferably 6 or less.

A substituent may be bonded to the ring. Examples of the substituent include a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, an ester group, a halogenated alkyl group, and a cyano group. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine, and fluorine is preferred. The hydrocarbon group (hereinafter sometimes referred to as the hydrocarbon group R) is preferably an aliphatic hydrocarbon group, an aralkyl group, and the aliphatic hydrocarbon group may be a linear aliphatic hydrocarbon group, but is more preferably a branched aliphatic hydrocarbon group.

The number of carbon atoms in the hydrocarbon group R is not particularly limited, and is preferably 1 to 30, for example. The number of carbon atoms in the hydrocarbon group R is more preferably 3 or more, even more preferably 6 or more, and more preferably 28 or less, even more preferably 26 or less. However, when the hydrocarbon group R is an aralkyl group, the lower limit of the number of carbon atoms is preferably 7 or more. When the compound of the present invention is a polymeric compound, the number of carbon atoms in the hydrocarbon group R is preferably larger, and the larger the carbon number, the better the solubility in the solvent. In the case of a polymeric compound, the number of carbon atoms in the hydrocarbon group R is preferably 8 or more, more preferably 10 or more, and even more preferably 12 or more. When the compound of the present invention is a low molecular weight compound, the number of carbon atoms in the hydrocarbon group R is preferably smaller, and the smaller the carbon number, the better the orientation, the easier it is for electrons to move between molecules, and the electron mobility is improved. In the case of a low molecular weight compound, the number of carbon atoms in the hydrocarbon group R is preferably 24 or less, more preferably 20 or less, and even more preferably 14 or less.

Examples of the hydrocarbon group R include alkyl groups having one carbon atom, such as a methyl group; alkyl groups having two carbon atoms, such as an ethyl group; alkyl groups having three carbon atoms, such as an n-propyl group or an isopropyl group; alkyl groups having four carbon atoms, such as an n-butyl group; alkyl groups having five carbon atoms, such as an n-pentyl group; alkyl groups having six carbon atoms, such as an n-hexyl group; alkyl groups having seven carbon atoms, such as an n-heptyl group; an n-octyl group, a 1-n-butylbutyl group, a 1-n-propylpentyl group, and the like. alkyl groups having 8 carbon atoms, such as an n-nonyl group, a 1-n-propylhexyl group, a 2-n-propylhexyl group, a 1-ethylheptyl group, a 2-ethylheptyl group, a 3-ethylhexyl group, a 4-ethylhexyl group, a 1-methylheptyl group, a 2-methylheptyl group, a 6-methylheptyl group, a 2,4,4-trimethylpentyl group, or a 2,5-dimethylhexyl group; alkyl groups having 9 carbon atoms, such as an n-decyl group, a 1-n-pentylpentyl group, a 1-n-butylhexyl group, a 2-n-butylhexyl group, a 1-n-propylheptyl group, a 1-ethyloctyl group, a 2-ethyloctyl group, a 1-methylnonyl group, a 2-methylnonyl group, a 3,7-dimethyloctyl group, etc. alkyl groups having 10 carbon atoms, such as an n-undecyl group, a 1-n-butylheptyl group, a 2-n-butylheptyl group, a 1-n-propyloctyl group, a 2-n-propyloctyl group, a 1-ethylnonyl group, or a 2-ethylnonyl group; alkyl groups having 11 carbon atoms, such as an n-dodecyl group, a 1-n-pentylheptyl group, a 2-n-pentylheptyl group, a 1-n-butyloctyl group, a 2-n-butyloctyl group, a 1-n-propylnonyl group, or a 2-ethylnonyl group; an alkyl group having 12 carbon atoms, such as an n-propylnonyl group; an alkyl group having 13 carbon atoms, such as an n-tridecyl group, a 1-n-pentyloctyl group, a 2-n-pentyloctyl group, a 1-n-butylnonyl group, a 2-n-butylnonyl group, a 1-methyldodecyl group, or a 2-methyldodecyl group; an n-tetradecyl group, a 1-n-heptylheptyl group, a 1-n-hexyloctyl group, a 2-n-hexyloctyl group, a 1-n-pentylnonyl group, a 2- Alkyl groups having 14 carbon atoms, such as n-pentylnonyl groups; alkyl groups having 15 carbon atoms, such as n-pentadecyl groups, 1-n-heptyloctyl groups, 1-n-hexylnonyl groups, and 2-n-hexylnonyl groups; alkyl groups having 16 carbon atoms, such as n-hexadecyl groups, 2-n-hexyldecyl groups, 1-n-octyloctyl groups, 1-n-heptylnonyl groups, and 2-n-heptylnonyl groups; alkyl groups having 16 carbon atoms, such as n-heptadecyl groups and 1-n-octylnonyl groups. alkyl groups having a prime number of 17; alkyl groups having 18 carbon atoms such as n-octadecyl group and 1-n-nonylnonyl group; alkyl groups having 19 carbon atoms such as n-nonadecyl group; alkyl groups having 20 carbon atoms such as n-eicosyl group and 2-n-octyldodecyl group; alkyl groups having 21 carbon atoms such as n-heneicosyl group; alkyl groups having 22 carbon atoms such as n-docosyl group; alkyl groups having 23 carbon atoms such as n-tricosyl group; alkyl groups having 24 carbon atoms such as n-tetracosyl group and 2-n-decyltetradecyl group; alkyl groups having 25 carbon atoms such as n-pentacosyl; alkyl groups having 26 carbon atoms such as n-hexacosyl; alkyl groups having 27 carbon atoms such as n-heptacosyl; alkyl groups having 28 carbon atoms such as n-octacosyl; alkyl groups having 29 carbon atoms such as n-nonacosyl; alkyl groups having 30 carbon atoms such as n-triacontyl; aralkyl groups such as phenylmethyl group and phenylethyl group; and the like.

The alkoxy group is represented by ^-OR5 , where ^R5 is a hydrocarbon group. Examples of the hydrocarbon group represented by ^R5 include the same as the hydrocarbon group R described above. The number of carbon atoms in the hydrocarbon group represented by ^R5 is preferably 1 to 30, more preferably 3 or more, even more preferably 6 or more, and more preferably 28 or less, even more preferably 26 or less.

Examples of acyl groups include acetyl, propionyl, isopropionyl, butyryl, isobutyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, lauroyl, myristoyl, palmitoyl, stearoyl, oleoyl, linoleoyl, and linolenoyl groups.

Examples of ester groups include acetoxy groups, acyloxy groups, alkoxycarbonyl groups, and phosphate ester groups.

A halogenated alkyl group refers to a substituent in which some of the hydrogen atoms in the hydrocarbon group R described above are replaced with halogen atoms.

Examples of heteroaromatic fused ring units include units represented by the following formulas (Ac-1) to (Ac-17).

[In formulas (Ac-1) to (Ac-17), T ¹ and T ² each independently represent a single bond, -CH=CH-, -C≡C-, a thiophene ring optionally substituted with a hydrocarbon group, a thiazole ring optionally substituted with a hydrocarbon group, a pyridine ring optionally substituted with a hydrocarbon group, or a pyrazine ring optionally substituted with a hydrocarbon group.
R ¹ is a hydrogen atom, a hydrocarbon group, or -(CH ₂ ) _p -OR ³ , where R ³ is a hydrocarbon group. When the acceptor unit has a plurality of R ¹ , ^{the plurality of R 1 may} be the same or different from each other ^.
R ² is a hydrocarbon group. When the acceptor unit has a plurality of R ² , the plurality of R ² may include the same R ² or different R ² .
A ¹ and A ² are each independently -(CH ₂ ) _q -OR ⁴ , a thiophene ring optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group, a thiazole ring optionally substituted with a hydrocarbon group or an organosilyl group, or a phenyl group optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, an organosilyl group, a halogen atom, or a halogenated alkyl group, and R ⁴ is a hydrocarbon group.
D ¹ is CH or a nitrogen atom. When the acceptor unit has a plurality of D ¹ , the plurality of D ¹ may include the same D ¹ or different D ¹ .
^D2 is a carbon atom, a silicon atom, or a nitrogen atom.
n is 0 or 1.
When the units represented by formulae (Ac-1) to (Ac-17) are at the terminals of the compounds, * may be a hydrogen atom.
When a compound has multiple acceptor units, ^T1 , ^T2 , ^R1 , ^R2 , ^A1 , ^A2 , ^D1 , and ^D2 may each be the same between the units or different from each other.
The ring may have the above-mentioned substituents bonded thereto.

When T ¹ and T ² are thiophene rings, examples of the hydrocarbon group that the thiophene ring may have as a substituent include the same as the hydrocarbon group R described above. The number of carbon atoms in the hydrocarbon group is preferably 1 to 30, more preferably 3 or more, even more preferably 6 or more, and more preferably 28 or less, even more preferably 26 or less.

When T ¹ and T ² are thiazole rings, examples of the hydrocarbon group that the thiazole ring may have as a substituent include the same as the above-described hydrocarbon group R. The number of carbon atoms in the hydrocarbon group is preferably 1 to 30, more preferably 3 or more, even more preferably 6 or more, and more preferably 28 or less, even more preferably 26 or less.

When T ¹ and T ² are pyridine rings, examples of the hydrocarbon group with which the pyridine ring may be substituted include the same as those described above for the hydrocarbon group R. The number of carbon atoms in the hydrocarbon group is preferably 1 to 30, more preferably 3 or more, even more preferably 6 or more, and more preferably 28 or less, even more preferably 26 or less.

When T ¹ and T ² are pyrazine rings, examples of the hydrocarbon group that the pyrazine ring may have as a substituent include the same as the hydrocarbon group R described above. The number of carbon atoms in the hydrocarbon group is preferably 1 to 30, more preferably 3 or more, even more preferably 6 or more, and more preferably 28 or less, even more preferably 26 or less.

In formulae (Ac-1) to (Ac-17), T ¹ and T ² are each preferably independently a single bond, a thiophene ring which may be substituted with a hydrocarbon group, a thiazole ring which may be substituted with a hydrocarbon group, or a pyridine ring which may be substituted with a hydrocarbon group. In particular, in the case of a polymeric compound, T ¹ and T ² are each preferably independently a single bond, a thiophene ring which may be substituted with a hydrocarbon group, a thiazole ring which may be substituted with a hydrocarbon group, or a pyridine ring which may be substituted with a hydrocarbon group, and in the case of a low molecular weight compound, T ¹ and T ² are each preferably independently a single bond.

When ^R1 is a hydrocarbon group, examples of the hydrocarbon group include the same as the hydrocarbon group R described above. The number of carbon atoms in the hydrocarbon group represented by ^R1 is preferably 1 to 30, more preferably 3 or more, even more preferably 6 or more, and more preferably 28 or less, even more preferably 26 or less. The hydrocarbon group is preferably an aliphatic hydrocarbon group. In the case of a polymeric compound, a branched aliphatic hydrocarbon group is preferable. This can ensure solubility in a solvent. In the case of a low molecular weight compound, a linear aliphatic hydrocarbon group is preferable. This is expected to improve the orientation, and therefore the electron mobility is thought to be improved.

When ^R1 is -( _CH2 ) _p - ^OR3 , examples of the hydrocarbon group represented by ^R3 include the same as the hydrocarbon group R described above. The number of carbon atoms in the hydrocarbon group represented by ^R3 is preferably 1 to 30, more preferably 3 or more, even more preferably 6 or more, more preferably 28 or less, even more preferably 26 or less. p is, for example, an integer of 1 to 5.

In formulae (Ac-1) to (Ac-17), R ¹ is preferably a hydrocarbon group. When the acceptor unit has a plurality of R ¹ , the plurality of R ¹ may include the same R ¹ or different R ¹ .

Examples of the hydrocarbon group represented by ^R2 include the same as those described above for the hydrocarbon group R. The number of carbon atoms in the hydrocarbon group represented by ^R2 is preferably 1 to 30, more preferably 3 or more, and even more preferably 6 or more, and more preferably 28 or less, and even more preferably 26 or less.

When A ¹ and A ² are -(CH ₂ ) _q -OR ⁴ , examples of the hydrocarbon group represented by R ⁴ include the same as the hydrocarbon group R described above. The number of carbon atoms in the hydrocarbon group represented by R ⁴ is preferably 1 to 30, more preferably 3 or more, even more preferably 6 or more, more preferably 28 or less, even more preferably 26 or less. q is, for example, an integer of 1 to 5.

When A ¹ and A ² are thiophene rings, the alkoxy group which the thiophene ring may have as a substituent is represented by -OR ⁵¹ , where R ⁵¹ is a hydrocarbon group. Examples of the hydrocarbon group represented by R ⁵¹ include the same as the hydrocarbon group R described above. The number of carbon atoms in the hydrocarbon group represented by R ⁵¹ is preferably 1 to 30, more preferably 3 or more, even more preferably 6 or more, and more preferably 28 or less, even more preferably 26 or less.

The thioalkoxy group which the thiophene ring may have as a substituent is represented by ^-SR6 , where ^R6 is a hydrocarbon group. Examples of the hydrocarbon group represented by ^R6 include the same as the hydrocarbon group R described above. The number of carbon atoms in the hydrocarbon group represented by ^R6 is preferably 1 to 30, more preferably 3 or more, even more preferably 6 or more, and more preferably 28 or less, even more preferably 26 or less.

Examples of the hydrocarbon group that the thiophene ring may have as a substitute include the same as the hydrocarbon group R described above. The number of carbon atoms in the hydrocarbon group is preferably 1 to 30, more preferably 3 or more, even more preferably 6 or more, and more preferably 28 or less, even more preferably 26 or less.

The organosilyl group that may be substituted on the thiophene ring is a monovalent group in which one or more hydrocarbon groups are substituted on the Si atom. The hydrocarbon group substituted on the Si atom is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms.

The number of carbon atoms in the aliphatic hydrocarbon group substituting the Si atom is preferably 1 to 18, and more preferably 1 to 8. Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an isobutyl group, an octyl group, and an octadecyl group.

The number of carbon atoms in the aromatic hydrocarbon group substituting the Si atom is preferably 6 to 8, more preferably 6 to 7, and particularly preferably 6. An example of the aromatic hydrocarbon group is a phenyl group.

The hydrocarbon group to be substituted on the Si atom is preferably an aliphatic hydrocarbon group, more preferably a branched aliphatic hydrocarbon group, and particularly preferably an isopropyl group.

The number of hydrocarbon groups substituted on the Si atom is preferably 2 or more, and more preferably 3. When the number of hydrocarbon groups substituted on the Si atom is 2 or more, the hydrocarbon groups substituted on the Si atom may be different, but are preferably the same.

Specific examples of the case where the number of hydrocarbon groups substituting the Si atom is three include alkylsilyl groups such as trimethylsilyl, ethyldimethylsilyl, isopropyldimethylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, triethylsilyl, triisobutylsilyl, tripropylsilyl, tributylsilyl, dimethylphenylsilyl, and methyldiphenylsilyl; arylsilyl groups such as triphenylsilyl and tert-butylchlorodiphenylsilyl; and the like. Among these, alkylsilyl groups are preferred, with trimethylsilyl and triisopropylsilyl groups being particularly preferred.

When A ¹ and A ² are thiazole rings, examples of the hydrocarbon group that the thiazole ring may have as a substituent include the same as the above-described hydrocarbon group R. The number of carbon atoms in the hydrocarbon group is preferably 1 to 30, more preferably 3 or more, even more preferably 6 or more, and more preferably 28 or less, even more preferably 26 or less.

Organosilyl groups that may be substituted on the thiazole ring include those similar to the organosilyl groups described above.

When A ¹ and A ² are phenyl groups, examples of the alkoxy group which the phenyl group may have as a substituent include the same alkoxy groups as those explained above.

Examples of thioalkoxy groups with which a phenyl group may be substituted include the same thioalkoxy groups as described above.

Examples of the hydrocarbon group that the phenyl group may have as a substitute include the same as the hydrocarbon group R described above. The number of carbon atoms in the hydrocarbon group is preferably 1 to 30, more preferably 3 or more, even more preferably 6 or more, and more preferably 28 or less, even more preferably 26 or less.

Organosilyl groups with which the phenyl group may be substituted include those similar to the organosilyl groups described above.

Examples of halogen atoms that may be substituted on a phenyl group include the same as those described above.

Examples of halogenated alkyl groups that may be substituted on phenyl groups include groups in which some or all of the hydrogen atoms in a hydrocarbon group are substituted with halogen atoms, and among these, groups in which all of the hydrogen atoms are substituted with halogen atoms (perfluoroalkyl groups) are preferred. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine, and among these, fluorine is preferred. Examples of halogenated alkyl groups include trifluoromethyl groups, trifluoroethyl groups, and perfluoroethyl groups.

^D2 is a carbon atom, a silicon atom, or a nitrogen atom, and when ^D2 is a carbon atom or a silicon atom, n is 1, and when ^D2 is a nitrogen atom, n is 0.

It is preferable that the above formula (Ac-1) is any one of the following formulas (Ac-1-1) to (Ac-1-4).

The above formula (Ac-2) is preferably the following formula (Ac-2-1) or formula (Ac-2-2).

The above formula (Ac-3) is preferably the following formula (Ac-3-1) or formula (Ac-3-2).

It is preferable that the above formula (Ac-4) is any one of the following formulas (Ac-4-1) to (Ac-4-6).

The above formula (Ac-5) is preferably the following formula (Ac-5-1) or formula (Ac-5-2).

The above formula (Ac-6) is preferably the following formula (Ac-6-1).

It is preferable that the above formula (Ac-7) is any one of the following formulas (Ac-7-1) to (Ac-7-7).

It is preferable that the above formula (Ac-8) is any one of the following formulas (Ac-8-1) to (Ac-8-3).

The above formula (Ac-9) is preferably the following formula (Ac-9-1) or formula (Ac-9-2).

The above formula (Ac-10) is preferably the following formula (Ac-10-1).

The above formula (Ac-11) is preferably the following formula (Ac-11-1).

It is preferable that the above formula (Ac-12) is the following formula (Ac-12-1).

The above formula (Ac-13) is preferably the following formula (Ac-13-1).

The above formula (Ac-14) is preferably the following formula (Ac-14-1) or formula (Ac-14-2).

It is preferable that the above formula (Ac-15) is any one of the following formulas (Ac-15-1) to (Ac-15-3).

It is preferable that the above formula (Ac-16) is the following formula (Ac-16-1).

The above formula (Ac-17) is preferably the following formula (Ac-17-1).

The heteroaromatic fused ring type unit is preferably a unit represented by any one of the above formulas (Ac-1), (Ac-7), (Ac-10), (Ac-13), (Ac-15), or (Ac-17), more preferably a unit represented by any one of the above formulas (Ac-1-1) to (Ac-1-4), (Ac-7-1) to (Ac-7-7), (Ac-10-1), (Ac-13-1), (Ac-15-1), (Ac-15-2), or (Ac-17-1), and even more preferably a unit represented by any one of the above formulas (Ac-1-1), (Ac-7-2), (Ac-7-5), (Ac-10-1), (Ac-13-1), (Ac-15-1), (Ac-15-2), or (Ac-17-1). In particular, in the case of a low molecular weight compound, the heteroaromatic fused ring unit is preferably a unit represented by the above formula (Ac-15), more preferably a unit represented by the above formula (Ac-15-1) or formula (Ac-15-2), and even more preferably a unit represented by the above formula (Ac-15-1).

(2) Aromatic Fused Ring Unit An aromatic fused ring unit is a structural unit which has a fused ring structure, in which at least one of the rings is an aromatic ring, and the element constituting the ring is a carbon atom.

The number of rings constituting the condensed ring structure is not particularly limited, but is preferably, for example, 2 or more and 10 or less. The number of rings may be 3 or more and 8 or less.

The elements constituting the ring are carbon atoms, and do not include heteroatoms. Heteroatoms are atoms other than carbon atoms. The elements constituting the ring refer to all the elements constituting each ring structure contained in the condensed ring structure, and when at least one of the rings in the condensed ring structure is an aromatic ring, the aromatic ring essentially refers to an aromatic hydrocarbon ring.

The ring may have a substituent bonded thereto. Examples of the substituent include a halogen atom, a hydrocarbon group, an acyl group, an ester group, a halogenated alkyl group, and a cyano group.

Examples of halogen atoms include fluorine, chlorine, bromine, iodine, etc., with fluorine being preferred.

The hydrocarbon group is preferably an aliphatic hydrocarbon group, and may be a linear aliphatic hydrocarbon group, but is more preferably a branched aliphatic hydrocarbon group.

Examples of the hydrocarbon group include the same as the hydrocarbon group R described above. The number of carbon atoms in the hydrocarbon group is not particularly limited, and is preferably, for example, 1 to 30, more preferably 3 or more, even more preferably 6 or more, more preferably 28 or less, even more preferably 26 or less.

Examples of acyl groups include acetyl, propionyl, isopropionyl, butyryl, isobutyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, lauroyl, myristoyl, palmitoyl, stearoyl, oleoyl, linoleoyl, and linolenoyl groups.

Examples of ester groups include acetoxy groups, acyloxy groups, alkoxycarbonyl groups, and phosphate ester groups.

A halogenated alkyl group refers to a substituent in which some of the hydrogen atoms in the hydrocarbon group R described above are replaced with halogen atoms.

An example of an aromatic fused ring unit is a unit represented by the following formula (Ac-21):

[In formula (Ac-21), T ¹ and T ² each independently represent a single bond, -CH═CH-, -C≡C-, a thiophene ring optionally substituted with a hydrocarbon group, a thiazole ring optionally substituted with a hydrocarbon group, a pyridine ring optionally substituted with a hydrocarbon group, or a pyrazine ring optionally substituted with a hydrocarbon group.
^R2 is a hydrocarbon group, and ^R2 may be the same or different from each other.
When the unit represented by formula (Ac-21) is at the end of the compound, * may be a hydrogen atom.
When a compound has multiple acceptor units, T ¹ , T ² and R ² may each be the same between the units or different from each other.
The ring may have the above-mentioned substituents bonded thereto.

The explanation of T ¹ and T ² can be referred to in the above (1). T ¹ and T ² may be different from each other, but are preferably the same.

Examples of the hydrocarbon group represented by ^R2 include the same as those described above for the hydrocarbon group R. The number of carbon atoms in the hydrocarbon group is preferably 1 to 30, more preferably 3 or more, and even more preferably 6 or more, and more preferably 28 or less, and even more preferably 26 or less.

The above formula (Ac-21) is preferably the following formula (Ac-21-1).

(3) Monocyclic Unit The monocyclic unit is a structural unit that has an aromatic ring and does not have a condensed ring structure.

The aromatic ring may be an aromatic hydrocarbon ring, a heteroaromatic ring (sometimes called an aromatic heterocycle), or multiple aromatic rings bonded together via carbon atoms or heteroatoms.

The ring may have a substituent bonded thereto. Examples of the substituent include a halogen atom, a hydrocarbon group, an acyl group, an ester group, a halogenated alkyl group, and a cyano group.

Examples of halogen atoms include fluorine, chlorine, bromine, iodine, etc., with fluorine being preferred.

The hydrocarbon group is preferably an aliphatic hydrocarbon group, and may be a linear aliphatic hydrocarbon group, but is more preferably a branched aliphatic hydrocarbon group.

Examples of the hydrocarbon group include the same as the hydrocarbon group R described above. The number of carbon atoms in the hydrocarbon group is not particularly limited, and is preferably, for example, 1 to 30, more preferably 3 or more, even more preferably 6 or more, more preferably 28 or less, even more preferably 26 or less.

Examples of acyl groups include acetyl, propionyl, isopropionyl, butyryl, isobutyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, lauroyl, myristoyl, palmitoyl, stearoyl, oleoyl, linoleoyl, and linolenoyl groups.

Examples of ester groups include acetoxy groups, acyloxy groups, alkoxycarbonyl groups, and phosphate ester groups.

A halogenated alkyl group refers to a substituent in which some of the hydrogen atoms in the hydrocarbon group R described above are replaced with halogen atoms.

Examples of monocyclic units include units represented by the following formulas (Ac-31) to (Ac-33).

[In formulas (Ac-31) to (Ac-33), T ¹ and T ² each independently represent a single bond, -CH=CH-, -C≡C-, a thiophene ring optionally substituted with a hydrocarbon group, a thiazole ring optionally substituted with a hydrocarbon group, a pyridine ring optionally substituted with a hydrocarbon group, or a pyrazine ring optionally substituted with a hydrocarbon group.
When the units represented by formulae (Ac-31) to (Ac-33) are at the terminals of the compounds, * may be a hydrogen atom.
When a compound has a plurality of acceptor units, T ¹ and T ² may be the same or different between the units.
The ring may have the above-mentioned substituents bonded thereto.

The explanation of ^T1 and ^T2 can be referred to in (1) above.

The above formula (Ac-31) is preferably any one of the following formulas (Ac-31-1) to (Ac-31-3). The above formula (Ac-32) is preferably the following formula (Ac-32-1). The above formula (Ac-33) is preferably the following formula (Ac-33-1) or formula (Ac-33-2).

The compound of the present invention may be, for example, a polymeric compound having donor units and acceptor units as repeating units. In the case of a polymeric compound, the donor units and acceptor units may be arranged randomly, but are preferably arranged alternately.

The multiple donor units constituting the polymeric compound of the present invention contain at least one unit represented by the above formula (Do-A) and may further contain a unit represented by the following formula (Do-K). In the following formula (Do-K), * represents a bond. When a donor unit containing a unit represented by the following formula (Do-K) is at the end of the compound, * may be a hydrogen atom.

The unit represented by the above formula (Do-K) also has excellent electron donating properties. Furthermore, by including a unit represented by the above formula (Do-K), it is expected that the orientation will be improved due to intermolecular interactions, and the stability of the device will be improved due to the deepening of the LUMO. Therefore, by including a unit represented by the above formula (Do-K) in the donor unit, it is possible to appropriately adjust the performance and solubility.

When the entire donor units of the multiple donor units constituting the polymer compound of the present invention are taken as 100 mol%, the total of the units represented by the above formula (Do-A) and the units represented by the above formula (Do-K) is, for example, preferably 50 mol% or more, more preferably 70 mol% or more, and even more preferably 90 mol% or more. The entire donor units (100 mol%) may be units represented by the above formula (Do-A) and units represented by the above formula (Do-K).

When the multiple donor units constituting the polymer compound of the present invention contain both the units represented by the above formula (Do-A) and the units represented by the above formula (Do-K), the mixing ratio of the units represented by the above formula (Do-A) and the units represented by the above formula (Do-K) [units represented by formula (Do-A)/units represented by the above formula (Do-K)] is not particularly limited, but is preferably 3/7 to 7/3 in molar ratio. More preferably, the mixing ratio is 4/6 to 6/4 in molar ratio.

The compound of the present invention may be, for example, a low molecular weight compound having a total of two or three donor units and acceptor units. In the case of a low molecular weight compound, it is preferable that the compound is a trimer compound in which two acceptor units are linked to a donor unit.

The molecular weight of the compounds of the present invention depends on the molecular weight of the donor units and acceptor units that constitute the compound, and therefore, depending on the molecular weight of the donor units and acceptor units, the molecular weight of a low molecular weight compound may be larger than the molecular weight of a high molecular weight compound.

The weight average molecular weight (Mw) of the polymeric compound of the present invention is, for example, preferably 1500 or more, more preferably 3000 or more, and even more preferably 7000 or more. The upper limit of the weight average molecular weight (Mw) of the polymeric compound is not particularly limited, but may be, for example, 300,000 or less, or may be 200,000 or less.

The number average molecular weight (Mn) of the polymeric compound of the present invention is, for example, preferably 1000 or more, more preferably 2000 or more, and even more preferably 4000 or more. The upper limit of the number average molecular weight (Mn) of the polymeric compound is not particularly limited, but may be, for example, 300,000 or less, or may be 200,000 or less.

The molecular weight of the low molecular weight compound of the present invention is, for example, preferably 2500 or less. The molecular weight is more preferably 2300 or less, and even more preferably 1300 or less.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the compounds of the present invention can be calculated based on a calibration curve prepared using gel permeation chromatography with polystyrene as a standard sample.

The ionization energy of the compound of the present invention is preferably -4 eV or less, more preferably -4.5 eV or less, even more preferably -5 eV or less, and particularly preferably -5.1 eV or less. The lower limit of the ionization energy is not particularly limited, but is preferably -7 eV or more, more preferably -6.5 eV or more, and even more preferably -6.2 eV or more.

The present invention also includes an organic semiconductor material containing the above compound. For example, a donor unit containing a unit represented by the above formula (Do-A) has excellent electron donating properties, and therefore a compound having one or more donor units and one or more acceptor units, in which the donor units and the acceptor units are linked to each other, is useful as an organic semiconductor material. In addition, since the compound of the present invention contains a unit represented by the above formula (Do-A) that is spiro-converted into an acetal structure, it has good solubility in a solvent. Therefore, an organic semiconductor material containing the compound of the present invention has good solubility in a solvent, and the film quality of the film applied to the substrate is good, resulting in good electron mobility.

Examples of the solvent include halogenated organic solvents and non-halogenated organic solvents. The compound of the present invention has good solubility in solvents, particularly halogenated organic solvents and/or non-halogenated organic solvents. Examples of halogenated organic solvents include chloroform, tetrachloroethane, and chlorobenzene. Examples of non-halogenated organic solvents include toluene, 1-methylnaphthalene, and 2-methylnaphthalene. It is preferable that the compound of the present invention is soluble in at least a halogenated organic solvent.

The organic semiconductor material of the present invention can be preferably used as an n-type organic semiconductor material.

The present invention also includes an organic electronic device containing the organic semiconductor material. That is, the organic semiconductor material can be suitably used as a material for organic electronic devices, such as organic electroluminescence elements, organic thin-film transistor elements, organic photoelectric conversion elements, and organic thin-film solar cell modules.

Next, a method for producing the compounds of the present invention will be described.

The compound of the present invention can be produced, for example, by a coupling reaction between a compound in which tin having an organic substituent is bonded to a bond of a donor unit (hereinafter sometimes referred to as a donor raw material) and a compound in which a halogen atom is bonded to a bond of an acceptor unit (hereinafter sometimes referred to as an acceptor raw material) (hereinafter sometimes referred to as a coupling process).

The donor raw material can be a compound represented by the following formula (do-A) corresponding to the (Do-A) unit.

In the formula (do-A), R ^a is the same as defined above. In the compound represented by the formula (do-A), when R ^a is an ethylene group having 2 carbon atoms, the compound represented by the formula (do-A) is represented by the following formula (do-a).

R ¹¹ and R ¹² represent an organic substituent, and are each independently a hydrocarbon group. Among the multiple R ¹¹ , there may be the same R ¹¹ as each other or different R ¹¹ , and among the multiple R ¹² , there may be the same R ¹² as each other or different R ^12. Examples of the hydrocarbon group represented by R ¹¹ and R ¹² include the same as the hydrocarbon group R described above. The number of carbon atoms of the hydrocarbon group represented by R ¹¹ and R ¹² is preferably 1 to 10, more preferably 2 or more, even more preferably 3 or more, more preferably 5 or less, even more preferably 4 or less. R ¹¹ and R ¹² may be different from each other, but are preferably the same.

The compound represented by formula (do-A) can be produced based on the method described in JP 2009-215278 A.

The unit represented by formula (Do-K) can be synthesized by coupling the compound represented by formula (Do-A) and then changing the acetal structure to a ketone structure.

Examples of the halogen atom that bonds to the acceptor raw material include fluorine, chlorine, bromine, and iodine, with bromine being preferred.

Examples of acceptor raw materials include the above-mentioned (1) compounds in which a halogen atom is bonded to a bond of a heteroaromatic fused ring unit, (2) compounds in which a halogen atom is bonded to a bond of an aromatic fused ring unit, and (3) compounds in which a halogen atom is bonded to a bond of a monocyclic unit.

(1) Examples of compounds in which a halogen atom is bonded to a bond of a heteroaromatic fused ring unit include compounds represented by the following formulae (ac-1) to (ac-17). Note that in the following formulae (ac-1) to (ac-17), compounds in which the heteroaromatic fused ring unit has two bonds and a halogen atom Y is bonded to each bond are shown, but when a compound represented by the following formulae (ac-1) to (ac-17) is bonded to a donor unit as an end, a compound with one bond may be used.

In formulas (ac-1) to (ac-17), T ¹ , T ² , R ¹ , R ² , A ¹ , A ² , D ¹ , D ² and n are the same as defined above for formulas (Ac-1) to (Ac-17).
Y represents a halogen atom.
When two or more of the acceptor materials represented by formulae (ac-1) to (ac-17) are used in combination, T ¹ , T ² , R ¹ , R ² , A ¹ , A ² , D ¹ , D ² , and Y may be the same or different between the acceptor materials.
The ring may have the above-mentioned substituents bonded thereto.

Examples of halogen atoms Y include fluorine, chlorine, bromine, and iodine, with bromine being preferred.

(2) An example of a compound in which a halogen atom is bonded to a bond of an aromatic fused ring unit is a compound represented by the following formula (ac-21). Note that in the following formula (ac-21), a compound in which an aromatic fused ring unit has two bonds and a halogen atom is bonded to each bond is shown, but when a compound represented by the following (ac-21) is bonded to a donor unit as an end, a compound with one bond can be used.

[In formula (ac-21), T ¹ , T ² and R ² are the same as in formula (Ac-21).
Y represents a halogen atom.
When two or more kinds of acceptor materials represented by formula (ac-21) are used in combination, T ¹ , T ² , R ² and Y may be the same or different between the acceptor materials.
The ring may have the above-mentioned substituents bonded thereto.

Examples of halogen atoms Y include fluorine, chlorine, bromine, and iodine, with bromine being preferred.

(3) Examples of compounds in which a halogen atom is bonded to a bond of a monocyclic unit include compounds represented by the following formulae (ac-31) to (ac-33). Note that in the following formulae (ac-31) to (ac-33), compounds in which a monocyclic unit has two bonds and a halogen atom is bonded to each bond are shown, but when a compound represented by the following formulae (ac-31) to (ac-33) is bonded to a donor unit as an end, a compound with one bond may be used.

In formulas (ac-31) to (ac-33), ^T1 and ^T2 are the same as those explained above in formulas (Ac-31) to (Ac-33).
Y represents a halogen atom.
When two or more of the acceptor materials represented by formulae (ac-31) to (ac-33) are used in combination, T ¹ , T ² and Y may be the same or different between the acceptor materials.
The ring may have the above-mentioned substituents bonded thereto.

Examples of halogen atoms Y include fluorine, chlorine, bromine, and iodine, with bromine being preferred.

It is preferable to subject the organotin compound represented by the above formula (do-A) and the halide of the acceptor unit to a coupling reaction in the presence of a metal catalyst.

Examples of metal catalysts used in the coupling reaction 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. Among these, palladium-based catalysts are preferred. The valence of palladium contained in the palladium-based catalyst is not particularly limited, and may be zero or two valences.

Examples of palladium catalysts include palladium chloride (II), palladium bromide (II), palladium iodide (II), palladium oxide (II), palladium sulfide (II), palladium telluride (II), palladium hydroxide (II), palladium selenide (II), palladium cyanide (II), palladium acetate (II), palladium trifluoroacetate (II), palladium acetylacetonate (II), diacetate bis(triphenylphosphine)palladium (II), tetrakis(triphenylphosphine)palladium (0), dichlorobis(triphenylphosphine)palladium (II), dichlorobis(acetonitrile)palladium (II), dichlorobis(benzonitrile)palladium (II), dichloro[1,2-bis(diphenylphosphino)ethane]palladium (II), dichloro[1,3-bis(diphenylphosphino)propane]palladium (II), dichloro[1,4-bis(diphenylphosphino)propane]palladium (II), bis(diphenylphosphino)butane]palladium(II), dichloro[1,1-bis(diphenylphosphinoferrocene)]palladium(II), dichloro[1,1-bis(diphenylphosphino)ferrocene]palladium(II) dichloromethane adduct, bis(dibenzylideneacetone)palladium(0), tris(dibenzylideneacetone)dipalladium(0), tris(dibenzylideneacetone)dipalladium(0) chloroform adduct, dichloro[1 ,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(II), bis(tri-tert-butylphosphine)palladium(0), dichloro[2,5-norbornadiene]palladium(II), dichlorobis(ethylenediamine)palladium(II), dichloro(1,5-cyclooctadiene)palladium(II), dichlorobis(methyldiphenylphosphine)palladium(II). Of these, tris(dibenzylideneacetone)dipalladium(0) and tris(dibenzylideneacetone)dipalladium(0) chloroform adduct are preferably used.

Examples of copper-based catalysts include copper, copper halide compounds such as copper (I) fluoride, copper (I) chloride, copper (I) bromide, copper (I) iodide, copper (II) fluoride, copper (II) chloride, copper (II) bromide, and copper (II) iodide; copper (I) oxide, copper (I) sulfide, copper (II) oxide, copper (II) sulfide, copper (I) acetate, copper (II) acetate, and copper (II) sulfate.

Metal catalysts may be used alone or in combination of two or more types.

In the coupling step, the molar ratio of the organotin compound represented by the above formula (do-A) to the metal catalyst (organotin compound represented by the formula (do-A) : metal catalyst) is, for example, about 1:0.0001 to 1:0.5, preferably 1:0.001 to 1:0.4, more preferably 1:0.005 to 1:0.3, and even more preferably 1:0.01 to 1:0.2.

In the coupling step, a ligand may be coordinated to the metal catalyst. Examples of the ligand include trimethylphosphine, triethylphosphine, tri(n-butyl)phosphine, tri(isopropyl)phosphine, tri(tert-butyl)phosphine, bis(tert-butyl)methylphosphine, tricyclohexylphosphine, diphenyl(methyl)phosphine, triphenylphosphine, tris(o-tolyl)phosphine, tris(m-tolyl)phosphine, tris(p-tolyl)phosphine, tris(2-furyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(3-methoxyphenyl)phosphine, tris(4 -methoxyphenyl)phosphine, tri-tert-butylphosphonium tetrafluoroborate, 2-dicyclohexylphosphinobiphenyl, 2-dicyclohexylphosphino-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-t 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(dicyclohexylphosphino)ethane, 1,3-bis(dicyclohexylphosphino)propane, 1,4-bis(dicyclohexylphosphino)butane, 1,2-bis(diphenylphosphinoethylene, 1,2-bis(diphenylphosphino)ethylene, 1,3-bis(dicyclohexylphosphino)propane, 1,4-bis(dicyclohexylphosphino)butane, 1,2-bis(diphenylphosphinoethylene), , 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-1,10-phenanthroline, and bathophenanthroline. Among these, trimethylphosphine, triethylphosphine, tri(n-butyl)phosphine, tri(isopropyl)phosphine, tri(tert-butyl)phosphine, bis(tert-butyl)methylphosphine, tricyclohexylphosphine, diphenyl(methyl)phosphine, triphenylphosphine, tris(o-tolyl)phosphine, tris(m-tolyl)phosphine, tris(p-tolyl)phosphine, tris(2-furyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(3-methoxyphenyl)phosphine and tris(4-methoxyphenyl)phosphine are preferred, and tris(2-methoxyphenyl)phosphine is more preferred.

The ligands may be used alone or in a mixture of two or more types.

When a ligand is coordinated to a metal catalyst, the molar ratio of the metal catalyst to the ligand (metal catalyst:ligand) is, for example, about 1:0.5 to 1:10, preferably 1:1 to 1:8, more preferably 1:1 to 1:7, and even more preferably 1:1 to 1:5.

In the coupling step, it is preferable to use a solvent. The solvent is not particularly limited as long as it does not affect the reaction. For example, ether-based solvents, aromatic solvents, ester-based solvents, hydrocarbon-based solvents, halogen-based solvents, ketone-based solvents, amide-based solvents, nitrile-based solvents, sulfoxide-based solvents, sulfone-based solvents, etc. can be used.

Examples of ether solvents include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, methyltetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, tert-butyl methyl ether, and dioxane. Examples of aromatic solvents include benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, and tetralin. Examples of ester solvents include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, and butyl acetate. Examples of hydrocarbon solvents include pentane, hexane, heptane, octane, and decalin. Examples of halogen solvents include dichloromethane, chloroform, dichloroethane, and dichloropropane. Examples of ketone solvents include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and 1,3-dimethyl-3,4,5,6-tetrahydro-(1H)-pyrimidine. Examples of nitrile solvents include acetonitrile. Examples of sulfoxide solvents include dimethyl sulfoxide. Examples of sulfone solvents include sulfolane. Among these, aromatic solvents are preferred, and chlorobenzene is more preferred.

The solvent may be used alone or in a mixture of two or more types.

The amount of solvent used in the coupling step is, for example, about 1 mL or more and 150 mL or less per 1 g of the total of the organotin compound represented by the above formula (do-A) and the halide of the acceptor unit, preferably 5 mL or more, more preferably 8 mL or more, and preferably 100 mL or less, more preferably 80 mL or less.

The reaction temperature in the coupling step is not particularly limited, but from the viewpoint of increasing the reaction yield, it is preferably 0°C or higher and 200°C or lower, more preferably 30°C or higher, even more preferably 40°C or higher, more preferably 180°C or lower, even more preferably 150°C or lower.

After the coupling reaction, solid-liquid separation is performed according to a conventional method, and the recovered solid is washed to produce a compound having one or more donor units each containing a unit represented by the above formula (Do-A) and one or more acceptor units, in which the donor units and the acceptor units are linked to each other. When the compound is a polymeric compound, for example, a polymeric compound can be produced by performing solid-liquid separation, washing the recovered solid with a Soxhlet filter, and extracting it. When the compound is a low molecular weight compound, for example, a low molecular weight compound can be produced by removing the catalyst by celite filtration, and then dispersing and washing the solid obtained by concentration.

A polymeric compound further containing a unit represented by the above formula (Do-K) as one of the multiple donor units constituting the polymeric compound can be produced by heating and stirring a polymeric compound having a donor unit containing a unit represented by the above formula (Do-A) and an acceptor unit as repeating units in the presence of water under acidic conditions, thereby converting the acetal structure into a ketone structure.

This application claims the benefit of priority based on Japanese Patent Application No. 2021-200324, filed on December 9, 2021. The entire contents of the specification of the above-mentioned Japanese Patent Application No. 2021-200324 are incorporated by reference into this application.

The present invention will be explained in more detail below with reference to examples. However, the present invention is not limited to the following examples, and it is of course possible to carry out the invention with modifications within the scope of the above and below-mentioned aims, all of which are included in the technical scope of the present invention. In the following, "%" means "% by mass" unless otherwise specified.

In Experiment 1, a polymeric compound was synthesized, and in Experiment 2, a low molecular weight compound was synthesized, and their solubility in solvents and suitability for use as organic semiconductor materials were evaluated. The measurement methods used in the examples are as follows.

[Measurement method]
(NMR Spectroscopic Measurement)
NMR spectrum measurement was performed using a Varian "400-MR" and a Bruker "AVANCE NEO 600" as NMR spectrum measurement devices.
(UV-Visible Absorption Spectrum Measurement of Polymer Compounds)
The ultraviolet-visible absorption spectrum was measured in the state of a solution in which the polymer compound was dissolved in a solvent. Specifically, the polymer compound was dissolved in chloroform to a concentration of 0.03 g/L, and the ultraviolet-visible absorption spectrum in the state of the solution was measured using an ultraviolet-visible spectrometer (Shimadzu Corporation, "UV-3600i Plus") and a cell with an optical path length of 1 cm.
(UV-Visible Absorption Spectrum Measurement of Low Molecular Weight Compounds)
The UV-visible absorption spectrum was measured in the state of a solution in which the low molecular weight compound was dissolved in a solvent. Specifically, the low molecular weight compound was dissolved in chloroform to a concentration of 0.03 g/L, and the UV-visible absorption spectrum in the state of the solution was measured using a UV-visible spectrometer (Shimadzu Corporation, "UV-3600i Plus") and a cell with an optical path length of 1 cm. The measurement results are shown by a solid line.

Compound H was prepared based on Example 2 of JP 2009-215278 A. Compound H is 2,5-Bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bisthiazole-7,2'-[1,3]dioxolane], hereinafter sometimes referred to as Ac-CBTZ-SB.

[Experiment 1]
Example 1
In a 20 mL flask, 2,5-Bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bisthiazole-7,2'-[1,3]dioxolane] (Ac-CBTZ-SB, 217 mg, 0.265 mmol), 3,6-Bis(5-bromo-2-thienyl)-2,5-bis(2-hexyldecyl)-2,5 -dihydropyrrolo[3,4-c]pyrrole-1,4-dione (HD-DPP-DB, 242 mg, 0.265 mmol), tris(dibenzylideneacetone)dipalladium(0) chloroform adduct (10 mg, 9.7 μmol), tris(2-methoxyphenyl)phosphine (16 mg, 45 μmol) and chlorobenzene (8 mL) were added and reacted at 130° C. for 24 hours. After the reaction was completed, the reaction solution was added to methanol (45 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, and 110.3 mg (yield 42%) of a dark blue solid was obtained. As a result of NMR spectrum measurement, the obtained dark blue solid was P-Ac-CBTZ-HD-DPP (hereinafter, sometimes referred to as polymer type compound 1). At this time, the UV-visible absorption spectrum of the obtained polymeric compound 1 was measured in a solution state, and the measurement results were also taken into consideration. The UV-visible absorption spectrum measurement results are shown by a solid line in Figure 1. The horizontal axis indicates the measurement wavelength, and the vertical axis indicates absorbance (hereinafter, the same applies to the results of the UV-visible absorption spectrum measurement).

Example 2
In a 20 mL flask, 2,5-Bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bisthiazole-7,2'-[1,3]dioxolane] (Ac-CBTZ-SB, 100 mg, 0.122 mmol), 3,6-Bis(5-bromo-2-thienyl)-2,5-bis(3,7-dimethyloctyl)-2, 5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (DMO-DPP-DB, 90.1 mg, 0.122 mmol), tris(dibenzylideneacetone)dipalladium(0)chloroform adduct (5 mg, 4.8 μmol), tris(2-methoxyphenyl)phosphine (6.7 mg, 19 μmol) and chlorobenzene (4 mL) were added and reacted at 130° C. for 24 hours. After the reaction was completed, the reaction solution 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, and 36.7 mg of a dark blue solid was obtained (yield 37%). As a result of NMR spectrum measurement, the obtained dark blue solid was P-Ac-CBTZ-DMO-DPP (hereinafter, sometimes referred to as polymer type compound 2). At this time, the UV-visible absorption spectrum of the obtained polymer-type compound 2 was measured in a solution state, and the measurement result was also taken into consideration. The measurement result of the UV-visible absorption spectrum is shown by a solid line in FIG.

Example 3
In a 20 mL flask, 2,5-Bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bisthiazole-7,2'-[1,3]dioxolane] (Ac-CBTZ-SB, 100 mg, 0.122 mmol), 3,6-Bis(5-bromo-2-pyridinyl)-2,5-dihydro-2,5-bis(2-octyl dodecyl)pyrrolo[3,4-c]pyrrole-1,4-dione (ODD-DPPDPy-DB, 116 mg, 0.122 mmol), tris(dibenzylideneacetone)dipalladium(0)chloroform adduct (5 mg, 4.8 μmol), tris(2-methoxyphenyl)phosphine (6.7 mg, 19 μmol) and chlorobenzene (4 mL) were added and reacted at 130 ° C. for 24 hours. After the reaction was completed, the reaction solution 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, and 107.2 mg (yield 86%) of a dark blue solid was obtained. As a result of NMR spectrum measurement, the obtained dark blue solid was found to be P-Ac-CBTZ-ODD-DPPDPy (hereinafter, sometimes referred to as polymer type compound 3). At this time, the ultraviolet-visible absorption spectrum of the obtained polymer type compound 3 was measured in a solution state, and the measurement result was also taken into consideration. The measurement result of the ultraviolet-visible absorption spectrum is shown by a solid line in FIG. 3.

Example 4
In a 20 mL flask, 2,5-Bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bisthiazole-7,2'-[1,3]dioxolane] (Ac-CBTZ-SB, 100 mg, 0.122 mmol), 5,13-Dibromo-2,9-bis(2-octyldodecyl)anthra[2,1,9-def:6,5,10- d'e'f']diisoquinoline-1,3,8,10(2H,9H)-tetrone (ODD-PDI-DB, 135 mg, 0.122 mmol), tris(dibenzylideneacetone)dipalladium(0)chloroform adduct (5 mg, 4.8 μmol), tris(2-methoxyphenyl)phosphine (6.7 mg, 19 μmol) and chlorobenzene (4 mL) were added and reacted at 130° C. for 24 hours. After the reaction was completed, the reaction solution 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, and 48.4 mg of a brown solid was obtained (yield 39%). As a result of NMR spectrum measurement, the obtained brown solid was P-Ac-CBTZ-ODD-PDI (hereinafter, sometimes referred to as polymer type compound 4). At this time, the ultraviolet-visible absorption spectrum of the obtained polymer-type compound 4 was measured in a solution state, and the measurement result was also taken into consideration. The measurement result of the ultraviolet-visible absorption spectrum is shown by a solid line in FIG.

Example 5
In a 20 mL flask, add 2,5-Bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bisthiazole-7,2'-[1,3]dioxolane] (Ac-CBTZ-SB, 100 mg, 0.00 mg). 122 mmol), 1,3-Dibromo-5,7-bis(2-butyloctyl)-4H,8H-benzo[1 ,2-c:4,5-c']dithiophene-4,8-dione (BO-BDT-DB, 87.5 mg, 0.122 mmol), tris(dibenzylideneacetone)dipalladium(0) chloroform adduct (5 mg, 4.8 μmol), tris(2-methoxyphenyl)phosphine (7.5 mg, 21 μmol) and chlorobenzene (4 mL) were added and reacted at 130°C for 24 hours. After the reaction was completed, the reaction solution 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, and 22.9 mg of a brown solid was obtained (yield 29%). As a result of NMR spectrum measurement, the obtained brown solid was P-Ac-CBTZ-BO-BDT (hereinafter, sometimes referred to as polymer type compound 5). At this time, the ultraviolet-visible absorption spectrum of the obtained polymer-type compound 5 was measured in a solution state, and the measurement result was also taken into consideration. The measurement result of the ultraviolet-visible absorption spectrum is shown by a solid line in FIG.

Example 6
In a 20 mL flask, add 2,5-Bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bisthiazole-7,2'-[1,3]dioxolane] (Ac-CBTZ-SB, 100 mg, 0.00 mg). 122 mmol), 4,9-Dibromo-2,7-bis(2-octyldodecyl)benzo[lmn][3,8]p Henanthroline-1,3,6,8(2H,7H)-tetrone (ODD-NDI-DB, 120 mg, 0.122 mmol), tris(dibenzylideneacetone)dipalladium(0) chloroform adduct (5 mg, 4.8 μmol), tris(2-methoxyphenyl)phosphine (7.5 mg, 21 μmol) and chlorobenzene (4 mL) were added and reacted at 130° C. for 24 hours. After the reaction was completed, the reaction solution 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, and 8.8 mg (yield 8%) of a dark blue solid was obtained. As a result of NMR spectrum measurement, the obtained dark blue solid was P-Ac-CBTZ-ODD-NDI (hereinafter, sometimes referred to as polymer type compound 6). At this time, the ultraviolet-visible absorption spectrum of the obtained polymer-type compound 6 was measured in a solution state, and the measurement result was also taken into consideration. The measurement result of the ultraviolet-visible absorption spectrum is shown by a solid line in FIG.

(Example 7)
In a 20 mL flask, add 2,5-Bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bisthiazole-7,2'-[1,3]dioxolane] (Ac-CBTZ-SB, 100 mg, 0.00 mg). 122 mmol), 6-Bromo-3-(5-bromo-2,3-dihydro-3-oxo-2-ethylhexyl-1H-isoindol-1-y lidene)-2,3-dihydro-2-ethylhexyl-1H-Isoindol-1-one (EH-IND-DB, 78.6 mg, 0.122 mmol), tris(dibenzylideneacetone)dipalladium(0) chloroform adduct (5 mg, 4.8 μmol), tris(2-methoxyphenyl)phosphine (6.7 mg, 19 μmol) and chlorobenzene (4 mL) were added and reacted at 130° C. for 24 hours. After the reaction was completed, the reaction solution was added to methanol (30 mL) and the precipitated solid was collected by filtration, and the obtained solid was washed with a Soxhlet (methanol, acetone, hexane). Then, as a result of Soxhlet extraction (chloroform), 23.4 mg of a navy blue solid was obtained (yield 34%). As a result of NMR spectrum measurement, the obtained dark blue solid was found to be P-Ac-CBTZ-EH-IND (hereinafter, sometimes referred to as polymer-type compound 7). At this time, the ultraviolet-visible absorption spectrum of the obtained polymer-type compound 7 was measured in a solution state, and the measurement result was also taken into consideration. The measurement result of the ultraviolet-visible absorption spectrum is shown by a solid line in FIG. 7.

(Example 8)
In a 20 mL flask, 2,5-Bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bisthiazole-7,2'-[1,3]dioxolane] (Ac-CBTZ-SB, 100 mg, 0.122 mmol), 4,9-Dibromo-2,7-bis(2-octyldodecyl)benzo[lmn][3,8]phenanthrolin-1, 3,6,8(2H,7H)-tetrone (ODD-NDI-DB, 121.4 mg, 0.122 mmol), tris(dibenzylideneacetone)dipalladium(0) chloroform adduct (5 mg, 4.8 μmol), tris(2-methoxyphenyl)phosphine (7.5 mg, 21 μmol) and chlorobenzene (4 mL) were added, and the temperature was raised stepwise from 50° C. to 100° C. while checking the solubility, and the reaction was carried out at 100° C. for 15 hours. The temperature was raised from 50° C. to 100° C. while checking the solubility, and the temperature was held at 50° C. for 1 hour, raised to 65° C. and held for 1 hour, raised to 75° C. and held for 1 hour, raised to 85° C. and held for 1 hour, and then raised to 100° C. After the reaction was completed, the reaction solution 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) yielded 43.2 mg (41% yield) of a dark blue solid. NMR spectrum measurement revealed that the dark blue solid was P-Ac-CBTZ-ODD-NDI (hereinafter, sometimes referred to as polymeric compound 8). At this time, the UV-visible absorption spectrum of the obtained polymeric compound 8 was measured in a solution state, and the measurement results were also taken into consideration. The measurement results of the UV-visible absorption spectrum are shown by a solid line in FIG. 8.

Example 9
In a 20 mL flask, add 2,5-Bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bisthiazole-7,2'-[1,3]dioxolane] (Ac-CBTZ-SB, 100 mg, 0.00 mg). 122 mmol), 4,9-Dibromo-2,7-bis(2-decyltetradecyl)benzo[lmn][3,8 ]phenanthroline-1,3,6,8(2H,7H)-tetrone (TD-NDI-DB, 134 mg, 0.122 mmol), tris(dibenzylideneacetone)dipalladium(0) chloroform adduct (5 mg, 4.8 μmol), tris(2-methoxyphenyl)phosphine (7.5 mg, 21 μmol) and chlorobenzene (4 mL) were added and reacted at 130° C. for 15 hours. After the reaction was completed, the reaction solution 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, and 42.4 mg of a dark blue solid was obtained (yield 36%). As a result of NMR spectrum measurement, the obtained dark blue solid was P-Ac-CBTZ-TD-NDI (hereinafter, sometimes referred to as polymer type compound 9). At this time, the UV-visible absorption spectrum of the obtained polymer compound 9 was measured in a solution state, and the measurement result was also taken into consideration. The measurement result of the UV-visible absorption spectrum is shown by a solid line in FIG.

Example 10
In a 20 mL flask, 2,5-Bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bisthiazole-7,2'-[1,3]dioxolane] (Ac-CBTZ-SB, 217 mg, 0.265 mmol), 3,6-Bis(5-bromo-2-thienyl)-2,5-bis(2-hexyldecyl)-2,5 -dihydropyrrolo[3,4-c]pyrrole-1,4-dione (HD-DPP-DB, 242 mg, 0.265 mmol), tris(dibenzylideneacetone)dipalladium(0)chloroform adduct (10 mg, 9.7 μmol), tris(2-methoxyphenyl)phosphine (16 mg, 45 μmol) and chlorobenzene (8 mL) were added and reacted at 130° C. for 24 hours. After the reaction was completed, the reaction solution was added to methanol (45 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, and 110.3 mg (yield 42%) of a dark blue solid was obtained. As a result of NMR spectrum measurement, the obtained dark blue solid was P-Ac-CBTZ-HD-DPP.

A portion of the dark blue solid obtained (41.2 mg, 41.9 μmol) was dissolved in chloroform, and methanesulfonic acid and water were added in large excess, followed by stirring at 60°C for 15 hours. After stirring, the mixture was concentrated, methanol was added, and the mixture was filtered, yielding 26.1 mg of a dark blue solid (yield 64%). NMR spectrum measurement revealed that the dark blue solid obtained was P-Ac-CBTZ-HD-DPP/P-CBTZ-HD-DPP (50/50) (hereinafter sometimes referred to as polymeric compound 10). At this time, the ultraviolet-visible absorption spectrum of the obtained polymeric compound 10 was measured in solution, and the measurement results were also taken into consideration. The measurement results of the ultraviolet-visible absorption spectrum are shown by a solid line in Figure 10.

(Example 11)
As a microwave reaction apparatus, Biotage's "Initiator+ Microwave System 356700" was used, and 2,5-Bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bisthiazole-7,2'-[1,3]dioxolane] (Ac-CBTZ-SB, 100 mg, 0.122 mmol), 1,3-Dibromo-5-(2-decyltetradecyl)- 4H-thieno[3,4-c]pyrrole-4,6(5H)-dione (TD-IMTH-DB, 79.0 mg, 0.122 mmol), tris(dibenzylideneacetone)dipalladium(0) chloroform adduct (5 mg, 4.8 μmol), tris(2-methoxyphenyl)phosphine (7.5 mg, 21 μmol) and chlorobenzene (4 mL) were added and the MW reaction was carried out at 180° C. for 10 minutes. After the reaction was completed, the reaction solution 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 63.7 mg of a dark blue solid (yield 89%). As a result of NMR spectrum measurement, the obtained dark blue solid was P-Ac-CBTZ-TD-IMTH (hereinafter, sometimes referred to as polymer type compound 11). At this time, the UV-visible absorption spectrum of the obtained polymer compound 11 was measured in a solution state, and the measurement result was also taken into consideration. The measurement result of the UV-visible absorption spectrum is shown by a solid line in FIG.

Example 12
In a 20 mL flask, add 2,5-Bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bisthiazole-7,2'-[1,3]dioxolane] (Ac-CBTZ-SB, 100 mg, 0.00 mg). 122 mmol), 4,9-Dibromo-2,7-bis(2-decyltetradecyl)benzo[lmn][3,8]phenanthroline -1,3,6,8(2H,7H)-tetrone (TD-NDI-DB, 134 mg, 0.122 mmol), tris(dibenzylideneacetone)dipalladium(0) chloroform adduct (5 mg, 4.8 μmol), tris(2-methoxyphenyl)phosphine (7.5 mg, 21 μmol) and chlorobenzene (4 mL) were added, and the temperature was raised stepwise from 50°C to 100°C while checking the solubility, and the reaction was carried out at 100°C for 15 hours. The temperature was raised from 50°C to 100°C by holding at 50°C for 1 hour while checking the solubility, raising the temperature to 70°C and holding for 1 hour, and then raising the temperature to 100°C. After the reaction was completed, the reaction solution 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) yielded 125 mg (yield 91%) of a dark blue solid. NMR spectrum measurement revealed that the dark blue solid was P-Ac-CBTZ-TD-NDI (hereinafter sometimes referred to as polymeric compound 12). At this time, the UV-visible absorption spectrum of the obtained polymeric compound 12 was measured in a solution state, and the measurement results were also taken into consideration. The measurement results of the UV-visible absorption spectrum are shown by a solid line in FIG. 12.

(Example 13)
In a 20 mL flask, add 2,5-Bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bisthiazole-7,2'-[1,3]dioxolane] (Ac-CBTZ-SB, 300 mg, 0.00 mg). 367 mmol), 4,9-Dibromo-2,7-bis(2-decyltetradecyl)benzo[lmn][3,8]p Henanthroline-1,3,6,8(2H,7H)-tetrone (TD-NDI-DB, 402 mg, 0.367 mmol), tris(dibenzylideneacetone)dipalladium(0)chloroform adduct (15 mg, 14.7 μmol), tris(2-methoxyphenyl)phosphine (22.0 mg, 62 μmol) and chlorobenzene (12 mL) were added and reacted at 130° C. for 24 hours. After the reaction was completed, the reaction solution was added to methanol (90 mL) and the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane, chloroform). The solid inside the Soxhlet cylindrical filter was then taken out and dissolved again in chloroform by ultrasonic and stirring operations, resulting in 285.3 mg of a dark blue solid (70% yield). As a result of NMR spectrum measurement of the chloroform soluble portion, the obtained dark blue solid was found to be P-Ac-CBTZ-TD-NDI (hereinafter, sometimes referred to as polymeric compound 13). At this time, the ultraviolet-visible absorption spectrum measurement of the obtained polymeric compound 13 was performed in a solution state, and the measurement result was also taken into consideration. The measurement result of the ultraviolet-visible absorption spectrum is shown by a solid line in FIG.

(Example 14)
In a 20 mL flask, 4-bromo-2,7-bis(2-decyltetradecyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetrone (TD-NDI-DB, 299.2 mg, 0.2727 mmol), 2-(tributylstannyl)-thiazole (Bu3Sn-Thz, 299.1 mg, 0.799 mmol), tetrakistriphenylphosphinepalladium(0) (34 mg, 30 μmol) and toluene (6.4 mL) were added and reacted at 110° C. for 16 hours. After completion of the reaction, the mixture was washed with brine, extracted with toluene and concentrated. Further, methanol (10 mL) was added, and the precipitated solid was collected by filtration to obtain 247.9 mg of a yellow solid (yield: 82.2%). As a result of NMR spectrum measurement, the obtained yellow solid was TD-NDI-2Thz (hereinafter, sometimes referred to as Compound 14).
^1H NMR (400MHz, _CDCl3 ): 8.915 (s, 1H), 8.018 (d, 2H), 7.645 (d, 2H), 4.024 (d, 4H), 1.895 (bs, 2H), 1.199 (bs, 80H), 0.847 (t, 12H)

(Example 15)
Compound 14 (TD-NDI-2Thz, 18.1 mg, 0.02 mmol) obtained in Example 14 and tetrahydrofuran (0.25 mL) were added to a 20 mL flask, cooled to -78 ° C., and then normal butyl lithium (1.6 mol / L, 0.05 mL) was added and reacted for 1 hour. Then, 1,3-Dibromo-5,5-dimethylhydantoin (DBH, 15.51 mg, 0.06 mmol) was added and reacted at room temperature for 1 hour. After the reaction was completed, the mixture was extracted with ethyl acetate, washed with sodium sulfite and water, and the organic layer was dried over magnesium sulfate and then concentrated. Column chromatography (chloroform / ethyl acetate = 10), methanol (10 mL) was added, and the precipitated solid was collected by filtration. As a result, a yellow solid was obtained in 15 mg (yield 72.5%). As a result of NMR spectrum measurement, the obtained yellow solid was found to be TD-NDI-2Thz-Br (hereinafter, sometimes referred to as compound 15).
^1H NMR (400MHz, _CDCl3 ): 9.140 (s, 2H), 7.931 (s, 2H), 4.085 (d, 4H), 1.227-1.186 (bs, 80H), 0.855 (t, 12H)

Example 16
In a 20 mL flask, 2,5-Bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bisthiazole-7,2'-[1,3]dioxolane] (Ac-CBTZ-SB), compound 15 obtained in Example 15, a catalytic amount of tris(dibenzylideneacetone)dipalladium(0) chloroform adduct, and tris(2-methoxyphenyl)phosphine as a ligand to be coordinated to the catalyst are heated in chlorobenzene to react. The molar ratio of Ac-CBTZ-SB to compound 15 is 1:1. P-Ac-CBTZ-TD-NDI-2Thz (hereinafter sometimes referred to as polymer compound 16) is isolated from the reaction solution.

As is clear from Figures 1 to 13, the polymeric compounds 1 to 13 of the present invention can absorb light in the long wavelength region.

Next, the molecular weights of the obtained polymeric compounds 1 to 13 were measured. Gel permeation chromatography (GPC) was used for measuring the molecular weight. In the measurement, the polymeric compound was dissolved in a mobile phase solvent (chloroform) to a concentration of 0.8 g/L, and the measurement was carried out under the following conditions. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymeric compound were calculated by conversion based on a calibration curve prepared using polystyrene as a standard sample. The GPC conditions in the measurement were as follows.
Apparatus: High-performance liquid chromatograph L-2420/L-2130 (Hitachi High-Tech Corporation)
Mobile phase: chloroform flow rate 1 mL/min
Column: Shodex GPC K-803L (Showa Denko K.K.)

The molecular weight measurement results are shown in Table 1 below. In addition, when two peaks indicating molecular weight were detected, the two molecular weights are shown in Table 1 below.

Next, the solubility of the obtained polymeric compounds 1 to 13 in a solvent was evaluated. The solvent used was chloroform, chlorobenzene, or toluene. When chloroform was used, chloroform was added so that the concentration of the polymeric compound was 5% by mass, and the mixture was heated at 60°C for 30 minutes. When chlorobenzene was used, chlorobenzene was added at room temperature so that the polymeric compounds 1 to 12 were 1 mg/mL. For polymeric compound 13, chlorobenzene was added at 1 mg/mL, and the mixture was heated at 130°C for 60 minutes. When toluene was used, toluene was added at room temperature so that the polymeric compounds 1 to 9, 11, and 12 were 1 mg/mL. For polymeric compound 13, toluene was added at 1 mg/mL, and the mixture was heated at 100°C for 60 minutes. For polymeric compound 10, evaluation using toluene was not performed.

After the addition of the solvent or after heating, whether the polymer compound was dissolved was visually observed and evaluated according to the following criteria. The evaluation results are shown in Table 1 below.
<Evaluation criteria>
A: Dissolved in the solvent.
Δ: A part of the polymer compound remained undissolved.
×: Not dissolved in the solvent.

Next, the ionization energy, band gap, electron mobility μe, threshold voltage, and on/off ratio were measured using the obtained polymer compounds 1 to 13. In addition, the LUMO value was calculated from the ionization energy value and the band gap value.

(Measurement of ionization energy)
The polymer compound was dissolved in chlorobenzene to a concentration of 8 mg/mL, and the resulting solution was drop-cast onto an ITO substrate to form a film. The ionization energy (eV) of this film was measured at room temperature and under reduced pressure (0.1 Pa or less) using an ionization energy measuring device (manufactured by Bunkoukeiki Co., Ltd., "BIP-KV202GD"). The measured ionization energy values (eV) are shown in Table 1 below.

(Band Gap)
The band gap of the polymer compound was calculated based on the rise of UV (ultraviolet-visible absorption spectrum) measurement of a thin film containing the polymer compound. That is, the polymer compound was dissolved in chlorobenzene so that the concentration was 8 mg/mL, and the obtained solution was spin-coated on a glass substrate (2.5 cm x 2.5 cm square, 0.8 to 1.0 mm thick) to form a thin film. UV measurement was performed on this thin film at room temperature and normal pressure using an ultraviolet-visible spectrometer (Shimadzu Corporation, "UV-3600i Plus"). The results of the UV measurement measured in the thin film state are shown by dotted lines in Figures 1 to 5 and Figures 7 to 13. Note that, for Example 6, UV measurement was not performed in the thin film state. In addition, the band gap (eV) was calculated based on the rise of UV. The calculated band gap values (eV) are shown in Table 1 below.

The band gap calculation method will be explained using FIG. 14. FIG. 14 is a schematic diagram created to explain the band gap calculation method, and is a schematic diagram in which auxiliary lines are drawn on the ultraviolet-visible absorption spectrum obtained by performing UV measurement of a thin film containing polymer-type compound 9. For the ultraviolet-visible absorption spectrum measured in the 200 nm to 1000 nm region, as shown in FIG. 14, a tangent line was drawn from near the peak top on the long wavelength side of the peak derived from the compound, and the rising wavelength λ was obtained from the intersection of the tangent line and the horizontal axis (wavelength). That is, a tangent line was drawn as an auxiliary line to the curve of the region in which absorption increases from the high wavelength side to the low wavelength side in the curve of the peak showing maximum absorption, and the wavelength at the intersection of this tangent line and the horizontal axis showing absorbance 0 was read, and this wavelength was taken as the UV rising wavelength λ. In the case of polymer-type compound 9 shown in FIG. 14, the rising wavelength λ is 841 nm.

If the band gap (energy gap) between the HOMO and LUMO is E, the Planck constant is h, and the speed of light in a vacuum is c, the following relationship holds:
E = hc/λ

Here, Planck's constant h is 6.626×10 ⁻³⁴ , and the speed of light c in a vacuum is 2.998×10 ⁸ , so when 841 is substituted for the rising wavelength λ, the band gap E becomes 1.47 eV as shown in the following formula.
E=1239.8/841≒1.47 (eV)

On the other hand, since the ionization energy value (HOMO value) is −5.96 eV, the LUMO value is −4.49 eV as shown below.
LUMO=-5.96+1.47=-4.49 (eV)

The LUMO values (eV) calculated based on the ionization energies and band gaps shown in Table 1 below are shown in Table 1 below.

(Measurement of electron mobility, threshold voltage, on/off ratio)
The silicon substrate treated with ozone was treated with hexamethyldisilazane (HMDS) or octadecyltrichlorosilane (ODTS). A chloroform solution containing a polymeric compound at a concentration of 0.5% by mass (7.4 mg/mL) was spin-coated on the treated substrate surface to prepare an organic field-effect transistor (OFET) element. For Example 13, chlorobenzene was used instead of chloroform, and a chlorobenzene solution containing a polymeric compound at a concentration of 0.5% by mass was spin-coated. The prepared OFET element was annealed at 100° C. for 1 hour, allowed to cool, annealed at 150° C. for 1 hour, and allowed to cool, after which the Id-Vg characteristics were measured. The Id-Vg characteristics were measured under a nitrogen atmosphere or under vacuum. The Id-Vg characteristics were measured using a Keithley Instruments 4200-SCS, and the channel length of the organic semiconductor element was 25 μm and the channel width was 294 mm. The Id-Vg characteristics were measured to determine the electron mobility μe (cm ² /Vs), threshold voltage Vth (V), and on/off ratio (I _on /I _off ). The Id-Vg characteristics measured after annealing at 150° C. for 1 hour are shown in Table 1 below. Note that "-" in the columns for ionization energy, band gap, and LUMO in Table 1 below indicates that the test was not performed.

From Table 1, the following can be considered. The polymeric compounds 1 to 13 of the present invention have one or more donor units and acceptor units having a specific structure, and are compounds in which the donor units and acceptor units are linked to each other, and in particular, are compounds having donor units and acceptor units as repeating units. The polymeric compounds 1 to 13 of the present invention had good solubility in solvents, particularly halogen-based organic solvents. The polymeric compounds 1 to 13 of the present invention can also be preferably used as organic semiconductor materials. The polymeric compounds 1 to 13 of the present invention also showed good electron mobility even after annealing at 150°C. As for the polymeric compound 16 obtained in Example 16, since it contains a thiazole unit, the distortion between the donor units and the acceptor units is reduced, resulting in a structure close to a plane, making it easier for the molecules to align with each other, and it is expected that the crystallinity and electron mobility will increase.

[Experiment 2]
(Example 21)
In a 20 mL flask, 2,5-Bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bisthiazole-7,2'-[1,3]dioxolane] (Ac-CBTZ-SB, 60 mg, 0.0735 mmol), 4-bromo-2,7-dibutyl-benzo[lmn][3,8]phenanthro Line-1,3,6,8(2H,7H)-tetrone (BU-NDI-MB, 67.3 mg, 0.147 mmol), tris(dibenzylideneacetone)dipalladium(0) chloroform adduct (6 mg, 5.9 μmol), tris(2-methoxyphenyl)phosphine (8.9 mg, 25.0 μmol) and chlorobenzene (4 mL) were added and reacted at 130° C. for 16 hours. After the reaction was completed, the mixture was filtered through Celite and concentrated. Furthermore, chloroform (3 mL) and methanol (7 mL) were added, and the precipitated solid was collected by filtration, resulting in 52.7 mg of a dark blue solid (yield 72.3%). As a result of NMR spectrum measurement, the dark blue solid obtained was Ac-CBTZ-2(Bu-NDI) (hereinafter, sometimes referred to as low molecular weight compound 1). The ultraviolet-visible absorption spectrum of the obtained low molecular weight compound 1 was measured in a solution state, and the measurement result is shown by a solid line in FIG.
^1H NMR (400MHz, CDCl ₃ ): 9.075 (s, 2H), 8.847 (d, 2H), 8.826 (d, 2H), 4.596 (s, 4H), 4.216-4.134 (m, 8H), 1.771-1.597 (m, 8H), 1.407-1.201 ( m, 16H), 0.862 (t, 12H)

(Example 22)
In a 20 mL flask, add 2,5-Bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bisthiazole-7,2'-[1,3]dioxolane](Ac-CBTZ-SB, 60mg, 0.0 735 mmol), 4-bromo-2,7-bis(2-ethylhexyl)-benzo[lmn][3,8]phena nthrone-1,3,6,8(2H,7H)-tetrone (EH-NDI-MB, 84.3 mg, 0.147 mmol), tris(dibenzylideneacetone)dipalladium(0) chloroform adduct (6 mg, 5.9 μmol), tris(2-methoxyphenyl)phosphine (8.9 mg, 25.0 μmol) and chlorobenzene (4 mL) were added and reacted at 130° C. for 16 hours. After the reaction was completed, the mixture was filtered through Celite and concentrated. Methanol (10 mL) was further added, and the precipitated solid was collected by filtration, resulting in 40.1 mg of a dark blue solid (yield 44.2%). As a result of NMR spectrum measurement, the dark blue solid obtained was Ac-CBTZ-2(EH-NDI) (hereinafter, sometimes referred to as low molecular weight compound 2).
^1H NMR (400MHz, _CDCl3 ): 9.367 (s, 2H), 8.818 (d, 2H), 8.788 (d, 2H), 4.597 (s, 4H), 4.218-4.139 (m, 8H), 1.407-1.201 (m, 49H), 0.951-0.864 (m, 32H)

(Example 23)
In a 20 mL flask, 2,5-Bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bisthiazole-7,2'-[1,3]dioxolane] (Ac-CBTZ-SB, 60 mg, 0.0735 mmol), 4-bromo-2,7-dihexyl-benzo[lmn][3,8]phenanthrol ine-1,3,6,8(2H,7H)-tetrone (Hex-NDI-MB, 75.3 mg, 0.147 mmol), tris(dibenzylideneacetone)dipalladium(0) chloroform adduct (6 mg, 5.9 μmol), tris(2-methoxyphenyl)phosphine (8.9 mg, 25.0 μmol) and chlorobenzene (4 mL) were added and reacted at 130° C. for 16 hours. After the reaction was completed, the mixture was filtered through Celite and concentrated. Methanol (7 mL) was further added, and the precipitated solid was collected by filtration, resulting in 59.9 mg of a dark blue solid (yield 73.3%). NMR spectrum measurement revealed that the dark blue solid was Ac-CBTZ-2(Hex-NDI) (hereinafter, sometimes referred to as low molecular weight compound 3). The ultraviolet-visible absorption spectrum of the obtained low molecular weight compound 3 was measured in a solution state, and the measurement result is shown by a solid line in FIG.
^1H NMR (400MHz, _CDCl3 ): 9.334 (s, 2H), 8.821 (d, 2H), 8.786 (d, 2H), 4.596 (s, 4H), 4.218 (quin, 8H), 1.836-1.588 (m, 4H), 1.547-1.318 (m , 32H), 0.894(t, 12H)

(Example 24)
In a 20 mL flask, 2,5-Bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bisthiazole-7,2'-[1,3]dioxolane] (Ac-CBTZ-SB, 60 mg, 0.0735 mmol), 4-bromo-2,7-dioctyl-benzo[lmn][3,8]phenanthrol ine-1,3,6,8(2H,7H)-tetrone (n-o-NDI-MB, 83.5 mg, 0.147 mmol), tris(dibenzylideneacetone)dipalladium(0) chloroform adduct (6 mg, 5.9 μmol), tris(2-methoxyphenyl)phosphine (8.9 mg, 25.0 μmol) and chlorobenzene (4 mL) were added and reacted at 130° C. for 16 hours. After the reaction was completed, the mixture was filtered through Celite and concentrated. Methanol (7 mL) was further added, and the precipitated solid was collected by filtration, resulting in 71.7 mg (yield 80%) of a dark blue solid. As a result of NMR spectrum measurement, the dark blue solid obtained was Ac-CBTZ-2(n-o-NDI) (hereinafter, sometimes referred to as low molecular weight compound 4). The UV-visible absorption spectrum of the obtained low molecular weight compound 4 was measured in a solution state, and the measurement result is shown by the solid line in FIG.
^１ Ｈ ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ _３ ）：９．３４１（ｓ，２Ｈ），８．８３２（ｄ，２Ｈ），８．７８７（ｄ，２Ｈ），４．５９６（ｓ，４Ｈ），４．２１８（ｑｕｉｎ，８Ｈ），１．５３５－１．１５３（ｍ，４８Ｈ），０．８２６（ｔ，１２Ｈ）

(Example 25)
In a 20 mL flask, 2,5-Bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bisthiazole-7,2'-[1,3]dioxolane] (Ac-CBTZ-SB, 60 mg, 0.0735 mmol), 4-bromo-2,7- Bis(2-decyltetradecyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetrone (DMO-NDI-MB, 91.2 mg, 0.147 mmol), tris(dibenzylideneacetone)dipalladium(0)chloroform adduct (6 mg, 5.9 μmol), tris(2-methoxyphenyl)phosphine (8.9 mg, 25.0 μmol) and chlorobenzene (4 mL) were added and reacted at 130 ° C. for 16 hours. After the reaction was completed, celite filtration was performed and the mixture was concentrated. Furthermore, methanol (7 mL) was added, and the precipitated solid was filtered off, resulting in the production of 85.9 mg (yield 95.5%) of a dark blue solid. As a result of NMR spectrum measurement, the obtained dark blue solid was found to be Ac-CBTZ-2(DMO-NDI) (hereinafter, sometimes referred to as low molecular weight compound 5). The ultraviolet-visible absorption spectrum measurement of the obtained low molecular weight compound 5 was carried out in a solution state, and the measurement result is shown by a solid line in FIG.
^1H NMR (400MHz, _CDCl3 ): 9.355 (s, 2H), 8.814 (d, 2H), 8.778 (d, 2H), 4.599 (s, 4H), 4.214 (quin, 8H), 1.505-1.123 (m, 48H), 1.008 (t, 24H) ,0.849(t,12H)

(Example 26)
In a 20 mL flask, 2,5-Bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bisthiazole-7,2'-[1,3]dioxolane] (Ac-CBTZ-SB, 60 mg, 0.0735 mmol), 4-bromo-2,7-didecylbenzo[lmn][3,8]phenanthrol ine-1,3,6,8(2H,7H)-tetrone (DE-NDI-MB, 92.5 mg, 0.147 mmol), tris(dibenzylideneacetone)dipalladium(0) chloroform adduct (6 mg, 5.9 μmol), tris(2-methoxyphenyl)phosphine (8.9 mg, 25.0 μmol) and chlorobenzene (4 mL) were added and reacted at 130° C. for 16 hours. After the reaction was completed, the mixture was filtered through Celite and concentrated. Methanol (7 mL) was further added, and the precipitated solid was collected by filtration, resulting in 57.5 mg of a dark blue solid (yield 71.0%). As a result of NMR spectrum measurement, the dark blue solid obtained was Ac-CBTZ-2(DE-NDI) (hereinafter, sometimes referred to as low molecular weight compound 6). The UV-visible absorption spectrum of the obtained low molecular weight compound 6 was measured in a solution state, and the measurement result is shown by the solid line in FIG.
^1H NMR (400MHz, _CDCl3 ): 9.341 (s, 2H), 8.820 (d, 2H), 8.785 (d, 2H), 4.596 (s, 4H), 4.180 (quin, 4H), 1.719 (bs, 4H), 1.423-1.340 (m, 56H) ,0.859(t,12H)

(Example 27)
In a 20 mL flask, 2,5-Bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bisthiazole-7,2'-[1,3]dioxolane] (Ac-CBTZ-SB, 60 mg, 0.0735 mmol), 4-bromo-2,7-bis(2-decyltetradecyl)benzo[lmn][3,8]phen Anthroline-1,3,6,8(2H,7H)-tetrone (TD-NDI-MB, 183.4 mg, 0.147 mmol), tris(dibenzylideneacetone)dipalladium(0) chloroform adduct (6 mg, 5.9 μmol), tris(2-methoxyphenyl)phosphine (8.9 mg, 25.0 μmol) and chlorobenzene (4 mL) were added and reacted at 130° C. for 16 hours. After the reaction was completed, the mixture was filtered through Celite and concentrated. Methanol (7 mL) was further added, and the precipitated solid was collected by filtration, resulting in 58.3 mg of a dark blue solid (yield 38.3%). As a result of NMR spectrum measurement, the dark blue solid obtained was Ac-CBTZ-2(TD-NDI) (hereinafter, sometimes referred to as low molecular weight compound 7). The ultraviolet-visible absorption spectrum of the obtained low molecular weight compound 7 was measured in a solution state, and the measurement result is shown by the solid line in FIG.
^1H NMR (400MHz, _CDCl3 ): 9.393 (s, 2H), 8.817 (d, 2H), 8.780 (d, 2H), 4.600 (s, 4H), 4.131 (t, 4H), 1.974 (bs, 4H), 1.546-0.867 (m, 168H), 0.8 18 (t, 12H)

図１５～図２０から明らかなように、本発明の低分子型化合物１、３～７は、溶液の状態でも、薄膜の状態でも、長波長領域の光を吸収できることが分かる。なお、低分子型化合物２は試料量が少なかったため紫外可視吸収スペクトルを測定できなかった。低分子型化合物８は、クロロホルムにほとんど溶解しなかったため、紫外可視吸収スペクトルを測定できなかった。 (Example 28)
In a 20 mL flask, 2,5-Bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bisthiazole-7,2'-[1,3]dioxolane] (Ac-CBTZ-SB, 60 mg, 0.0735 mmol), 4-bromo-2,7-bis(2-phenylethyl)benzo[lmn][3,8]phenan throline-1,3,6,8(2H,7H)-tetrone (PhEt-NDI-MB, 81.8 mg, 0.147 mmol), tris(dibenzylideneacetone)dipalladium(0) chloroform adduct (6 mg, 5.9 μmol), tris(2-methoxyphenyl)phosphine (8.9 mg, 25.0 μmol) and chlorobenzene (4 mL) were added and reacted at 130° C. for 16 hours. After the reaction was completed, the mixture was filtered through Celite and concentrated. Methanol (7 mL) was further added, and the precipitated solid was collected by filtration, resulting in 68.3 mg of a dark blue solid (yield 84.2%). As a result of NMR spectrum measurement, the dark blue solid obtained was Ac-CBTZ-2(PhEt-NDI) (hereinafter, sometimes referred to as low molecular weight compound 8).
^1H NMR (400MHz, CDCl ₃ ): 8.931 (s, 2H), 8.806 (d, 2H), 8.772 (d, 2H), 7.732-7.205 (m, 10H), 4.441-4.390 (m, 4H), 3.055-3.006 (m, 8H)

15 to 20, it is clear that the low molecular weight compounds 1, 3 to 7 of the present invention can absorb light in the long wavelength region whether in solution or in thin film form. Note that the UV-visible absorption spectrum of low molecular weight compound 2 could not be measured because the sample amount was small. The UV-visible absorption spectrum of low molecular weight compound 8 could not be measured because it was hardly dissolved in chloroform.

Next, the solubility of the obtained low molecular weight compounds 1 to 8 in solvents was evaluated. The solvent used was chloroform, chlorobenzene, toluene, tetrachloroethane, or 1-methylnaphthalene. When chloroform was used, chloroform was added at room temperature so that the concentration of the low molecular weight compound was 1% by mass. When chlorobenzene was used, chlorobenzene was added at room temperature so that the concentration of the low molecular weight compound was 1% by mass. When toluene was used, toluene was added at room temperature so that the concentration of the low molecular weight compound was 1% by mass. When tetrachloroethane was used, tetrachloroethane was added at room temperature so that the concentration of the low molecular weight compound was 1% by mass, and then heated to 110°C. When 1-methylnaphthalene was used, 1-methylnaphthalene was added at room temperature so that the concentration of the low molecular weight compound was 1% by mass, and then heated to 110°C. The solubility of low molecular weight compound 1 in chloroform was evaluated by adding chloroform at room temperature so that the concentration of low molecular weight compound 1 was 1% by mass, and then heating to 50°C. The solubility of low molecular weight compound 1 in chlorobenzene was evaluated by adding chlorobenzene at room temperature so that the concentration of low molecular weight compound 1 became 1 mass %, and then heating to 110°C.

After the solvent was added, the solution was visually observed to see whether the low molecular weight compound was dissolved, and was evaluated based on the following criteria. The evaluation results are shown in Table 2 below. In Table 2 below, "-" indicates that no evaluation was performed.
<Evaluation criteria>
A: Dissolved in the solvent.
Δ: A part of the low molecular weight compound remained undissolved.
×: Not dissolved in the solvent.

Next, the ionization energy, band gap, electron mobility μe, threshold voltage, and on/off ratio were measured using the obtained low molecular weight compounds 1, 3 to 7. The measurement conditions for the ionization energy, band gap, electron mobility μe, threshold voltage, and on/off ratio were the same as those for the measurement using the polymeric compound. The measurement results are shown in Table 2 below. The results of UV measurements taken in a thin film state are shown by dotted lines in Figures 15 to 20. When preparing an organic field effect transistor (OFET) element for measuring the electron mobility μe, threshold voltage, and on/off ratio, chloroform, chlorobenzene, or tetrachloroethane was used as the solvent for the spin-coated solution. The solvents used are also shown in Table 2 below. The LUMO value was calculated from the ionization energy and band gap.

Next, for the low molecular weight compounds 2 and 8, trimer compounds in which the substituent bonded to the nitrogen constituting the acceptor unit is a methyl group were designed, and the ionization energy value (HOMO value) and LUMO value were predicted by DFT calculation. The trimer compound used in the calculation is shown in the formula below. Gaussian 16 was used as the calculation software for the DFT calculation. The ionization energy value and the LUMO value (eV) are shown in Table 2 below. In addition, the band gap (eV) calculated from the ionization energy value and the LUMO value is also shown in Table 2 below. In addition, the electron mobility μe, threshold voltage, and on/off ratio were measured using the low molecular weight compound 2. The measurement conditions for the electron mobility μe, threshold voltage, and on/off ratio are the same as when the measurement was performed using the polymer type compound. The measurement results are shown in Table 2 below. Note that the electron mobility μe, threshold voltage, and on/off ratio were not measured for the low molecular weight compound 8.

From Table 2, the following can be considered. The low molecular weight compounds 1 to 8 of the present invention are compounds having one or more donor units and acceptor units each having a specific structure, and the donor units and acceptor units are linked to each other, and in particular, are compounds having a total of three donor units and acceptor units (more specifically, trimer compounds in which two acceptor units are linked to a toner unit). The low molecular weight compounds 1 to 8 of the present invention had good solubility in solvents. In addition, the low molecular weight compounds 1 to 8 of the present invention can be preferably used as organic semiconductor materials. In addition, the low molecular weight compounds 1 to 7 of the present invention showed good electron mobility even after annealing at 150°C.

Claims (10)

A compound having a total of two or three donor units each including a unit represented by the following formula (Do-A) and an acceptor unit, the donor units and the acceptor units being linked to each other,
The acceptor unit has a fused ring structure, at least one of the rings is an aromatic ring, and the elements constituting the ring are a carbon atom and a heteroatom. The acceptor unit is a low molecular weight compound including a heteroaromatic fused ring unit represented by any one of the following formulas (Ac-1) to (Ac-17):

[In formula (Do-A), R ^a represents an alkylene group having 2 to 6 carbon atoms, and * represents a bond.]

[In formulas (Ac-1) to (Ac-17), T ¹ and T ² each independently represent a single bond, -CH=CH-, -C≡C-, a thiophene ring optionally substituted with a hydrocarbon group, a thiazole ring optionally substituted with a hydrocarbon group, a pyridine ring optionally substituted with a hydrocarbon group, or a pyrazine ring optionally substituted with a hydrocarbon group.
R ¹ is a hydrogen atom, a hydrocarbon group, or -(CH ₂ ) _p -OR ³ , where R ³ is a hydrocarbon group and p is an integer of 1 to 5. ^When the acceptor unit has a plurality of ^{R 1} , the plurality of R ¹ may be the same or different from each other.
R ² is a hydrocarbon group. When the acceptor unit has a plurality of R ² , the plurality of R ² may include the same R ² or different R ² .
A ¹ and A ² are each independently -(CH ₂ ) _q -OR ⁴ , a thiophene ring optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group, a thiazole ring optionally substituted with a hydrocarbon group or an organosilyl group, or a phenyl group optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, an organosilyl group, a halogen atom, or a halogenated alkyl group, R ⁴ is a hydrocarbon group, and q is an integer from 1 to 5 .
D ¹ is CH or a nitrogen atom. When the acceptor unit has a plurality of D ¹ , the plurality of D ¹ may include the same D ¹ or different D ¹ .
^D2 is a carbon atom, a silicon atom, or a nitrogen atom.
n is 0 or 1.
When the unit represented by any one of Formulae (Ac-1) to (Ac-17) is at the end of the compound, * is a hydrogen atom.
When a compound has multiple acceptor units, ^T1 , ^T2 , ^R1 , ^R2 , ^A1 , ^A2 , ^D1 , and ^D2 may each be the same between the units or different from each other.
The ring may have at least one substituent bonded thereto selected from the group consisting of a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, an ester group, a halogenated alkyl group, and a cyano group .] The polymerizable compound has two or more donor units and two or more acceptor units each including a unit represented by the following formula (Do-A), and the donor units and the acceptor units are linked to each other:
The acceptor unit has a fused ring structure, at least one of the rings is an aromatic ring, and the elements constituting the ring are a carbon atom and a heteroatom. The polymer compound includes a heteroaromatic fused ring unit represented by any one of the following formulas (Ac-1) to (Ac-17).

[In formula (Do-A), R ^a represents an alkylene group having 2 to 6 carbon atoms, and * represents a bond.]

[In formulas (Ac-1) to (Ac-17), T ¹ and T ² each independently represent a single bond, -CH=CH-, -C≡C-, a thiophene ring optionally substituted with a hydrocarbon group, a thiazole ring optionally substituted with a hydrocarbon group, a pyridine ring optionally substituted with a hydrocarbon group, or a pyrazine ring optionally substituted with a hydrocarbon group.
R ¹ is a hydrogen atom, a hydrocarbon group, or -(CH ₂ ) _p -OR ³ , where R ³ is a hydrocarbon group and p is an integer of 1 to 5. ^When the acceptor unit has a plurality of ^{R 1} , the plurality of R ¹ may be the same or different from each other.
^R2 is a hydrocarbon group. When the acceptor unit has a plurality of ^R2 , the plurality of ^R2 may include the same ^R2 or different ^R2 .
A ¹ and A ² are each independently -(CH ₂ ) _q -OR ⁴ , a thiophene ring optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group, a thiazole ring optionally substituted with a hydrocarbon group or an organosilyl group, or a phenyl group optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, an organosilyl group, a halogen atom, or a halogenated alkyl group, R ⁴ is a hydrocarbon group, and q is an integer from 1 to 5 .
D ¹ is CH or a nitrogen atom. When the acceptor unit has a plurality of D ¹ , ^{the plurality of D 1 may} be the same as each other or may be different from each other ^.
D2 is a carbon atom, a silicon atom, or a nitrogen atom.
n is 0 or 1.
When the units represented by formulae (Ac-1) to (Ac-17) are at the terminals of the compounds, * may be a hydrogen atom.
When a compound has multiple acceptor units, ^T1 , ^T2 , ^R1 , ^R2 , ^A1 , ^A2 , ^D1 , and ^D2 may each be the same between the units or different from each other.
At least one substituent selected from the group consisting of a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, an ester group, a halogenated alkyl group, and a cyano group may be bonded to the ring.] The polymer compound according to claim 2, which has the donor unit and the acceptor unit as repeating units. The polymer compound according to claim 3, in which the donor units and the acceptor units are arranged alternately. The polymeric compound according to claim 3, having a weight average molecular weight (Mw) of 1500 or more. 4. The polymer compound according to claim 3, wherein the donor units contained in the polymer compound further include a unit represented by the following formula (Do-K):

[In formula (Do-K), * represents a bond.] The low molecular weight compound according to claim 1, wherein the donor unit is linked to two of the acceptor units. An organic semiconductor material comprising the low molecular weight compound according to claim 1. An organic semiconductor material comprising the polymer compound according to claim 2. 10. An organic electronic device comprising the organic semiconductor material of claim 8 or 9.

Images