TW202330554A

TW202330554A - Compound, organic semiconductor material, and organic electronic device

Info

Publication number: TW202330554A
Application number: TW111147509A
Authority: TW
Inventors: 家裕隆; 陣内青萌; 三枝真理奈; 萩谷一剛
Original assignee: 國立大學法人大阪大學; 日商東洋紡股份有限公司
Priority date: 2021-12-09
Filing date: 2022-12-09
Publication date: 2023-08-01
Also published as: WO2023106405A1; JPWO2023106405A1

Abstract

Provided is a compound which can be advantageously used as an organic semiconductor material and has satisfactory solubility in solvents. An organic semiconductor material including such compound is provided. An organic electronic device including such organic semiconductor material is provided. This compound comprises one or more donating units including a unit represented by formula (Do-A) and one or more accepting units, the donating units and the accepting units having been connected to each other. In formula (Do-A), Ra represents a C2-C10 alkylene group and * indicates a linking bond.

Description

化合物、有機半導體材料、以及有機電子器件Compounds, Organic Semiconductor Materials, and Organic Electronic Devices

本發明係關於一種具有包含特定之單位之供體性單元及受體性單元之化合物、包含該化合物之有機半導體材料、以及包含該有機半導體材料之有機電子器件。The present invention relates to a compound having a donor unit and an acceptor unit comprising a specific unit, an organic semiconductor material comprising the compound, and an organic electronic device comprising the organic semiconductor material.

有機半導體材料係有機電子學領域中重要的材料，使用有單體化合物或高分子化合物作為有機半導體材料。有機半導體材料可分類為電子供應性之p型有機半導體材料及電子接受性之n型有機半導體材料，藉由使p型有機半導體材料及n型有機半導體材料適當地組合而可製造各種有機電子器件。作為有機電子器件，例如可例舉：藉由電子與電洞再結合所形成之激子(exciton)之作用而發光之有機電致發光元件、控制電流量或電壓量之有機薄膜電晶體元件、有機光電轉換元件、將光轉換成電力之有機薄膜太陽能電池模組等。Organic semiconductor materials are important materials in the field of organic electronics, and monomeric compounds or polymer compounds are used as organic semiconductor materials. Organic semiconductor materials can be classified into electron-donating p-type organic semiconductor materials and electron-accepting n-type organic semiconductor materials, and various organic electronic devices can be manufactured by properly combining p-type organic semiconductor materials and n-type organic semiconductor materials . As an organic electronic device, for example, an organic electroluminescent element that emits light through the action of an exciton (exciton) formed by the recombination of an electron and an electric hole, an organic thin film transistor element that controls the amount of current or voltage, Organic photoelectric conversion elements, organic thin-film solar cell modules that convert light into electricity, etc.

作為有機半導體材料的一例，專利文獻1中提出有用作n型有機半導體材料之聚合物。專利文獻1中所提出之聚合物係具有下述通式(II)所表示之重複單位之至少1個、及下述通式(III)所表示之重複單位之至少1個之含氮縮合環聚合物。式(II)中，作為Z ¹及Z ²，例示有S(硫原子)，式(III)中，作為Ar ¹，例示有2價之芳香族烴基或2價之雜環基。 As an example of an organic semiconductor material, Patent Document 1 proposes a polymer used as an n-type organic semiconductor material. The polymer proposed in Patent Document 1 is a nitrogen-containing condensed ring 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) polymer. In formula (II), Z ¹ and Z ² are exemplified by S (sulfur atom), and in formula (III), Ar ¹ is exemplified by a divalent aromatic hydrocarbon group or a divalent heterocyclic group.

[化1] [先前技術文獻] [專利文獻] [chemical 1] [Prior Art Document] [Patent Document]

[專利文獻1]日本特開2009-215278號公報。[Patent Document 1] Japanese Unexamined Patent Publication No. 2009-215278.

[發明所欲解決之課題][Problem to be Solved by the Invention]

有機電子器件例如藉由下述方式來製造，亦即，藉由真空蒸鍍法將有機半導體材料製成有機薄膜，或者藉由預定之製膜法將有機半導體材料經溶解於溶媒等中而成之溶液製成有機薄膜。若有機半導體材料可溶於溶媒(尤其是有機溶媒)，則例如能夠於印刷製程中進行製膜，因此能夠實現有機薄膜之大面積化及製造成本之削減。因此，對於有機半導體材料，期望於溶媒中之溶解性良好。但是，於上述專利文獻1之實施例中，使用含氮縮合環化合物作為有機半導體材料，藉由真空蒸鍍法製作有機半導體元件。可認為採用真空蒸鍍法之原因在於，含氮縮合環化合物不易溶解於溶媒，於專利文獻1中未對含氮縮合環化合物於溶媒中之溶解性進行研究。本發明者等人對有機半導體材料的溶解性進行研究，結果判斷得知有改善之空間。Organic electronic devices are produced, for example, by making an organic thin film from an organic semiconductor material by a vacuum evaporation method, or by dissolving an organic semiconductor material in a solvent or the like by a predetermined film forming method. solution to form an organic film. If the organic semiconductor material is soluble in a solvent (especially an organic solvent), it can, for example, be formed into a film during a printing process, so that the area of the organic thin film can be increased and the production cost can be reduced. Therefore, it is desirable for an organic semiconductor material to have good solubility in a solvent. However, in the embodiment of the above-mentioned Patent Document 1, a nitrogen-containing condensed ring compound is used as an organic semiconductor material, and an organic semiconductor device is fabricated by a vacuum evaporation method. It can be considered that the reason for adopting the vacuum evaporation method is that nitrogen-containing condensed ring compounds are not easily soluble in solvents, and the solubility of nitrogen-containing condensed ring compounds in solvents has not been studied in Patent Document 1. The inventors of the present invention have studied the solubility of organic semiconductor materials, and found that there is room for improvement.

本發明之目的在於提供一種可較佳地用作有機半導體材料且於溶媒中之溶解性良好之化合物。另外，本發明之另一目的在於提供一種包含此種化合物之有機半導體材料。另外，本發明之另一目的在於提供一種包含此種有機半導體材料之有機電子器件。 [用以解決課題之手段] The object of the present invention is to provide a compound which can be preferably used as an organic semiconductor material and has good solubility in a solvent. In addition, another object of the present invention is to provide an organic semiconductor material comprising such a compound. In addition, another object of the present invention is to provide an organic electronic device comprising such an organic semiconductor material. [Means to solve the problem]

本發明包含以下之發明。 [1]一種化合物，具有包含下述式(Do-A)所表示之單位之供體性單元及受體性單元各1個以上，且供體性單元與受體性單元相互連結著。下述式(Do-A)中，R ^a表示碳數2至10之伸烷基，*表示鍵結部位。 [化2] [2]如[1]所記載之化合物，其中前述受體性單元包含選自由下述(1)至(3)所組成之群組中的至少1種：(1)雜芳香族縮環型單元，具有縮環結構，且環之至少1個為芳香族環，構成環之元素為碳原子及雜原子；(2)芳香族縮環型單元，具有縮環結構，且環之至少1個為芳香族環，構成環之元素為碳原子；及(3)單環型單元，具有芳香族環且不具有縮環結構。 [3]如[1]或[2]所記載之化合物，其具有前述供體性單元及前述受體性單元作為重複單位。 [4]如[3]所記載之化合物，其中前述供體性單元與前述受體性單元交替地配置。 [5]如[3]或[4]所記載之化合物，其重量平均分子量(Mw)為1500以上。 [6]如[3]至[5]中任一項所記載之化合物，其中前述高分子型化合物中所含之多個供體性單元進而包含下述式(Do-K)所表示之單位。下述式(Do-K)中，*表示鍵結部位。 [化3] [7]如[1]所記載之化合物，其具有前述供體性單元及前述受體性單元合計2個或3個。 [8]如[1]所記載之化合物，其中於前述供體性單元上連結有2個前述受體性單元。 [9]一種有機半導體材料，包含如[1]至[8]中任一項所記載之化合物。 [10]一種有機電子器件，包含如[9]所記載之有機半導體材料。 [發明功效] The present invention includes the following inventions. [1] A compound having one or more each of a donor unit and an acceptor unit comprising a unit represented by the following formula (Do-A), and the donor unit and the acceptor unit 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 bonding site. [Chem 2] [2] The compound as described in [1], wherein the accepting unit includes at least one selected from the group consisting of the following (1) to (3): (1) Heteroaromatic ring-condensed type Units with a condensed ring structure, and at least one of the rings is an aromatic ring, and the elements constituting the ring are carbon atoms and heteroatoms; (2) Aromatic ring-condensed units have a condensed ring structure, and at least one of the rings is It is an aromatic ring, and the elements constituting the ring are carbon atoms; and (3) a monocyclic unit, which has an aromatic ring and does not have a condensed ring structure. [3] The compound according to [1] or [2], which has the aforementioned donating unit and the aforementioned accepting unit as repeating units. [4] The compound according to [3], wherein the donating units and the accepting units are arranged alternately. [5] The compound described in [3] or [4], which has a weight average molecular weight (Mw) of 1500 or more. [6] The compound as described in any one of [3] to [5], wherein the plurality of donating 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 bonding site. [Chem 3] [7] The compound according to [1], which has a total of two or three of the aforementioned donating unit and the aforementioned accepting unit. [8] The compound according to [1], wherein two of the acceptor units are linked to the donor unit. [9] An organic semiconductor material comprising the compound described in any one of [1] to [8]. [10] An organic electronic device comprising the organic semiconductor material as described in [9]. [Efficacy of the invention]

根據本發明，可提供一種可較佳地用作有機半導體材料且於溶媒中之溶解性良好之化合物。另外，根據本發明，可提供一種包含此種化合物之有機半導體材料、以及包含此種有機半導體材料之有機電子器件。According to the present invention, it is possible to provide a compound which can be preferably used as an organic semiconductor material and has good solubility in a solvent. In addition, according to the present invention, there can be provided an organic semiconductor material including the compound, and an organic electronic device including the organic semiconductor material.

本發明之化合物具有包含下述式(Do-A)所表示之單位之供體性單元及受體性單元各1個以上，且供體性單元與受體性單元相互連結著。下述式(Do-A)中，R ^a表示碳數2至10之伸烷基，*表示鍵結部位。於包含下述式(Do-A)所表示之單位之供體性單元為化合物之末端之情形時，*可為氫原子。 The compound of the present invention has at least one donor unit and one acceptor unit each comprising a unit represented by the following formula (Do-A), and the donor unit and the acceptor unit 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 bonding site. When the donating unit including the unit represented by the following formula (Do-A) is the terminal of the compound, * may be a hydrogen atom.

[化4] [chemical 4]

所謂構成化合物之供體性單元，意指電子供應性之結構單位。所謂構成化合物之受體性單元，意指電子接受性之結構單位。The term "donating unit constituting a compound" means an electron-donating structural unit. The term "accepting unit constituting a compound" means an electron-accepting structural unit.

式(Do-A)所表示之單位在電子供應性優異。另外，式(Do-A)所表示之單位尚具有包含縮醛結構之螺環骨架，因此於溶媒中之溶解性良好。因此，若使用將包含式(Do-A)所表示之單位之供體性單元與受體性單元組合而成之化合物，則該化合物於溶媒中之溶解性變得良好。因而，將該化合物塗佈於基板而成之膜的膜質變得良好，該膜的電子遷移率變得良好。另外，若使用將包含式(Do-A)所表示之單位之供體性單元與受體性單元組合而成之化合物，則游離能(ionization energy)之值(HOMO(Highest Occupied Molecular Orbital；最高佔據分子軌域)之值)與LUMO(Lowest Unoccupied Molecular Orbital；最低未佔據分子軌域)之值之帶隙變小，電子變得容易遷移。進而，藉由於分子間發揮靜電相互作用而配向性亦變得良好，可期待電子遷移率提升。另外，LUMO之值例如成為-3.5eV以下，具有大氣穩定性。因此，具有包含該式(Do-A)所表示之單位之供體性單元及受體性單元各1個以上，且供體性單元與受體性單元相互連結之化合物例如可較佳地用作有機半導體材料。The unit represented by the formula (Do-A) is excellent in electron availability. In addition, the unit represented by the formula (Do-A) still has a spiro ring skeleton including an acetal structure, so it has good solubility in solvents. Therefore, when a compound comprising a donor unit and an acceptor unit composed of a unit represented by formula (Do-A) is used, the solubility of the compound in a solvent becomes favorable. Therefore, the film quality of the film obtained by applying the compound on the substrate becomes good, and the electron mobility of the film becomes good. In addition, if a compound composed of a donor unit and an acceptor unit comprising a unit represented by the formula (Do-A) is used, the value of ionization energy (HOMO (Highest Occupied Molecular Orbital; Highest Occupied Molecular Orbital; highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbital; the lowest unoccupied molecular orbital) value of the band gap becomes smaller, electrons become easier to move. Furthermore, since the electrostatic interaction between molecules is exerted, the alignment becomes good, and an improvement in electron mobility can be expected. In addition, the value of LUMO is, for example, -3.5 eV or less, and has atmospheric stability. Therefore, a compound having at least one donor unit and one acceptor unit each comprising a unit represented by the formula (Do-A), and a compound in which the donor unit and the acceptor unit are linked to each other can be preferably used, for example. as organic semiconductor materials.

本發明之化合物具有包含上述式(Do-A)所表示之單位之供體性單元及受體性單元各1個以上，且供體性單元與受體性單元相互連結著。以下，有時將此種化合物中具有供體性單元及受體性單元合計2個或3個之化合物稱為低分子型化合物。另外，以下有時將具有包含上述式(Do-A)所表示之單位之供體性單元及受體性單元作為重複單位之化合物稱為高分子型化合物。換言之，高分子型化合物係具有包含上述式(Do-A)所表示之單位之供體性單元及受體性單元各2個以上，且供體性單元與受體性單元相互連結之化合物。將低分子型化合物中具有供體性單元及受體性單元合計2個之化合物(亦即，1個供體性單元與1個受體性單元相互連結之化合物)稱為二聚物型化合物。以下，有時將低分子型化合物中具有供體性單元及受體性單元合計3個且供體性單元與受體性單元相互連結之化合物稱為三聚物型化合物，或簡稱為三聚物。三聚物型化合物亦可為於1個受體性單元上連結有2個供體性單元之化合物，但較佳為於1個供體性單元上連結有2個受體性單元之化合物。於為低分子型化合物之情形時，相較於高分子型化合物而於溶媒中之溶解性變得更良好。其結果，藉由使用低分子型化合物，例如可藉由旋轉塗佈而製造均質的薄膜，因此電子遷移率變得良好。The compound of the present invention has at least one donor unit and one acceptor unit each comprising a unit represented by the above formula (Do-A), and the donor unit and the acceptor unit are linked to each other. Hereinafter, among such compounds, a compound having a total of 2 or 3 donor units and acceptor units may be referred to as a low-molecular-weight compound. In addition, a compound having a donor unit and an acceptor unit including a unit represented by the above formula (Do-A) as a repeating unit may be referred to as a polymer compound below. In other words, the polymer compound is a compound having two or more donor units and acceptor units each comprising a unit represented by the above formula (Do-A), and the donor unit and the acceptor unit are linked to each other. Among low-molecular-weight compounds, a compound having a total of two donor units and an acceptor unit (that is, a compound in which one donor unit and one acceptor unit are linked together) is called a dimer compound. . Hereinafter, among low-molecular-weight compounds, a compound having a total of three donor units and an acceptor unit in which the donor unit and the acceptor unit are linked is sometimes referred to as a trimer compound, or simply referred to as a trimer compound. things. The trimer compound may be a compound in which two donor units are linked to one acceptor unit, but is preferably a compound in which two acceptor units are linked to one donor unit. In the case of a low-molecular-weight compound, the solubility in a solvent becomes better than that of a high-molecular-weight compound. As a result, by using a low-molecular-weight compound, a homogeneous thin film can be produced by, for example, spin coating, and thus electron mobility becomes good.

式(Do-A)中，前述R ^a的碳數較佳為2至8，更佳為2至6，進而較佳為2至4。伸烷基可為直鏈伸烷基，亦可為具有支鏈之伸烷基，但較佳為直鏈伸烷基。作為R ^a，例如可例舉：伸乙基、伸正丙基、1-甲基-乙烷-1,2-基、1,2-二甲基-乙烷-1,2-基、1-甲基-丙烷-1,3-基等，這些當中，較佳為伸乙基、伸正丙基。 In the formula (Do-A), the carbon number of the aforementioned R ^a is preferably 2-8, more preferably 2-6, and still more preferably 2-4. The alkylene group may be straight-chain or branched, but is preferably straight-chain. As R ^a , for example, ethylidene, n-propyl, 1-methyl-ethane-1,2-yl, 1,2-dimethyl-ethane-1,2-yl, 1- Methyl-propan-1,3-yl and the like, among these, ethylene and n-propyl are preferred.

於式(Do-A)所表示之單位中，前述R ^a為碳數2之伸乙基之情形時，式(Do-A)所表示之單位由下述式(Do-a)所表示。 In the unit represented by the formula (Do-A), when the aforementioned R ^a is an ethylenyl group having 2 carbon atoms, the unit represented by the formula (Do-A) is represented by the following formula (Do-a).

[化5] [chemical 5]

構成本發明之化合物之供體性單元只要包含上述式(Do-A)所表示之單位即可，亦可包含公知的供體性單元或後述之式(Do-K)所表示之單位等其他供體性單元。將供體性單元整體設為100mol%時，上述式(Do-A)所表示之單位之比率例如較佳為40mol%以上，更佳為50mol%以上，進而較佳為80mol%以上。亦可供體性單元之整體(100mol%)為上述式(Do-A)所表示之單位。The donating unit constituting the compound of the present invention may include a unit represented by the above-mentioned formula (Do-A), and may include a known donating unit or a unit represented by the formula (Do-K) described later. donor unit. The ratio of the unit represented by the above formula (Do-A) is, for example, preferably at least 40 mol%, more preferably at least 50 mol%, and still more preferably at least 80 mol%, when the whole of the donating unit is 100 mol%. The whole (100 mol%) of the donor unit may be a unit represented by the above-mentioned formula (Do-A).

與構成化合物之供體性單元組合之受體性單元可使用公知的受體性單元。受體性單元例如較佳為包含選自由下述(1)至(3)所組成之群組中的至少1種。 (1) 雜芳香族縮環型單元，具有縮環結構，且環之至少1個為芳香族環，構成環之元素為碳原子及雜原子。 (2) 芳香族縮環型單元，具有縮環結構，且環之至少1個為芳香族環，構成環之元素為碳原子。 (3) 單環型單元，具有芳香族環且不具有縮環結構。 Known acceptor units can be used as the acceptor unit combined with the donor unit constituting the compound. For example, the receptive unit preferably contains at least one selected from the group consisting of the following (1) to (3). (1) The heteroaromatic condensed ring unit has a condensed ring structure, and at least one of the rings is an aromatic ring, and the elements constituting the ring are carbon atoms and heteroatoms. (2) An aromatic condensed ring type unit, which has a condensed ring structure, and at least one of the rings is an aromatic ring, and the element constituting the ring is a carbon atom. (3) A monocyclic unit having an aromatic ring and not having a condensed ring structure.

以下，對(1)至(3)之單元進行說明。Hereinafter, the means of (1) to (3) will be described.

(1)雜芳香族縮環型單元所謂雜芳香族縮環型單元，係指具有縮環結構，且環之至少1個為芳香族環，構成環之元素為碳原子及雜原子之結構單位。所謂雜原子，係指碳原子以外之原子。換言之，雜芳香族縮環型單元係含有芳香族環之縮環型單元，且構成該縮環型單元之縮環之環之至少1個為由碳原子及雜原子所構成之雜環之單元。亦即，具有縮環結構之縮環型單元具有至少1個雜環。雜原子各自例如為氮原子、硫原子、或氧原子。 (1) Heteroaromatic condensed ring unit The so-called heteroaromatic condensed ring unit refers to a structural unit having a condensed ring structure, at least one of which is an aromatic ring, and the elements constituting the ring are carbon atoms and heteroatoms. The term "heteroatom" refers to an atom other than a carbon atom. In other words, the heteroaromatic condensed ring unit is a condensed ring unit containing an aromatic ring, and at least one of the condensed rings constituting the condensed ring unit is a heterocyclic unit composed of carbon atoms and heteroatoms . That is, the condensed ring-type unit having a condensed ring structure has at least one heterocyclic ring. The heteroatoms are each, for example, a nitrogen atom, a sulfur atom, or an oxygen atom.

構成縮環結構之環的數量並無特別限定，例如較佳為2以上至10以下。環的數量可為3以上且可為8以下。The number of rings constituting the condensed ring structure is not particularly limited, for example, preferably 2 or more and 10 or less. The number of rings may be 3 or more and 8 or less.

芳香族環可為芳香族烴環，亦可為雜芳香族環(有時亦稱為芳香族雜環)。The aromatic ring may be an aromatic hydrocarbon ring or a heteroaromatic ring (sometimes also referred to as an aromatic heterocycle).

構成環之元素為碳原子及雜原子，環包含至少1個雜原子，剩餘部分為碳原子。雜原子的數量可為2個以上，亦可為3個以上。雜原子的數量的上限取決於構成縮環結構之原子的數量，例如較佳為10個以下，更佳為8個以下，進而較佳為6個以下。The elements constituting the ring are carbon atoms and heteroatoms, the ring contains at least one heteroatom, and the remainder is carbon atoms. The number of heteroatoms may be 2 or more, or 3 or more. The upper limit of the number of heteroatoms depends on the number of atoms constituting the condensed ring structure, and is, for example, preferably 10 or less, more preferably 8 or less, further preferably 6 or less.

於環上亦可鍵結有取代基。作為取代基，例如可例舉鹵素原子、烴基、烷氧基、醯基、酯基、鹵化烷基、氰基等。作為鹵素原子，例如可例舉氟、氯、溴、碘等，當中較佳為氟。烴基(以下，有時稱為烴基R)較佳為脂肪族烴基、芳烷基等，前述脂肪族烴基亦可為直鏈狀之脂肪族烴基，但更佳為具有支鏈之脂肪族烴基。A substituent may be bonded to the ring. As a substituent, a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, an ester group, a halogenated alkyl group, a cyano group etc. are mentioned, for example. The halogen atom may, for example, be fluorine, chlorine, bromine or iodine, among which fluorine is preferred. The hydrocarbon group (hereinafter sometimes referred to as hydrocarbon group R) is preferably an aliphatic hydrocarbon group, an aralkyl group, etc., and the above-mentioned aliphatic hydrocarbon group may also be a straight-chain aliphatic hydrocarbon group, but is more preferably a branched-chain aliphatic hydrocarbon group.

烴基R的碳數並無特別限定，例如較佳為1至30。烴基R的碳數更佳為3以上，進而較佳為6以上，且更佳為28以下，進而較佳為26以下。其中，於烴基R為芳烷基之情形時，碳數的下限較佳為7以上。於本發明之化合物為高分子型化合物之情形時，烴基R的碳數以大為佳，碳數越大，於溶媒中之溶解性越良好。高分子型化合物之情形時的烴基R的碳數較佳為8以上，更佳為10以上，進而較佳為12以上。於本發明之化合物為低分子型化合物之情形時，烴基R的碳數以小為佳，碳數越小，配向性越好，電子容易於分子間遷移，電子遷移率提升。低分子型化合物之情形時的烴基R的碳數較佳為24以下，更佳為20以下，進而較佳為14以下。The carbon number of the hydrocarbon group R is not particularly limited, and is preferably 1-30, for example. The carbon number of the hydrocarbon group R is more preferably 3 or more, still more preferably 6 or more, and more preferably 28 or less, and still more preferably 26 or less. However, when the hydrocarbon group R is an aralkyl group, the lower limit of the carbon number is preferably 7 or more. When the compound of the present invention is a polymer compound, the carbon number of the hydrocarbon group R is preferably large, and the larger the carbon number, the better the solubility in the solvent. In the case of a polymer compound, the carbon number of the hydrocarbon group R is preferably 8 or more, more preferably 10 or more, and still more preferably 12 or more. When the compound of the present invention is a low-molecular compound, the carbon number of the hydrocarbon group R is preferably small. The smaller the carbon number, the better the alignment, and the electrons are easy to transfer between molecules, and the electron mobility is improved. In the case of a low-molecular-weight compound, the carbon number of the hydrocarbon group R is preferably 24 or less, more preferably 20 or less, and still more preferably 14 or less.

作為烴基R，例如可例舉：甲基等碳數1之烷基；乙基等碳數2之烷基；正丙基、異丙基等碳數3之烷基；正丁基等碳數4之烷基；正戊基等碳數5之烷基；正己基等碳數6之烷基；正庚基等碳數7之烷基；正辛基、1-正丁基丁基、1-正丙基戊基、1-乙基己基、2-乙基己基、3-乙基己基、4-乙基己基、1-甲基庚基、2-甲基庚基、6-甲基庚基、2,4,4-三甲基戊基、2,5-二甲基己基等碳數8之烷基；正壬基、1-正丙基己基、2-正丙基己基、1-乙基庚基、2-乙基庚基、1-甲基辛基、2-甲基辛基、6-甲基辛基、2,3,3,4-四甲基戊基、3,5,5-三甲基己基等碳數9之烷基；正癸基、1-正戊基戊基、1-正丁基己基、2-正丁基己基、1-正丙基庚基、1-乙基辛基、2-乙基辛基、1-甲基壬基、2-甲基壬基、3,7-二甲基辛基等碳數10之烷基；正十一烷基、1-正丁基庚基、2-正丁基庚基、1-正丙基辛基、2-正丙基辛基、1-乙基壬基、2-乙基壬基等碳數11之烷基；正十二烷基、1-正戊基庚基、2-正戊基庚基、1-正丁基辛基、2-正丁基辛基、1-正丙基壬基、2-正丙基壬基等碳數12之烷基；正十三烷基、1-正戊基辛基、2-正戊基辛基、1-正丁基壬基、2-正丁基壬基、1-甲基十二烷基、2-甲基十二烷基等碳數13之烷基；正十四烷基、1-正庚基庚基、1-正己基辛基、2-正己基辛基、1-正戊基壬基、2-正戊基壬基等碳數14之烷基；正十五烷基、1-正庚基辛基、1-正己基壬基、2-正己基壬基等碳數15之烷基；正十六烷基、2-正己基癸基、1-正辛基辛基、1-正庚基壬基、2-正庚基壬基等碳數16之烷基；正十七烷基、1-正辛基壬基等碳數17之烷基；正十八烷基、1-正壬基壬基等碳數18之烷基；正十九烷基等碳數19之烷基；正二十烷基、2-正辛基十二烷基等碳數20之烷基；正二十一烷基等碳數21之烷基；正二十二烷基等碳數22之烷基；正二十三烷基等碳數23之烷基；正二十四烷基、2-正癸基十四烷基等碳數24之烷基；正二十五烷基等碳數25之烷基；正二十六烷基等碳數26之烷基；正二十七烷基等碳數27之烷基；正二十八烷基等碳數28之烷基；正二十九烷基等碳數29之烷基；正三十烷基等碳數30之烷基；苯基甲基、苯基乙基等芳烷基等。Examples of the hydrocarbon group R include: alkyl groups having 1 carbon number such as methyl groups; alkyl groups having 2 carbon atoms such as ethyl groups; alkyl groups having 3 carbon atoms such as n-propyl groups and isopropyl groups; Alkyl with 4 carbons; alkyl with 5 carbons such as n-pentyl; alkyl with 6 carbons such as n-hexyl; alkyl with 7 carbons such as n-heptyl; n-octyl, 1-n-butylbutyl, 1 -n-propylpentyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 1-methylheptyl, 2-methylheptyl, 6-methylheptyl Alkyl groups with 8 carbons such as 2,4,4-trimethylpentyl and 2,5-dimethylhexyl; n-nonyl, 1-n-propylhexyl, 2-n-propylhexyl, 1- Ethylheptyl, 2-ethylheptyl, 1-methyloctyl, 2-methyloctyl, 6-methyloctyl, 2,3,3,4-tetramethylpentyl, 3,5 , 5-trimethylhexyl and other alkyl groups with 9 carbons; n-decyl, 1-n-pentylpentyl, 1-n-butylhexyl, 2-n-butylhexyl, 1-n-propylheptyl, 1 -Alkyl groups with 10 carbons such as ethyloctyl, 2-ethyloctyl, 1-methylnonyl, 2-methylnonyl, 3,7-dimethyloctyl; n-undecyl, 1-n-butylheptyl, 2-n-butylheptyl, 1-n-propyloctyl, 2-n-propyloctyl, 1-ethylnonyl, 2-ethylnonyl and other alkyl groups with 11 carbons; Dodecyl, 1-n-pentylheptyl, 2-n-pentylheptyl, 1-n-butyloctyl, 2-n-butyloctyl, 1-n-propylnonyl, 2-n-propyl Alkyl groups with 12 carbons such as nonyl; n-tridecyl, 1-n-pentyloctyl, 2-n-pentyloctyl, 1-n-butylnonyl, 2-n-butylnonyl, 1-methyldodecyl Alkyl, 2-methyldodecyl and other alkyl groups with 13 carbons; n-tetradecyl, 1-n-heptylheptyl, 1-n-hexyloctyl, 2-n-hexyloctyl, Alkyl groups with 14 carbons such as pentylnonyl and 2-n-pentylnonyl; n-pentadecyl, 1-n-heptyloctyl, 1-n-hexylnonyl, 2-n-hexylnonyl and other carbon numbers 15 alkyl groups; n-hexadecyl, 2-n-hexyldecyl, 1-n-octyl octyl, 1-n-heptylnonyl, 2-n-heptylnonyl and other alkyl groups with 16 carbons; normal Alkyl groups with 17 carbons such as heptadecyl and 1-n-octylnonyl; alkyl groups with 18 carbons such as n-octadecyl and 1-n-nonylnonyl; alkanes with 19 carbons such as n-nonadecyl Alkyl groups with 20 carbons such as n-eicosyl, 2-n-octyl dodecyl, etc.; alkyl groups with 21 carbons such as n-docosyl; alkyl groups with 22 carbons such as n-docosyl Alkyl group; alkyl group with 23 carbons such as n-tricosyl group; alkyl group with 24 carbons such as n-tetradecyl group and 2-n-decyltetradecyl group; n-pentacyl group with other carbon number Alkyl group with 25 carbons; alkyl group with 26 carbons such as n-hexacyl group; alkyl group with 27 carbons such as n-hexacyl group; alkyl group with 28 carbons such as n-octadecyl group; Alkyl groups with 29 carbon atoms such as nonalkyl; alkyl groups with 30 carbon atoms such as n-triaconyl groups; aralkyl groups such as phenylmethyl groups and phenylethyl groups, etc.

烷氧基係由-OR ⁵所表示，R ⁵為烴基。作為R ⁵所表示之烴基，可例舉與上述所說明之烴基R相同之烴基。R ⁵所表示之烴基的碳數較佳為1至30，更佳為3以上，進而較佳為6以上，且更佳為28以下，進而較佳為26以下。 The alkoxy group is represented by -OR ⁵ , and R ⁵ is a hydrocarbon group. The hydrocarbon group represented by R ⁵ may, for example, be the same as the hydrocarbon group R described above. The carbon number of the hydrocarbon group represented by R ⁵ is preferably 1 to 30, more preferably 3 or more, further preferably 6 or more, and more preferably 28 or less, and still more preferably 26 or less.

作為醯基，例如可例舉：乙醯基、丙醯基、異丙醯基、丁醯基、異丁醯基、戊醯基、己醯基、庚醯基、辛醯基、壬醯基、癸醯基、月桂醯基、肉豆蔻醯基、棕櫚醯基、硬脂醯基、油醯基、亞麻醯基(linoleoyl)、次亞麻醯基(linolenoyl)等。Examples of the acyl group include: acetyl, propionyl, isopropyl, butyryl, isobutyryl, pentyl, hexyl, heptyl, octyl, nonyl, decanyl, lauryl Acyl, myristyl, palmityl, stearyl, oleyl, linoleoyl, linolenoyl, etc.

作為酯基，例如可例舉：乙醯氧基、醯氧基、烷氧基羰基、磷酸酯基等。As an ester group, an acetyloxy group, an acyloxy group, an alkoxycarbonyl group, a phosphate ester group etc. are mentioned, for example.

鹵化烷基意指上述所說明之烴基R之一部分氫被取代為鹵素原子之取代基。The halogenated alkyl group means a substituent in which a part of the hydrogen of the hydrocarbon group R described above is replaced with a halogen atom.

作為雜芳香族縮環型單元，例如可例舉下述式(Ac-1)至式(Ac-17)所表示之單元。As a heteroaromatic ring-condensing type unit, the unit represented by following formula (Ac-1) - a formula (Ac-17) is mentioned, for example.

[化6] [chemical 6]

[式(Ac-1)至式(Ac-17)中，T ¹及T ²分別獨立地為單鍵，或為-CH=CH-，或為-C≡C-，或為可經烴基取代之噻吩環，或為可經烴基取代之噻唑環，或為可經烴基取代之吡啶環，或為可經烴基取代之吡嗪環。 R ¹為氫原子，或為烴基，或為-(CH ₂) _p-OR ³，R ³為烴基。於受體性單元具有多個R ¹時，該多個R ¹中，可存在相互相同之R ¹，亦可存在相互不同之R ¹。 R ²為烴基。於受體性單元具有多個R ²時，該多個R ²中，可存在相互相同之R ²，亦可存在相互不同之R ²。 A ¹及A ²分別獨立地為-(CH ₂) _q-OR ⁴，或為可經烷氧基、硫代烷氧基、烴基、或有機矽基取代之噻吩環，或為可經烴基或有機矽基取代之噻唑環，或為可經烷氧基、硫代烷氧基、烴基、有機矽基、鹵素原子、或鹵化烷基取代之苯基，R ⁴為烴基。 D ¹為CH或氮原子。於受體性單元具有多個D ¹時，該多個D ¹中，可存在相互相同之D ¹，亦可存在相互不同之D ¹。 D ²為碳原子、矽原子、或氮原子。 n為0或1。 *表示鍵結部位。於式(Ac-1)至式(Ac-17)所表示之單元為化合物之末端之情形時，*可為氫原子。於化合物具有多個受體性單元時，T ¹、T ²、R ¹、R ²、A ¹、A ²、D ¹、及D ²各自於單元間可相同，亦可相互不同。於環上亦可鍵結有上述取代基。] [In formula (Ac-1) to formula (Ac-17), T ¹ and T ² are each independently a single bond, or -CH=CH-, or -C≡C-, or can be substituted by a hydrocarbon group The thiophene ring is either a thiazole ring which may be substituted by a hydrocarbon group, or a pyridine ring which may be substituted by a hydrocarbon group, or a pyrazine ring which may be substituted by a hydrocarbon group. R ¹ is a hydrogen atom, or a hydrocarbon group, or -(CH ₂ ) _p -OR ³ , and R ³ is a hydrocarbon group. When the acceptor unit has a plurality of R ^{1 s} , among the plurality of R ^{1 s} , R ^{1 s} that are the same as each other may exist, or R ^{1 s} that are different from each other may exist. R ² is a hydrocarbon group. When the acceptor unit has a plurality of R ² , among the plurality of R ² , the same R ² may be present, or the R ² may be different from each other. A ¹ and A ² are each independently -(CH ₂ ) _q -OR ⁴ , or a thiophene ring that may be substituted by an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilicon group, or a thiophene ring that may be substituted by a hydrocarbon group or A thiazole ring substituted with an organosilicon group, or a phenyl group which may be substituted by an alkoxy group, a thioalkoxy group, a hydrocarbon group, an organosilicon group, a halogen atom, or a halogenated alkyl group, and ^R4 is a hydrocarbon group. D ¹ is CH or a nitrogen atom. When the acceptor unit has a plurality of D ^{1 s} , among the plurality of D ^{1 s} , there may be mutually identical D ^{1 s} , or mutually different D ^{1 s} may exist. D ² is a carbon atom, a silicon atom, or a nitrogen atom. n is 0 or 1. * Indicates a bonding site. When the unit represented by formula (Ac-1) to formula (Ac-17) is the terminal of the compound, * may be a hydrogen atom. When the compound has multiple acceptor units, T ¹ , T ² , R ¹ , R ² , A ¹ , A ² , D ¹ , and D ² may be the same or different among the units. The above substituents may also be bonded to the ring. ]

於T ¹、T ²為噻吩環之情形時，作為噻吩環可經取代而具有之烴基，可例舉與上述所說明之烴基R相同之烴基。烴基的碳數較佳為1至30，更佳為3以上，進而較佳為6以上，且更佳為28以下，進而較佳為26以下。 When T ¹ and T ² are thiophene rings, the hydrocarbon groups that may be substituted for the thiophene rings include the same hydrocarbon groups as the hydrocarbon group R described above. The carbon number of the hydrocarbon group is preferably 1 to 30, more preferably 3 or more, further preferably 6 or more, and more preferably 28 or less, further preferably 26 or less.

於T ¹、T ²為噻唑環之情形時，作為噻唑環可經取代而具有之烴基，可例舉與上述所說明之烴基R相同之烴基。烴基的碳數較佳為1至30，更佳為3以上，進而較佳為6以上，且更佳為28以下，進而較佳為26以下。 When T ¹ and T ² are thiazole rings, the hydrocarbon groups that may be substituted for the thiazole rings include the same hydrocarbon groups as the hydrocarbon groups R described above. The carbon number of the hydrocarbon group is preferably 1 to 30, more preferably 3 or more, further preferably 6 or more, and more preferably 28 or less, further preferably 26 or less.

於T ¹、T ²為吡啶環之情形時，作為吡啶環可經取代而具有之烴基，可例舉與上述所說明之烴基R相同之烴基。烴基的碳數較佳為1至30，更佳為3以上，進而較佳為6以上，且更佳為28以下，進而較佳為26以下。 When T ¹ and T ² are pyridine rings, the hydrocarbon groups which may be substituted for the pyridine rings include the same hydrocarbon groups as the hydrocarbon group R described above. The carbon number of the hydrocarbon group is preferably 1 to 30, more preferably 3 or more, further preferably 6 or more, and more preferably 28 or less, further preferably 26 or less.

於T ¹、T ²為吡嗪環之情形時，作為吡嗪環可經取代而具有之烴基，可例舉與上述所說明之烴基R相同之烴基。烴基的碳數較佳為1至30，更佳為3以上，進而較佳為6以上，且更佳為28以下，進而較佳為26以下。 When T ¹ and T ² are pyrazine rings, the hydrocarbon groups which may be substituted for the pyrazine rings include the same hydrocarbon groups as the hydrocarbon group R described above. The carbon number of the hydrocarbon group is preferably 1 to 30, more preferably 3 or more, further preferably 6 or more, and more preferably 28 or less, further preferably 26 or less.

式(Ac-1)至式(Ac-17)中，T ¹及T ²較佳為分別獨立地為單鍵，或為可經烴基取代之噻吩環，或為可經烴基取代之噻唑環，或為可經烴基取代之吡啶環。尤其是，於高分子型化合物之情形時，式(Ac-1)至式(Ac-17)中，T ¹及T ²較佳為分別獨立地為單鍵，或為可經烴基取代之噻吩環，或為可經烴基取代之噻唑環，或為可經烴基取代之吡啶環，於低分子型化合物之情形時，式(Ac-1)至式(Ac-17)中，T ¹及T ²較佳為分別獨立地為單鍵。 In formula (Ac-1) to formula (Ac-17), T ¹ and T ² are preferably each independently a single bond, or a thiophene ring that may be substituted by a hydrocarbyl group, or a thiazole ring that may be substituted by a hydrocarbyl group, Or a pyridine ring which may be substituted with a hydrocarbyl group. In particular, in the case of polymer compounds, in formula (Ac-1) to formula (Ac-17), T ¹ and T ² are preferably each independently a single bond, or thiophene which may be substituted by a hydrocarbon group Ring, or a thiazole ring that can be substituted by a hydrocarbon group, or a pyridine ring that can be substituted by a hydrocarbon group, in the case of low molecular weight compounds, in formula (Ac-1) to formula (Ac-17), T ¹ and T ² are preferably each independently a single bond.

於R ¹為烴基之情形時，作為烴基，可例舉與上述所說明之烴基R相同之烴基。R ¹所表示之烴基的碳數較佳為1至30，更佳為3以上，進而較佳為6以上，且更佳為28以下，進而較佳為26以下。烴基較佳為脂肪族烴基。於高分子型化合物之情形時，較佳為具有支鏈之脂肪族烴基。藉此，能夠確保於溶媒中之溶解性。於低分子型化合物之情形時，較佳為直鏈狀之脂肪族烴基。藉此，預計配向性提升，因此可認為電子遷移率提升。 When R ¹ is a hydrocarbon group, the hydrocarbon group may, for example, be the same as the hydrocarbon group R described above. The carbon number of the hydrocarbon group represented by R ¹ is preferably 1 to 30, more preferably 3 or more, further preferably 6 or more, and more preferably 28 or less, and still more preferably 26 or less. The hydrocarbon group is preferably an aliphatic hydrocarbon group. In the case of a polymer compound, it is preferably an aliphatic hydrocarbon group having a branch. Thereby, solubility in a solvent can be ensured. In the case of a low-molecular-weight compound, it is preferably a straight-chain aliphatic hydrocarbon group. Accordingly, since the alignment is expected to be improved, it can be considered that the electron mobility is improved.

於R ¹為-(CH ₂) _p-OR ³之情形時，作為R ³所表示之烴基，可例舉與上述所說明之烴基R相同之烴基。R ³所表示之烴基的碳數較佳為1至30，更佳為3以上，進而較佳為6以上，且更佳為28以下，進而較佳為26以下。p例如為1至5之整數。 When R ¹ is -(CH ₂ ) _p -OR ³ , the hydrocarbon group represented by R ³ may, for example, be the same as the hydrocarbon group R described above. The carbon number of the hydrocarbon group represented by R ³ is preferably 1 to 30, more preferably 3 or more, further preferably 6 or more, and more preferably 28 or less, and still more preferably 26 or less. p is an integer of 1 to 5, for example.

式(Ac-1)至式(Ac-17)中，R ¹較佳為烴基。於受體性單元具有多個R ¹時，該多個R ¹中，可存在相互相同之R ¹，亦可存在相互不同之R ¹。 In formula (Ac-1) to formula (Ac-17), R ¹ is preferably a hydrocarbon group. When the acceptor unit has a plurality of R ^{1 s} , among the plurality of R ^{1 s} , R ^{1 s} that are the same as each other may exist, or R ^{1 s} that are different from each other may exist.

作為R ²所表示之烴基，可例舉與上述所說明之烴基R相同之烴基。R ²所表示之烴基的碳數較佳為1至30，更佳為3以上，進而較佳為6以上，且更佳為28以下，進而較佳為26以下。 The hydrocarbon group represented by R ² may, for example, be the same as the hydrocarbon group R described above. The carbon number of the hydrocarbon group represented by R ² is preferably 1 to 30, more preferably 3 or more, further preferably 6 or more, and more preferably 28 or less, and still more preferably 26 or less.

於A ¹、A ²為-(CH ₂) _q-OR ⁴之情形時，作為R ⁴所表示之烴基，可例舉與上述所說明之烴基R相同之烴基。R ⁴所表示之烴基的碳數較佳為1至30，更佳為3以上，進而較佳為6以上，且更佳為28以下，進而較佳為26以下。q例如為1至5之整數。 When A ¹ and A ² are -(CH ₂ ) _q -OR ⁴ , the hydrocarbon group represented by R ⁴ may, for example, be the same as the hydrocarbon group R described above. The carbon number of the hydrocarbon group represented by R ⁴ is preferably 1 to 30, more preferably 3 or more, further preferably 6 or more, and more preferably 28 or less, and still more preferably 26 or less. q is an integer of 1 to 5, for example.

於A ¹、A ²為噻吩環之情形時，噻吩環可經取代而具有之烷氧基由-OR ⁵¹所表示，R ⁵¹為烴基。作為R ⁵¹所表示之烴基，可例舉與上述所說明之烴基R相同之烴基。R ⁵¹所表示之烴基的碳數較佳為1至30，更佳為3以上，進而較佳為6以上，且更佳為28以下，進而較佳為26以下。 When A ¹ and A ² are thiophene rings, the alkoxy groups that the thiophene rings may be substituted are represented by -OR ⁵¹ , and R ⁵¹ is a hydrocarbon group. The hydrocarbon group represented by R ⁵¹ may, for example, be the same as the hydrocarbon group R described above. The carbon number of the hydrocarbon group represented by R ⁵¹ is preferably 1 to 30, more preferably 3 or more, further preferably 6 or more, and more preferably 28 or less, and still more preferably 26 or less.

作為噻吩環可經取代而具有之硫代烷氧基由-SR ⁶所表示，R ⁶為烴基。作為R ⁶所表示之烴基，可例舉與上述所說明之烴基R相同之烴基。R ⁶所表示之烴基的碳數較佳為1至30，更佳為3以上，進而較佳為6以上，且更佳為28以下，進而較佳為26以下。 A thioalkoxy group which may be substituted as a thiophene ring is represented by -SR ⁶ , and R ⁶ is a hydrocarbon group. The hydrocarbon group represented by R ⁶ may, for example, be the same as the hydrocarbon group R described above. The carbon number of the hydrocarbon group represented by R ⁶ is preferably 1 to 30, more preferably 3 or more, further preferably 6 or more, and more preferably 28 or less, further preferably 26 or less.

作為噻吩環可經取代而具有之烴基，可例舉與上述所說明之烴基R相同之烴基。烴基的碳數較佳為1至30，更佳為3以上，進而較佳為6以上，且更佳為28以下，進而較佳為26以下。As a hydrocarbon group which a thiophene ring may have by substitution, the same thing as the hydrocarbon group R demonstrated above is mentioned. The carbon number of the hydrocarbon group is preferably 1 to 30, more preferably 3 or more, further preferably 6 or more, and more preferably 28 or less, further preferably 26 or less.

作為噻吩環可經取代而具有之有機矽基，為於Si原子上取代有1個以上之烴基之1價之基。取代到Si原子上之烴基較佳為碳數1至20之脂肪族烴基或碳數6至10之芳香族烴基。The organosilicon group which may be substituted as a 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 carbons or an aromatic hydrocarbon group having 6 to 10 carbons.

取代到Si原子上之脂肪族烴基的碳數較佳為1至18，更佳為1至8。作為脂肪族烴基，例如可例舉：甲基、乙基、異丙基、第三丁基、異丁基、辛基、十八烷基。The carbon number of the aliphatic hydrocarbon group substituted on the Si atom is preferably 1-18, more preferably 1-8. Examples of the aliphatic hydrocarbon group include methyl, ethyl, isopropyl, t-butyl, isobutyl, octyl, and octadecyl.

取代到Si原子上之芳香族烴基的碳數較佳為6至8，更佳為6至7，尤佳為6。作為芳香族烴基，例如可例舉苯基。The carbon number of the aromatic hydrocarbon group substituted on the Si atom is preferably 6-8, more preferably 6-7, especially preferably 6. As an aromatic hydrocarbon group, a phenyl group is mentioned, for example.

取代到Si原子上之烴基中，較佳為脂肪族烴基，更佳為具有支鏈之脂肪族烴基，尤佳為異丙基。Among the hydrocarbon groups substituted on the Si atom, an aliphatic hydrocarbon group is preferable, an aliphatic hydrocarbon group having a branch is more preferable, and an isopropyl group is especially preferable.

取代到Si原子上之烴基的數量較佳為2個以上，進而較佳為3個。於取代到Si原子上之烴基的數量為2個以上之情形時，取代到Si原子上之烴基亦可不同，但較佳為相同。The number of hydrocarbon groups substituted on the Si atom is preferably 2 or more, more preferably 3. When the number of hydrocarbon groups substituted on the Si atom is two or more, the hydrocarbon groups substituted on the Si atom may be different, but are preferably the same.

作為取代到Si原子上之烴基的數量為3個之情形時的具體例，可例舉：三甲基矽基、乙基二甲基矽基、異丙基二甲基矽基、三異丙基矽基、第三丁基二甲基矽基、三乙基矽基、三異丁基矽基、三丙基矽基、三丁基矽基、二甲基苯基矽基、甲基二苯基矽基等烷基矽基；三苯基矽基、第三丁基氯二苯基矽基等芳基矽基等。當中，較佳為烷基矽基，尤佳為三甲基矽基、三異丙基矽基。Specific examples of the case where the number of hydrocarbon groups substituted on the Si atom is three include: trimethylsilyl, ethyldimethylsilyl, isopropyldimethylsilyl, triisopropyl Silyl base, tertiary butyldimethylsilyl, triethylsilyl, triisobutylsilyl, tripropylsilyl, tributylsilyl, dimethylphenylsilyl, methyl di Alkyl silyl groups such as phenyl silyl groups; aryl silyl groups such as triphenyl silyl groups and tertiary butylchlorodiphenyl silyl groups, etc. Among them, an alkylsilyl group is preferable, and a trimethylsilyl group and a triisopropylsilyl group are particularly preferable.

於A ¹、A ²為噻唑環之情形時，作為噻唑環可經取代而具有之烴基，可例舉與上述所說明之烴基R相同之烴基。烴基的碳數較佳為1至30，更佳為3以上，進而較佳為6以上，且更佳為28以下，進而較佳為26以下。 When A ¹ and A ² are a thiazole ring, the hydrocarbon group which may be substituted for the thiazole ring may, for example, be the same as the hydrocarbon group R described above. The carbon number of the hydrocarbon group is preferably 1 to 30, more preferably 3 or more, further preferably 6 or more, and more preferably 28 or less, further preferably 26 or less.

作為噻唑環可經取代而具有之有機矽基，可例舉與上述所說明之有機矽基相同之有機矽基。Examples of the organosilicon group which may be substituted for the thiazole ring include the same organosilicon groups as those described above.

於A ¹、A ²為苯基之情形時，作為苯基可經取代而具有之烷氧基，可例舉與上述所說明之烷氧基相同之烷氧基。 When A ¹ and A ² are phenyl groups, the alkoxy groups that the phenyl groups may be substituted include the same alkoxy groups as those described above.

作為苯基可經取代而具有之硫代烷氧基，可例舉與上述所說明之硫代烷氧基相同之硫代烷氧基。As the thioalkoxy group which may be substituted by the phenyl group, there may be mentioned the same thioalkoxy groups as those described above.

作為苯基可經取代而具有之烴基，可例舉與上述所說明之烴基R相同之烴基。烴基的碳數較佳為1至30，更佳為3以上，進而較佳為6以上，且更佳為28以下，進而較佳為26以下。As a hydrocarbon group which a phenyl group may have by substitution, the same thing as the hydrocarbon group R demonstrated above is mentioned. The carbon number of the hydrocarbon group is preferably 1 to 30, more preferably 3 or more, further preferably 6 or more, and more preferably 28 or less, further preferably 26 or less.

作為苯基可經取代而具有之有機矽基，可例舉與上述所說明之有機矽基相同之有機矽基。Examples of the organosilicon group that may have a phenyl group that may be substituted include the same organosilicon groups as those described above.

作為苯基可經取代而具有之鹵素原子，可例舉與上述所說明之鹵素原子相同之鹵素原子。As a halogen atom which a phenyl group may have by substitution, the same thing as the halogen atom demonstrated above is mentioned.

作為苯基可經取代而具有之鹵化烷基，可例舉烴基之一部分或全部氫原子由鹵素原子取代之基，當中較佳為全部氫原子由鹵素原子取代之基(全氟烷基)。作為鹵素原子，例如可例舉氟、氯、溴、碘等，當中較佳為氟。作為鹵化烷基，例如可例舉三氟甲基、三氟乙基、全氟乙基等。The halogenated alkyl group which may be substituted by the phenyl group may, for example, be a hydrocarbon group in which a part or all of hydrogen atoms are substituted by halogen atoms, and among them, a group in which all hydrogen atoms are substituted by halogen atoms (perfluoroalkyl group) is preferred. The halogen atom may, for example, be fluorine, chlorine, bromine or iodine, among which fluorine is preferred. As a halogenated alkyl group, a trifluoromethyl group, a trifluoroethyl group, a perfluoroethyl group etc. are mentioned, for example.

D ²為碳原子、矽原子、或氮原子，D ²為碳原子或矽原子之情形時的n為1，D ²為氮原子之情形時的n為0。 D ² is a carbon atom, a silicon atom, or a nitrogen atom, n is 1 when D ² is a carbon atom or a silicon atom, and n is 0 when D ² is a nitrogen atom.

上述式(Ac-1)較佳為下述式(Ac-1-1)至式(Ac-1-4)中之任一者。The above formula (Ac-1) is preferably any one of the following formula (Ac-1-1) to formula (Ac-1-4).

[化7] [chemical 7]

上述式(Ac-2)較佳為下述式(Ac-2-1)或式(Ac-2-2)。The above formula (Ac-2) is preferably the following formula (Ac-2-1) or formula (Ac-2-2).

[化8] [chemical 8]

上述式(Ac-3)較佳為下述式(Ac-3-1)或式(Ac-3-2)。The above formula (Ac-3) is preferably the following formula (Ac-3-1) or formula (Ac-3-2).

[化9] [chemical 9]

上述式(Ac-4)較佳為下述式(Ac-4-1)至式(Ac-4-6)中之任一者。The above formula (Ac-4) is preferably any one of the following formula (Ac-4-1) to formula (Ac-4-6).

[化10] [chemical 10]

上述式(Ac-5)較佳為下述式(Ac-5-1)或式(Ac-5-2)。The above formula (Ac-5) is preferably the following formula (Ac-5-1) or formula (Ac-5-2).

[化11] [chemical 11]

上述式(Ac-6)較佳為下述式(Ac-6-1)。The above formula (Ac-6) is preferably the following formula (Ac-6-1).

[化12] [chemical 12]

上述式(Ac-7)較佳為下述式(Ac-7-1)至式(Ac-7-7)中之任一者。The above formula (Ac-7) is preferably any one of the following formulas (Ac-7-1) to (Ac-7-7).

[化13] [chemical 13]

上述式(Ac-8)較佳為下述式(Ac-8-1)至式(Ac-8-3)中之任一者。The above formula (Ac-8) is preferably any one of the following formulas (Ac-8-1) to (Ac-8-3).

[化14] [chemical 14]

上述式(Ac-9)較佳為下述式(Ac-9-1)或式(Ac-9-2)。The above formula (Ac-9) is preferably the following formula (Ac-9-1) or formula (Ac-9-2).

[化15] [chemical 15]

上述式(Ac-10)較佳為下述式(Ac-10-1)。The above formula (Ac-10) is preferably the following formula (Ac-10-1).

[化16] [chemical 16]

上述式(Ac-11)較佳為下述式(Ac-11-1)。The above formula (Ac-11) is preferably the following formula (Ac-11-1).

[化17] [chemical 17]

上述式(Ac-12)較佳為下述式(Ac-12-1)。The above formula (Ac-12) is preferably the following formula (Ac-12-1).

[化18] [chemical 18]

上述式(Ac-13)較佳為下述式(Ac-13-1)。The above formula (Ac-13) is preferably the following formula (Ac-13-1).

[化19] [chemical 19]

上述式(Ac-14)較佳為下述式(Ac-14-1)或式(Ac-14-2)。The above formula (Ac-14) is preferably the following formula (Ac-14-1) or formula (Ac-14-2).

[化20] [chemical 20]

上述式(Ac-15)較佳為下述式(Ac-15-1)至式(Ac-15-3)中之任一者。The above formula (Ac-15) is preferably any one of the following formulas (Ac-15-1) to (Ac-15-3).

[化21] [chem 21]

上述式(Ac-16)較佳為下述式(Ac-16-1)。The above formula (Ac-16) is preferably the following formula (Ac-16-1).

[化22] [chem 22]

上述式(Ac-17)較佳為下述式(Ac-17-1)。The above formula (Ac-17) is preferably the following formula (Ac-17-1).

[化23] [chem 23]

雜芳香族縮環型單元較佳為上述式(Ac-1)、式(Ac-7)、式(Ac-10)、式(Ac-13)、式(Ac-15)、或式(Ac-17)中之任一者所表示之單元，更佳為上述式(Ac-1-1)至式(Ac-1-4)、式(Ac-7-1)至式(Ac-7-7)、式(Ac-10-1)、式(Ac-13-1)、式(Ac-15-1)、式(Ac-15-2)、或式(Ac-17-1)中之任一者所表示之單元，進而較佳為上述式(Ac-1-1)、式(Ac-7-2)、式(Ac-7-5)、式(Ac-10-1)、式(Ac-13-1)、式(Ac-15-1)、式(Ac-15-2)、或式(Ac-17-1)中之任一者所表示之單元。尤其是，於低分子型化合物之情形時，雜芳香族縮環型單元較佳為上述式(Ac-15)所表示之單元，更佳為上述式(Ac-15-1)或式(Ac-15-2)所表示之單元，進而較佳為上述式(Ac-15-1)所表示之單元。The heteroaromatic ring-condensing unit is preferably the above formula (Ac-1), formula (Ac-7), formula (Ac-10), formula (Ac-13), formula (Ac-15), or formula (Ac -17) The unit represented by any one of the above-mentioned formula (Ac-1-1) to formula (Ac-1-4), formula (Ac-7-1) to formula (Ac-7- 7), formula (Ac-10-1), formula (Ac-13-1), formula (Ac-15-1), formula (Ac-15-2), or formula (Ac-17-1) The unit represented by any one is more preferably the above-mentioned formula (Ac-1-1), formula (Ac-7-2), formula (Ac-7-5), formula (Ac-10-1), formula A unit represented by any one of (Ac-13-1), formula (Ac-15-1), formula (Ac-15-2), or formula (Ac-17-1). In particular, in the case of low-molecular-weight compounds, the heteroaromatic ring-condensing unit is preferably a unit represented by the above formula (Ac-15), more preferably the above formula (Ac-15-1) or the formula (Ac The unit represented by -15-2) is more preferably a unit represented by the above-mentioned formula (Ac-15-1).

(2)芳香族縮環型單元所謂芳香族縮環型單元，係指具有縮環結構，且環之至少1個為芳香族環，構成環之元素為碳原子之結構單位。 (2) Aromatic condensed ring unit The term "aromatic condensed ring unit" refers to a structural unit having a condensed ring structure, at least one of which is an aromatic ring, and the element constituting the ring is a carbon atom.

構成環之元素為碳原子，且不含雜原子。所謂雜原子，係指碳原子以外之原子。所謂構成環之元素，意指構成縮環結構中所含之各環結構之全部元素，於縮環結構之環之至少1個為芳香族環時，該芳香族環實質上意指芳香族烴環。The elements constituting the ring are carbon atoms and do not contain heteroatoms. The term "heteroatom" refers to an atom other than a carbon atom. The element constituting the ring means all the elements constituting each ring structure contained in the condensed ring structure. When at least one of the rings of the condensed ring structure is an aromatic ring, the aromatic ring means an aromatic hydrocarbon substantially. ring.

於環上亦可鍵結有取代基。作為取代基，例如可例舉鹵素原子、烴基、醯基、酯基、鹵化烷基、氰基等。A substituent may be bonded to the ring. As a substituent, a halogen atom, a hydrocarbon group, an acyl group, an ester group, a halogenated alkyl group, a cyano group etc. are mentioned, for example.

作為鹵素原子，例如可例舉氟、氯、溴、碘等，當中較佳為氟。The halogen atom may, for example, be fluorine, chlorine, bromine or iodine, among which fluorine is preferred.

烴基較佳為脂肪族烴基，亦可為直鏈狀之脂肪族烴基，但更佳為具有支鏈之脂肪族烴基。The hydrocarbon group is preferably an aliphatic hydrocarbon group, and may be a straight-chain aliphatic hydrocarbon group, but is more preferably a branched-chain aliphatic hydrocarbon group.

作為烴基，可例舉與上述所說明之烴基R相同之烴基。烴基的碳數並無特別限定，例如較佳為1至30，更佳為3以上，進而較佳為6以上，且更佳為28以下，進而較佳為26以下。The hydrocarbon group may, for example, be the same as the hydrocarbon group R described above. The carbon number of the hydrocarbon group is not particularly limited, for example, it is preferably 1 to 30, more preferably 3 or more, further preferably 6 or more, and more preferably 28 or less, and still more preferably 26 or less.

作為醯基，例如可例舉：乙醯基、丙醯基、異丙醯基、丁醯基、異丁醯基、戊醯基、己醯基、庚醯基、辛醯基、壬醯基、癸醯基、月桂醯基、肉豆蔻醯基、棕櫚醯基、硬脂醯基、油醯基、亞麻醯基、次亞麻醯基等。Examples of the acyl group include: acetyl, propionyl, isopropyl, butyryl, isobutyryl, pentyl, hexyl, heptyl, octyl, nonyl, decanyl, lauryl Acyl, myristyl, palmityl, stearyl, oleyl, linolenoyl, sublinolenoyl, etc.

芳香族縮環型單元例如可例舉下述式(Ac-21)所表示之單元。As the aromatic ring-condensed unit, for example, a unit represented by the following formula (Ac-21) may be mentioned.

[化24] [chem 24]

[式(Ac-21)中，T ¹及T ²分別獨立地為單鍵，或為-CH=CH-，或為-C≡C-，或為可經烴基取代之噻吩環，或為可經烴基取代之噻唑環，或為可經烴基取代之吡啶環，或為可經烴基取代之吡嗪環。 R ²為烴基，R ²相互可相同亦可不同。 *表示鍵結部位。於式(Ac-21)所表示之單元為化合物之末端之情形時，*可為氫原子。於化合物具有多個受體性單元時，T ¹、T ²、及R ²各自於單元間可相同，亦可相互不同。於環上亦可鍵結有上述取代基。] [In formula (Ac-21), T ¹ and T ² are each independently a single bond, or -CH=CH-, or -C≡C-, or a thiophene ring that may be substituted by a hydrocarbon group, or a thiophene ring that may be The thiazole ring substituted by hydrocarbyl, or the pyridine ring which may be substituted by hydrocarbyl, or the pyrazine ring which may be substituted by hydrocarbyl. R ² is a hydrocarbon group, and R ² may be the same or different from each other. * Indicates a bonding site. When the unit represented by the formula (Ac-21) is a terminal of the compound, * may be a hydrogen atom. When the compound has a plurality of acceptor units, T ¹ , T ² , and R ² may be the same or different among the units. The above substituents may also be bonded to the ring. ]

T ¹及T ²之說明可引用上述(1)中之說明。T ¹與T ²亦可相互不同，但較佳為相同。 The description of T ¹ and T ² can refer to the description in (1) above. T ¹ and T ² may also be different from each other, but are preferably the same.

作為R ²所表示之烴基，可例舉與上述所說明之烴基R相同之烴基。烴基的碳數較佳為1至30，更佳為3以上，進而較佳為6以上，且更佳為28以下，進而較佳為26以下。 The hydrocarbon group represented by R ² may, for example, be the same as the hydrocarbon group R described above. The carbon number of the hydrocarbon group is preferably 1 to 30, more preferably 3 or more, further preferably 6 or more, and more preferably 28 or less, further preferably 26 or less.

上述式(Ac-21)較佳為下述式(Ac-21-1)。The above formula (Ac-21) is preferably the following formula (Ac-21-1).

[化25] [chem 25]

(3)單環型單元所謂單環型單元，係指具有芳香族環且不具有縮環結構之結構單位。 (3) Single ring unit The so-called monocyclic unit refers to a structural unit having an aromatic ring and not having a condensed ring structure.

芳香族環可為芳香族烴環，亦可為雜芳香族環(有時亦稱為芳香族雜環)，亦可為多個芳香族環經由碳原子或雜原子鍵結之環。The aromatic ring may be an aromatic hydrocarbon ring, a heteroaromatic ring (sometimes also referred to as an aromatic heterocycle), or a ring in which multiple aromatic rings are bonded via carbon atoms or heteroatoms.

單環型單元例如可例舉下述式(Ac-31)至式(Ac-33)所表示之單元。As a monocyclic unit, the unit represented by following formula (Ac-31) - a formula (Ac-33) is mentioned, for example.

[化26] [chem 26]

[式(Ac-31)至式(Ac-33)中，T ¹及T ²分別獨立地為單鍵，或為-CH=CH-，或為-C≡C-，或為可經烴基取代之噻吩環，或為可經烴基取代之噻唑環，或為可經烴基取代之吡啶環，或為可經烴基取代之吡嗪環。 *表示鍵結部位。於式(Ac-31)至式(Ac-33)所表示之單元為化合物之末端之情形時，*可為氫原子。於化合物具有多個受體性單元時，T ¹及T ²各自於單元間可相同，亦可相互不同。於環上亦可鍵結有上述取代基。] [In formula (Ac-31) to formula (Ac-33), T ¹ and T ² are each independently a single bond, or -CH=CH-, or -C≡C-, or can be substituted by a hydrocarbon group The thiophene ring is either a thiazole ring which may be substituted by a hydrocarbon group, or a pyridine ring which may be substituted by a hydrocarbon group, or a pyrazine ring which may be substituted by a hydrocarbon group. * Indicates a bonding site. When the unit represented by formula (Ac-31) to formula (Ac-33) is the terminal of the compound, * may be a hydrogen atom. When the compound has multiple acceptor units, T ¹ and T ² may be the same or different among the units. The above substituents may also be bonded to the ring. ]

T ¹及T ²之說明可引用上述(1)中之說明。 The description of T ¹ and T ² can refer to the description in (1) above.

上述式(Ac-31)較佳為下述式(Ac-31-1)至式(Ac-31-3)中之任一者。上述式(Ac-32)較佳為下述式(Ac-32-1)。上述式(Ac-33)較佳為下述式(Ac-33-1)或式(Ac-33-2)。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).

[化27] [chem 27]

本發明之化合物例如可為具有供體性單元及受體性單元作為重複單位之高分子型化合物。於為高分子型化合物之情形時，供體性單元與受體性單元可無規地配置，但較佳為交替地配置。The compound of the present invention may be, for example, a polymer compound having a donor unit and an acceptor unit as repeating units. In the case of a polymer compound, the donor unit and the acceptor unit may be arranged randomly, but are preferably arranged alternately.

構成本發明之高分子型化合物之多個供體性單元可包含至少1個以上之上述式(Do-A)所表示之單位，且進而包含下述式(Do-K)所表示之單位。下述式(Do-K)中，*表示鍵結部位。於包含下述式(Do-K)所表示之單位之供體性單元為化合物之末端之情形時，*可為氫原子。The plurality of donating units constituting the polymer compound of the present invention may contain at least one unit represented by the above-mentioned formula (Do-A), and may further contain a unit represented by the following formula (Do-K). In the following formula (Do-K), * represents a bonding site. When the donating unit including the unit represented by the following formula (Do-K) is the terminal of the compound, * may be a hydrogen atom.

[化28] [chem 28]

上述式(Do-K)所表示之單位在電子供應性亦優異。另外，藉由包含上述式(Do-K)所表示之單位，可期待由分子間之相互作用所帶來的配向性提升、及由LUMO之深化所帶來的器件之穩定性提升。因此，藉由供體性單元進而包含上述式(Do-K)所表示之單位，能夠適宜調整性能及溶解性。The unit represented by the above formula (Do-K) is also excellent in electron donating properties. In addition, by including the unit represented by the above-mentioned formula (Do-K), the improvement of alignment due to the interaction between molecules and the improvement of the stability of the device due to the deepening of LUMO can be expected. Therefore, by further including the unit represented by the above formula (Do-K) as a donating unit, performance and solubility can be appropriately adjusted.

關於構成本發明之高分子型化合物之多個供體性單元，於將供體性單元整體設為100mol%時，上述式(Do-A)所表示之單位與上述式(Do-K)所表示之單位之合計例如較佳為50mol%以上，更佳為70mol%以上，進而較佳為90mol%以上。亦可供體性單元之整體(100mol%)為上述式(Do-A)所表示之單位及上述式(Do-K)所表示之單位。With regard to the plurality of donating units constituting the polymer compound of the present invention, the unit represented by the above formula (Do-A) is the same as the unit represented by the above formula (Do-K) when the whole of the donating units is taken as 100 mol%. The total of the units indicated is, for example, preferably at least 50 mol%, more preferably at least 70 mol%, and still more preferably at least 90 mol%. The whole (100 mol%) of the donor unit may be the unit represented by the above-mentioned formula (Do-A) and the unit represented by the above-mentioned formula (Do-K).

於構成本發明之高分子型化合物之多個供體性單元含有上述式(Do-A)所表示之單位及上述式(Do-K)所表示之單位之兩者之情形時，上述式(Do-A)所表示之單位與上述式(Do-K)所表示之單位之混合比[式(Do-A)所表示之單位/上述式(Do-K)所表示之單位]並無特別限定，較佳為以莫耳比計為3/7至7/3。混合比更佳為以莫耳比計為4/6至6/4。When the multiple donating units constituting the polymer compound of the present invention contain both the unit represented by the above formula (Do-A) and the unit represented by the above formula (Do-K), the above formula ( The mixing ratio of the unit represented by Do-A) and the unit represented by the above formula (Do-K) [the unit represented by the formula (Do-A)/the unit represented by the above formula (Do-K)] is not particularly special The limit is preferably 3/7 to 7/3 in terms of molar ratio. The mixing ratio is more preferably 4/6 to 6/4 in molar ratio.

本發明之化合物例如可為具有供體性單元及受體性單元合計2個或3個之低分子型化合物。於為低分子型化合物之情形時，較佳為於供體性單元上連結有2個受體性單元之三聚物型化合物。The compound of the present invention may be, for example, a low-molecular-weight compound having a total of 2 or 3 donor units and acceptor units. In the case of a low-molecular-weight compound, a trimer-type compound in which two acceptor units are linked to the donor unit is preferred.

本發明之化合物的分子量取決於構成該化合物之供體性單元及受體性單元的分子量，因此根據供體性單元及受體性單元的分子量，有時低分子型化合物的分子量大於高分子型化合物的分子量。The molecular weight of the compound of the present invention depends on the molecular weight of the donor unit and the acceptor unit constituting the compound. Therefore, depending on the molecular weight of the donor unit and the acceptor unit, the molecular weight of the low-molecular-weight compound may be larger than that of the high-molecular-weight compound. The molecular weight of the compound.

本發明之高分子型化合物的重量平均分子量(Mw)例如較佳為1500以上，更佳為3000以上，進而較佳為7000以上。高分子型化合物的重量平均分子量(Mw)的上限並無特別限定，例如只要為300000以下即可，亦可為200000以下。The weight average molecular weight (Mw) of the polymer compound of the present invention is, for example, preferably at least 1500, more preferably at least 3000, and still more preferably at least 7000. The upper limit of the weight average molecular weight (Mw) of a polymer compound is not specifically limited, For example, what is necessary is just to be 300,000 or less, and 200,000 or less may be sufficient.

本發明之高分子型化合物的數量平均分子量(Mn)例如較佳為1000以上，更佳為2000以上，進而較佳為4000以上。高分子型化合物的數量平均分子量(Mn)的上限並無特別限定，例如只要為300000以下即可，亦可為200000以下。The number average molecular weight (Mn) of the polymer compound of the present invention is, for example, preferably at least 1,000, more preferably at least 2,000, and still more preferably at least 4,000. The upper limit of the number average molecular weight (Mn) of a polymer compound is not specifically limited, For example, what is necessary is just to be 300000 or less, and it may be 200000 or less.

本發明之低分子型化合物的分子量例如較佳為2500以下。該分子量更佳為2300以下，進而較佳為1300以下。The molecular weight of the low-molecular-weight compound of the present invention is preferably, for example, 2,500 or less. The molecular weight is more preferably 2300 or less, further preferably 1300 or less.

本發明之化合物的重量平均分子量(Mw)及數量平均分子量(Mn)可使用凝膠滲透層析法，基於將聚苯乙烯作為標準試樣所製作之校準曲線而算出。The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the compound of the present invention can be calculated using gel permeation chromatography based on a calibration curve prepared using polystyrene as a standard sample.

本發明之化合物的游離能較佳為-4eV以下，更佳為-4.5eV以下，進而較佳為-5eV以下，尤佳為-5.1eV以下。游離能的下限並無特別限定，例如較佳為-7eV以上，更佳為-6.5eV以上，進而較佳為-6.2eV以上。The free energy of the compound of the present invention is preferably -4eV or less, more preferably -4.5eV or less, still more preferably -5eV or less, especially preferably -5.1eV or less. The lower limit of the ionization energy is not particularly limited, for example, it is preferably -7 eV or higher, more preferably -6.5 eV or higher, and still more preferably -6.2 eV or higher.

本發明中亦包括包含上述化合物之有機半導體材料。例如，由於包含上述式(Do-A)所表示之單位之供體性單元在電子供應性優異，故而具有該供體性單元及受體性單元各1個以上且供體性單元與受體性單元相互連結之化合物作為有機半導體材料有用。另外，本發明之化合物包含以縮醛結構來螺環化之上述式(Do-A)所表示之單位，因此於溶媒中之溶解性變得良好。因此，包含本發明之化合物之有機半導體材料於溶媒中之溶解性變得良好，塗佈於基板之膜的膜質變得良好，電子遷移率變得良好。Organic semiconductor materials comprising the above-mentioned compounds are also included in the present invention. For example, since the donor unit comprising the unit represented by the above formula (Do-A) is excellent in electron donating properties, there are at least one donor unit and one acceptor unit each, and the donor unit and the acceptor Compounds in which functional units are connected to each other are useful as organic semiconductor materials. Moreover, the compound of this invention contains the unit represented by the said formula (Do-A) spirocyclized with an acetal structure, Therefore The solubility to a solvent becomes favorable. Therefore, the solubility of the organic semiconductor material containing the compound of the present invention in a solvent becomes good, the film quality of the film coated on the substrate becomes good, and the electron mobility becomes good.

上述溶媒可例舉鹵素系有機溶媒及非鹵素系有機溶媒。本發明之化合物於溶媒中之溶解性、尤其是於鹵素系有機溶媒及／或非鹵素系有機溶媒中之溶解性良好。作為鹵素系有機溶媒，例如可例舉氯仿、四氯乙烷、氯苯等。作為非鹵素系有機溶媒，例如可例舉甲苯、1-甲基萘、2-甲基萘等。本發明之化合物較佳為至少溶解於鹵素系有機溶媒。The aforementioned solvent may, for example, be a halogen-based organic solvent or a non-halogen-based organic solvent. The compounds of the present invention have good solubility in solvents, especially in halogen-based organic solvents and/or non-halogen-based organic solvents. As a halogen type organic solvent, chloroform, tetrachloroethane, chlorobenzene etc. are mentioned, for example. As a non-halogen organic solvent, toluene, 1-methylnaphthalene, 2-methylnaphthalene, etc. are mentioned, for example. The compound of the present invention is preferably dissolved in at least a halogen-based organic solvent.

本發明之有機半導體材料可較佳地用作n型有機半導體材料。The organic semiconductor material of the present invention can be preferably used as an n-type organic semiconductor material.

本發明中亦包括包含上述有機半導體材料之有機電子器件。亦即，上述有機半導體材料可較佳地用作有機電子器件之原材料，例如可用作有機電致發光元件、有機薄膜電晶體元件、有機光電轉換元件、有機薄膜太陽能電池模組等有機電子器件之材料。Organic electronic devices comprising the above-mentioned organic semiconductor materials are also included in the present invention. That is, the above-mentioned organic semiconductor materials can be preferably used as raw materials for organic electronic devices, such as organic electroluminescent elements, organic thin film transistor elements, organic photoelectric conversion elements, organic thin film solar cell modules and other organic electronic devices The material.

其次，對可製造本發明之化合物之方法進行說明。Next, a method for producing the compound of the present invention will be described.

本發明之化合物例如可藉由使供體性單元之鍵結部位上鍵結有具有有機取代基之錫而成之化合物(以下，有時稱為供體原料)、與受體性單元之鍵結部位上鍵結有鹵素原子之化合物(以下，有時稱為受體原料)進行偶合反應而製造(以下，有時稱為偶合步驟)。The compound of the present invention can be, for example, a compound in which tin having an organic substituent is bonded to the bonding site of the donor unit (hereinafter sometimes referred to as a donor material), and the bond to the acceptor unit A compound having a halogen atom bonded to the junction site (hereinafter, sometimes referred to as an acceptor material) is produced by performing a coupling reaction (hereinafter, sometimes referred to as a coupling step).

供體原料可使用與前述(Do-A)單位對應之下述式(do-A)所表示之化合物。As the donor material, a compound represented by the following formula (do-A) corresponding to the above-mentioned (Do-A) unit can be used.

[化29] [chem 29]

式(do-A)中，R ^a與前述相同。於式(do-A)所表示之化合物中，前述R ^a為碳數2之伸乙基之情形時，式(do-A)所表示之化合物由下述式(do-a)所表示。 In formula (do-A), R ^a is the same as above. In the compound represented by the formula (do-A), when the aforementioned R ^a is an ethylenyl group having 2 carbon atoms, the compound represented by the formula (do-A) is represented by the following formula (do-a).

[化30] [chem 30]

R ¹¹及R ¹²表示有機取代基，分別獨立地為烴基。多個R ¹¹中，可存在相互相同之R ¹¹，亦可存在相互不同之R ¹¹，多個R ¹²中，可存在相互相同之R ¹²，亦可存在相互不同之R ¹²。作為R ¹¹、R ¹²所表示之烴基，可例舉與上述所說明之烴基R相同之烴基。R ¹¹、R ¹²所表示之烴基的碳數較佳為1至10，更佳為2以上，進而較佳為3以上，且更佳為5以下，進而較佳為4以下。R ¹¹與R ¹²亦可相互不同，但較佳為相同。 R ¹¹ and R ¹² represent organic substituents, each independently being a hydrocarbon group. Among the plurality of R ^11s ^, R ¹¹ may be the same as or different from each other, and R ¹² may be the same or different from each other among ^the plurality of R ^12s . The hydrocarbon group represented by R ¹¹ and R ¹² may, for example, be the same as the hydrocarbon group R described above. The carbon number of the hydrocarbon group represented by R ¹¹ and R ¹² is preferably 1 to 10, more preferably 2 or more, still more preferably 3 or more, more preferably 5 or less, still more preferably 4 or less. R ¹¹ and R ¹² may also be different from each other, but are preferably the same.

式(do-A)所表示之化合物可基於日本特開2009-215278號公報中所記載之方法來製造。The compound represented by the formula (do-A) can be produced based on the method described in JP-A-2009-215278.

此外，式(Do-K)所表示之單位可藉由使式(do-A)所表示之化合物偶合後，使縮醛結構轉化為酮結構而合成。In addition, the unit represented by the formula (Do-K) can be synthesized by converting the acetal structure into a ketone structure after coupling the compound represented by the formula (do-A).

作為受體原料上所鍵結之前述鹵素原子，例如可例舉氟、氯、溴、碘等，當中較佳為溴。Examples of the aforementioned halogen atoms bonded to the acceptor material include fluorine, chlorine, bromine, and iodine, among which bromine is preferred.

作為受體原料，例如可例舉：於上述之(1)雜芳香族縮環型單元之鍵結部位上鍵結有鹵素原子之化合物、於(2)芳香族縮環型單元之鍵結部位上鍵結有鹵素原子之化合物、於(3)單環型單元之鍵結部位上鍵結有鹵素原子之化合物。As the acceptor material, for example, a compound having a halogen atom bonded to the bonding site of the (1) heteroaromatic condensed ring type unit mentioned above, and a compound having a bonded site to (2) the aromatic condensed ring type unit A compound having a halogen atom bonded thereto, a compound having a halogen atom bonded to the bonding site of the (3) monocyclic unit.

於(1)雜芳香族縮環型單元之鍵結部位上鍵結有鹵素原子之化合物例如可例舉下述式(ac-1)至式(ac-17)所表示之化合物。此外，下述式(ac-1)至式(ac-17)中表示雜芳香族縮環型單元具有2個鍵結部位且各鍵結部位上鍵結有鹵素原子Y之化合物，但於使下述式(ac-1)至式(ac-17)所表示之化合物作為末端鍵結於供體性單元之情形時，使用使鍵結部位成為1個之化合物即可。(1) Compounds in which a halogen atom is bonded to the bonding site of the heteroaromatic ring-condensed unit include, for example, compounds represented by the following formulas (ac-1) to (ac-17). In addition, the following formulas (ac-1) to formula (ac-17) represent compounds in which the heteroaromatic ring-condensing unit has two bonding sites and a halogen atom Y is bonded to each bonding site, but when using When the compounds represented by the following formula (ac-1) to formula (ac-17) are bonded to the donor unit as the terminal, a compound having only one bonding site may be used.

[化31] [chem 31]

[式(ac-1)至式(ac-17)中，T ¹、T ²、R ¹、R ²、A ¹、A ²、D ¹、D ²、及n與關於前述式(Ac-1)至式(Ac-17)所說明之各者相同。 Y表示鹵素原子。於將式(ac-1)至式(ac-17)所表示之受體原料之2種以上組合使用時，T ¹、T ²、R ¹、R ²、A ¹、A ²、D ¹、D ²、及Y各自於受體原料間可相同，亦可相互不同。於環上亦可鍵結有上述取代基。] [In formula (ac-1) to formula (ac-17), T ¹ , T ² , R ¹ , R ² , A ¹ , A ² , D ¹ , D ² , and n are the same as those for the aforementioned formula (Ac-1 ) to formula (Ac-17) are the same. Y represents a halogen atom. When two or more acceptor materials represented by formula (ac-1) to formula (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 among the acceptor materials. The above substituents may also be bonded to the ring. ]

作為鹵素原子Y，例如可例舉氟、氯、溴、碘等，當中較佳為溴。The halogen atom Y includes, for example, fluorine, chlorine, bromine, iodine and the like, among which bromine is preferred.

於(2) 芳香族縮環型單元之鍵結部位上鍵結有鹵素原子之化合物例如可例舉下述式(ac-21)所表示之化合物。此外，下述式(ac-21)中表示芳香族縮環型單元具有2個鍵結部位且各鍵結部位上鍵結有鹵素原子之化合物，但於使下述式(ac-21)所表示之化合物作為末端鍵結於供體性單元之情形時，使用使鍵結部位成為1個之化合物即可。(2) The compound having a halogen atom bonded to the bonding site of the aromatic ring-condensed unit (2) may, for example, be a compound represented by the following formula (ac-21). In addition, the following formula (ac-21) represents a compound in which the aromatic condensed ring unit has two bonding sites and a halogen atom is bonded to each bonding site, but when the following formula (ac-21) is used In the case where the indicated compound is bound to the donor unit as a terminal, a compound having one binding site may be used.

[化32] [chem 32]

[式(ac-21)中，T ¹、T ²、及R ²與前述式(Ac-21)相同。 Y表示鹵素原子。於將式(ac-21)所表示之受體原料之2種以上組合使用時，T ¹、T ²、R ²、及Y各自於受體原料間可相同，亦可相互不同。於環上亦可鍵結有上述取代基。] [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 acceptor materials represented by the formula (ac-21) are used in combination, T ¹ , T ² , R ² , and Y may be the same or different among the acceptor materials. The above substituents may also be bonded to the ring. ]

(3) 單環型單元之鍵結部位上鍵結有鹵素原子之化合物例如可例舉下述式(ac-31)至式(ac-33)所表示之化合物。此外，下述式(ac-31)至式(ac-33)中表示單環型單元具有2個鍵結部位且各鍵結部位上鍵結有鹵素原子之化合物，但於使下述式(ac-31)至式(ac-33)所表示之化合物作為末端鍵結於供體性單元之情形時，使用使鍵結部位的數量為1個之化合物即可。(3) Compounds in which a halogen atom is bonded to the bonding site of the monocyclic unit include, for example, compounds represented by the following formula (ac-31) to formula (ac-33). In addition, the following formulas (ac-31) to (ac-33) represent compounds in which the monocyclic unit has two bonding sites and a halogen atom is bonded to each bonding site, but when the following formula ( When the compound represented by ac-31) to formula (ac-33) is bonded to the donor unit as the terminal, a compound having one bonding site may be used.

[化33] [chem 33]

[式(ac-31)至式(ac-33)中，T ¹及T ²與關於前述式(Ac-31)至式(Ac-33)所說明之各者相同。 Y表示鹵素原子。於將式(ac-31)至式(ac-33)所表示之受體原料之2種以上組合使用時，T ¹、T ²、及Y各自於受體原料間可相同，亦可相互不同。於環上亦可鍵結有上述取代基。] [In formula (ac-31) to formula (ac-33), T ¹ and T ² are the same as each of the above-mentioned formula (Ac-31) to formula (Ac-33). Y represents a halogen atom. When two or more acceptor materials represented by formula (ac-31) to formula (ac-33) are used in combination, T ¹ , T ² , and Y may be the same or different among the acceptor materials . The above substituents may also be bonded to the ring. ]

上述式(do-A)所表示之有機錫化合物與受體性單元之鹵化物較佳為於金屬觸媒之存在下進行偶合反應。The organotin compound represented by the above formula (do-A) and the halide of the acceptor unit are preferably subjected to a coupling reaction in the presence of a metal catalyst.

作為偶合反應中所使用之金屬觸媒，例如可例舉：鈀系觸媒、鎳系觸媒、鐵系觸媒、銅系觸媒、銠系觸媒、釕系觸媒等過渡金屬觸媒。這些當中，較佳為鈀系觸媒。鈀系觸媒中所含之鈀的價數並無特別限定，可為0價，亦可為2價。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, a palladium-based catalyst is preferable. The valence of palladium contained in the palladium-based catalyst is not particularly limited, and may be zero or divalent.

作為鈀系觸媒，例如可例舉：氯化鈀(II)、溴化鈀(II)、碘化鈀(II)、氧化鈀(II)、硫化鈀(II)、碲化鈀(II)、氫氧化鈀(II)、硒化鈀(II)、氰化鈀(II)、乙酸鈀(II)、三氟乙酸鈀(II)、乙醯乙酸鈀(II)、雙(三苯基膦)二乙酸鈀(II)、四(三苯基膦)鈀(0)、二氯雙(三苯基膦)鈀(II)、二氯雙(乙腈)鈀(II)、二氯雙(苯甲腈)鈀(II)、二氯[1,2-雙(二苯基膦基)乙烷]鈀(II)、二氯[1,3-雙(二苯基膦基)丙烷]鈀(II)、二氯[1,4-雙(二苯基膦基)丁烷]鈀(II)、二氯[1,1-雙(二苯基膦基二茂鐵)]鈀(II)、二氯[1,1-雙(二苯基膦基)二茂鐵]鈀(II)二氯甲烷加成物、雙(二亞苄基丙酮)鈀(0)、三(二亞苄基丙酮)二鈀(0)、三(二亞苄基丙酮)二鈀(0)氯仿加成物、二氯[1,3-雙(2,6-二異丙基苯基)咪唑-2-茚](3-氯吡啶基)鈀(II)、雙(三第三丁基膦)鈀(0)、二氯[2,5-降冰片二烯]鈀(II)、二氯雙(乙二胺)鈀(II)、二氯(1,5-環辛二烯)鈀(II)、二氯雙(甲基二苯基膦)鈀(II)。這些當中，較佳為使用三(二亞苄基丙酮)二鈀(0)、三(二亞苄基丙酮)二鈀(0)氯仿加成物。Examples of palladium-based catalysts include palladium(II) chloride, palladium(II) bromide, palladium(II) iodide, palladium(II) oxide, palladium(II) sulfide, and palladium(II) telluride , palladium(II) hydroxide, palladium(II) selenide, palladium(II) cyanide, palladium(II) acetate, palladium(II) trifluoroacetate, palladium(II) acetylacetate, bis(triphenylphosphine ) palladium(II) diacetate, tetrakis(triphenylphosphine)palladium(0), dichlorobis(triphenylphosphine)palladium(II), dichlorobis(acetonitrile)palladium(II), dichlorobis(benzene Dichloro[1,2-bis(diphenylphosphino)ethane]palladium(II), dichloro[1,3-bis(diphenylphosphino)propane]palladium( II), dichloro[1,4-bis(diphenylphosphino)butane]palladium(II), dichloro[1,1-bis(diphenylphosphinoferrocene)]palladium(II), Dichloro[1,1-bis(diphenylphosphino)ferrocene]palladium(II) dichloromethane adduct, bis(dibenzylideneacetone)palladium(0), tris(dibenzylideneacetone) ) Dipalladium (0), tris(dibenzylideneacetone) dipalladium (0) chloroform adduct, dichloro[1,3-bis(2,6-diisopropylphenyl)imidazole-2-indene ](3-chloropyridyl)palladium(II), bis(tri-tert-butylphosphine)palladium(0), dichloro[2,5-norbornadiene]palladium(II), dichlorobis(ethylenediene Amine) palladium(II), dichloro(1,5-cyclooctadiene)palladium(II), dichlorobis(methyldiphenylphosphine)palladium(II). Among these, tris(dibenzylideneacetone)dipalladium(0) and tris(dibenzylideneacetone)dipalladium(0) chloroform adducts are preferably used.

作為銅系觸媒，例如可例舉：銅、氟化銅(I)、氯化銅(I)、溴化銅(I)、碘化銅(I)、氟化銅(II)、氯化銅(II)、溴化銅(II)、碘化銅(II)等鹵化銅化合物；氧化銅(I)、硫化銅(I)、氧化銅(II)、硫化銅(II)、乙酸銅(I)、乙酸銅(II)、硫酸銅(II)等。Examples of copper-based catalysts include copper, copper (I) fluoride, copper (I) chloride, copper (I) bromide, copper (I) iodide, copper (II) fluoride, Copper(II), copper(II) bromide, copper(II) iodide and other copper halide compounds; copper(I) oxide, copper(I) sulfide, copper(II) oxide, copper(II) sulfide, copper acetate( I), copper (II) acetate, copper (II) sulfate, etc.

金屬觸媒可單獨使用1種，亦可混合使用2種以上。A metal catalyst may be used individually by 1 type, and may mix and use 2 or more types.

於偶合步驟中，上述式(do-A)所表示之有機錫化合物與金屬觸媒之莫耳比(式(do-A)所表示之有機錫化合物：金屬觸媒)例如為1：0.0001至1：0.5左右，較佳為1：0.001至1：0.4，更佳為1：0.005至1：0.3，進而較佳為1：0.01至1：0.2。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, 1:0.0001 to 1:0.5 or so, preferably 1:0.001 to 1:0.4, more preferably 1:0.005 to 1:0.3, further preferably 1:0.01 to 1:0.2.

於偶合步驟中，亦可使配位基配位於金屬觸媒。作為配位基，例如可例舉：三甲基膦、三乙基膦、三(正丁基)膦、三(異丙基)膦、三(第三丁基)膦、雙(第三丁基)甲基膦、三環己基膦、二苯基(甲基)膦、三苯基膦、三(鄰甲苯基)膦、三(間甲苯基)膦、三(對甲苯基)膦、三(2-呋喃基)膦、三(2-甲氧基苯基)膦、三(3-甲氧基苯基)膦、三(4-甲氧基苯基)膦、四氟硼酸三第三丁基鏻、2-二環己基膦基聯苯、2-二環己基膦基-2'-甲基聯苯、2-二環己基膦基-2',4',6'-三異丙基-1,1'-聯苯、2-二環己基膦基-2',6'-二甲氧基-1,1'-聯苯、2-二環己基膦基-2'-(N,N'-二甲基胺基)聯苯、2-二苯基膦基-2'-(N,N'-二甲基胺基)聯苯、2-(二第三丁基)膦基-2'-(N,N'-二甲基胺基)聯苯、2-(二第三丁基)膦基聯苯、2-(二第三丁基)膦基-2'-甲基聯苯、1,2-雙(二苯基膦基)乙烷、1,3-雙(二苯基膦基)丙烷、1,4-雙(二苯基膦基)丁烷、1,2-雙(二環己基膦基)乙烷、1,3-雙(二環己基膦基)丙烷、1,4-雙(二環己基膦基)丁烷、1,2-雙二苯基膦基乙烯、1,1'-雙(二苯基膦基)二茂鐵、1,2-乙二胺、N,N,N',N'-四甲基乙二胺、2,2'-聯吡啶、1,3-二苯基二氫亞咪唑基、1,3-二甲基二氫亞咪唑基、二乙基二氫亞咪唑基、1,3-雙(2,4,6-三甲基苯基)二氫亞咪唑基、1,3-雙(2,6-二異丙基苯基)二氫亞咪唑基、1,10-啡啉、5,6-二甲基-1,10-啡啉、4,7-二甲基-1,10-啡啉。這些當中，較佳為三甲基膦、三乙基膦、三(正丁基)膦、三(異丙基)膦、三(第三丁基)膦、雙(第三丁基)甲基膦、三環己基膦、二苯基(甲基)膦、三苯基膦、三(鄰甲苯基)膦、三(間甲苯基)膦、三(對甲苯基)膦、三(2-呋喃基)膦、三(2-甲氧基苯基)膦、三(3-甲氧基苯基)膦、三(4-甲氧基苯基)膦，更佳為三(2-甲氧基苯基)膦。During the coupling step, the ligand can also be coordinated to the metal catalyst. As the ligand, for example, trimethylphosphine, triethylphosphine, tri(n-butyl)phosphine, tri(isopropyl)phosphine, tri(tert-butyl)phosphine, bis(tert-butyl)phosphine, base) methylphosphine, tricyclohexylphosphine, diphenyl(methyl)phosphine, triphenylphosphine, tri(o-tolyl)phosphine, tri(m-tolyl)phosphine, tri(p-tolyl)phosphine, tri (2-furyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(3-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, trifluoroborate Butylphosphonium, 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-tert-butyl)phosphino -2'-(N,N'-dimethylamino)biphenyl, 2-(di-tert-butyl)phosphino-biphenyl, 2-(di-tert-butyl)phosphino-2'-methyl Biphenyl, 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-bisdiphenylphosphine ethylenediamine, 1,1'-bis(diphenylphosphino)ferrocene, 1,2-ethylenediamine, N,N,N',N'-tetramethylethylenediamine, 2,2'- Bipyridine, 1,3-diphenyldihydroimidazolyl, 1,3-dimethyldihydroimidazolyl, diethyldihydroimidazolyl, 1,3-bis(2,4,6- Trimethylphenyl) dihydroimidazolyl, 1,3-bis(2,6-diisopropylphenyl) dihydroimidazolyl, 1,10-phenanthroline, 5,6-dimethyl- 1,10-phenanthroline, 4,7-dimethyl-1,10-phenanthroline. Among these, trimethylphosphine, triethylphosphine, tri(n-butyl)phosphine, tri(isopropyl)phosphine, tri(tert-butyl)phosphine, bis(tert-butyl)methyl Phosphine, tricyclohexylphosphine, diphenyl(methyl)phosphine, triphenylphosphine, tri(o-tolyl)phosphine, tri(m-tolyl)phosphine, tri(p-tolyl)phosphine, tri(2-furan) base) phosphine, tris (2-methoxyphenyl) phosphine, tris (3-methoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, more preferably tris (2-methoxy phenyl) phosphine.

配位基可單獨使用1種，亦可混合使用2種以上。A ligand may be used individually by 1 type, and may mix and use 2 or more types.

於使配位基配位於金屬觸媒之情形時，金屬觸媒與配位基之莫耳比(金屬觸媒：配位基)例如為1：0.5至1：10左右，較佳為1：1至1：8，更佳為1：1至1：7，進而較佳為1：1至1：5。When the ligand is coordinated to the 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, further preferably 1:1 to 1:5.

於偶合步驟中，較佳為使用溶媒，只要不對反應造成影響，則溶媒並無特別限定，例如可使用醚系溶媒、芳香族系溶媒、酯系溶媒、烴系溶媒、鹵素系溶媒、酮系溶媒、醯胺系溶媒、腈系溶媒、亞碸系溶媒、碸系溶媒等。In the coupling step, it is preferable to use a solvent. As long as it does not affect the reaction, the solvent is not particularly limited. For example, ether solvents, aromatic solvents, ester solvents, hydrocarbon solvents, halogen solvents, and ketone solvents can be used. Solvents, amide-based solvents, nitrile-based solvents, argon-based solvents, argon-based solvents, etc.

作為醚系溶媒，例如可例舉二***、二丙醚、二異丙醚、二丁醚、四氫呋喃、甲基四氫呋喃、二甲氧基乙烷、環戊基甲醚、第三丁基甲醚、二噁烷等。作為芳香族系溶媒，例如可例舉苯、甲苯、二甲苯、均三甲苯、氯苯、二氯苯、四氫萘等。作為酯系溶媒，例如可例舉乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸異丙酯、乙酸丁酯等。作為烴系溶媒，例如可例舉戊烷、己烷、庚烷、辛烷、十氫萘等。作為鹵素系溶媒，例如可例舉二氯甲烷、氯仿、二氯乙烷、二氯丙烷等。作為酮系溶媒，例如可例舉丙酮、甲基乙基酮、甲基異丁基酮等。作為醯胺系溶媒，例如可例舉N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、1,3-二甲基-2-咪唑啶酮、1,3-二甲基-3,4,5,6-四氫-(1H)-嘧啶等。作為腈系溶媒，例如可例舉乙腈等。作為亞碸系溶媒，例如可例舉二甲基亞碸等。作為碸系溶媒，例如可例舉環丁碸等。這些當中，較佳為芳香族系溶媒，更佳為氯苯。Examples of ether solvents include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, methyl tetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, tertiary butyl methyl ether, Oxane etc. As an aromatic solvent, benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, tetralin, etc. are mentioned, for example. As an ester type solvent, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, etc. are mentioned, for example. As a hydrocarbon-based solvent, pentane, hexane, heptane, octane, decahydronaphthalene, etc. are mentioned, for example. As a halogen type solvent, methylene chloride, chloroform, dichloroethane, dichloropropane etc. are mentioned, for example. As a ketone solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. are mentioned, for example. Examples of amide-based solvents include N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, 1,3- Dimethyl-3,4,5,6-tetrahydro-(1H)-pyrimidine, etc. As a nitrile-type solvent, acetonitrile etc. are mentioned, for example. As the argon-based solvent, for example, dimethyl arsenic and the like may be mentioned. As a pyrene-based solvent, cyclobutane etc. are mentioned, for example. Among these, aromatic solvents are preferable, and chlorobenzene is more preferable.

溶媒可單獨使用1種，亦可混合使用2種以上。A solvent may be used individually by 1 type, and may mix and use 2 or more types.

偶合步驟中所使用之溶媒之量相對於上述式(do-A)所表示之有機錫化合物與受體性單元之鹵化物之合計1g，例如為1mL以上至150mL以下左右，較佳為5mL以上，更佳為8mL以上，且較佳為100mL以下，更佳為80mL以下。The amount of the solvent used in the coupling step is, for example, from 1 mL to 150 mL, preferably 5 mL or more, relative to 1 g of the total of the organotin compound represented by the above formula (do-A) and the halide of the acceptor unit , more preferably 8 mL or more, and preferably 100 mL or less, more preferably 80 mL or less.

偶合步驟中的反應溫度並無特別限定，就提高反應產率之觀點而言，較佳為0℃以上至200℃以下，更佳為30℃以上，進而較佳為40℃以上，更佳為180℃以下，進而較佳為150℃以下。The reaction temperature in the coupling step is not particularly limited, but from the viewpoint of increasing the reaction yield, it is preferably at least 0°C and at most 200°C, more preferably at least 30°C, further preferably at least 40°C, and more preferably at least 40°C. 180°C or lower, more preferably 150°C or lower.

偶合反應後，依據習用方法進行固液分離，將所回收之固體進行清洗，藉此可製造具有包含上述式(Do-A)所表示之單位之供體性單元及受體性單元各1個以上且供體性單元與受體性單元相互連結之化合物。於化合物為高分子型化合物之情形時，例如進行固液分離，將所回收之固體進行索氏清洗及萃取，藉此可製造高分子型化合物。於化合物為低分子型化合物之情形時，例如藉由矽藻土過濾去除觸媒後，進行濃縮並將所獲得之固體進行分散清洗，藉此可製造低分子型化合物。After the coupling reaction, the solid-liquid separation is carried out according to the usual method, and the recovered solid is washed, thereby producing one donor unit and one acceptor unit each comprising the unit represented by the above formula (Do-A) The above compounds in which the donor unit and the acceptor unit are linked to each other. When the compound is a high-molecular compound, for example, solid-liquid separation is performed, and the recovered solid is subjected to Soxhlet cleaning and extraction, thereby producing a high-molecular compound. When the compound is a low-molecular-weight compound, the low-molecular-weight compound can be produced by, for example, filtering through diatomaceous earth to remove the catalyst, and then concentrating and dispersing and washing the obtained solid.

進而包含上述式(Do-K)所表示之單位作為構成高分子型化合物之多個供體性單元之高分子型化合物可藉由下述方式來製造，亦即，將具有包含上述式(Do-A)所表示之單位之供體性單元及受體性單元作為重複單位之高分子型化合物於水之存在下且於酸性條件下進行加熱攪拌，藉此使縮醛結構轉化為酮結構。Further, a polymer compound comprising a unit represented by the above-mentioned formula (Do-K) as a plurality of donating units constituting the polymer compound can be produced by combining a compound having the above-mentioned formula (Do-K) -A) A macromolecular compound in which the donor unit and the acceptor unit of the unit represented by the repeating unit is heated and stirred in the presence of water under acidic conditions, thereby converting the acetal structure into a ketone structure.

本申請案主張基於2021年12月9日提出申請之日本專利申請案第2021-200324號之優先權的利益。上述日本專利申請案第2021-200324號之說明書的所有內容被引用至本申請案中以作參考。 [實施例] 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 aforementioned Japanese Patent Application No. 2021-200324 are incorporated by reference in this application. [Example]

以下，舉出實施例更具體地說明本發明，但本發明並不受下述實施例之限制，當然亦可於能夠符合前述及後述之主旨之範圍內施加變更而實施，這些均包含於本發明之技術範圍。此外，以下只要無特別說明，則「%」意指「質量%」。Hereinafter, the present invention will be described in more detail by citing the examples, but the present invention is not limited by the following examples, of course, it can also be implemented by adding changes within the range that can meet the aforementioned and the following gist, and these are all included in this document. The technical scope of the invention. In addition, unless otherwise specified below, "%" means "mass %".

於實驗1中合成高分子型化合物，於實驗2中合成低分子型化合物，並評價於溶媒中之溶解性、及是否可較佳地用作有機半導體材料。實施例中所使用之測定方法如下所述。In Experiment 1, polymer compounds were synthesized, and in Experiment 2, low-molecular compounds were synthesized, and their solubility in solvents and whether they could be better used as organic semiconductor materials were evaluated. The measurement methods used in the examples are as follows.

[測定方法] [NMR(Nuclear Magnetic Resonance，核磁共振)光譜測定] 作為NMR光譜測定裝置，使用Varian公司製造之「400-MR」及Bruker公司製造之「AVANCE NEO 600」，進行NMR光譜測定。 [高分子型化合物之紫外可見吸收光譜測定] 紫外可見吸收光譜之測定係以使高分子型化合物溶解於溶媒中而成之溶液之狀態測定。具體而言，將高分子型化合物以濃度成為0.03g/L之方式溶解於氯仿，使用紫外-可見分光裝置(島津製作所公司製造，「UV-3600i Plus」)及光程長度1cm之光學池(cell)，測定溶液狀態下之紫外可見吸收光譜。 [低分子型化合物之紫外可見吸收光譜測定] 紫外可見吸收光譜之測定係以使低分子型化合物溶解於溶媒中而成之溶液之狀態測定。具體而言，將低分子型化合物以濃度成為0.03g/L之方式溶解於氯仿，使用紫外-可見分光裝置(島津製作所公司製造，「UV-3600i Plus」)及光程長度1cm之光學池，測定溶液狀態下之紫外可見吸收光譜。測定結果以實線表示。 [test methods] [NMR (Nuclear Magnetic Resonance, nuclear magnetic resonance) spectrometry] NMR spectrum measurement was carried out using "400-MR" manufactured by Varian Co., Ltd. and "AVANCE NEO 600" manufactured by Bruker Corporation as NMR spectrometers. [UV-Vis Absorption Spectrum Determination of Polymer Compounds] The measurement of the ultraviolet-visible absorption spectrum is the measurement of the state of the solution formed by dissolving the polymer compound in the solvent. Specifically, a polymer compound was dissolved in chloroform so that the concentration became 0.03 g/L, and an ultraviolet-visible spectrometer (manufactured by Shimadzu Corporation, "UV-3600i Plus") and an optical cell with an optical path length of 1 cm ( cell), measure the UV-Vis absorption spectrum in the solution state. [UV-Vis Absorption Spectrum Measurement of Low Molecular Compounds] The measurement of the ultraviolet-visible absorption spectrum is measured in the state of a solution formed by dissolving a low-molecular compound in a solvent. Specifically, a low-molecular-weight compound was dissolved in chloroform so that the concentration became 0.03 g/L, and an ultraviolet-visible spectrometer (manufactured by Shimadzu Corporation, "UV-3600i Plus") and an optical cell with an optical path length of 1 cm was used. Measure the UV-Vis absorption spectrum in solution state. The measurement results are shown by solid lines.

基於日本特開2009-215278號公報之實施例2製備化合物H。化合物H為2,5-雙(三丁基錫烷基)螺[7H-環戊[1,2-d:4,3-d']雙噻唑-7,2'-[1,3]二氧戊環]，以下有時記為Ac-CBTZ-SB。Compound H was prepared based on Example 2 of JP-A-2009-215278. Compound H is 2,5-bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bithiazole-7,2'-[1,3]dioxolane Ring], sometimes referred to as Ac-CBTZ-SB below.

[實驗1] [實施例1] 對於20mL燒瓶加入2,5-雙(三丁基錫烷基)螺[7H-環戊[1,2-d:4,3-d']雙噻唑-7,2'-[1,3]二氧戊環](Ac-CBTZ-SB、217mg、0.265mmol)、3,6-雙(5-溴-2-噻吩基)-2,5-雙(2-己基癸基)-2,5-二氫吡咯并[3,4-c]吡咯-1,4-二酮(HD-DPP-DB、242mg、0.265mmol)、三(二亞苄基丙酮)二鈀(0)氯仿加成物(10mg、9.7μmol)、三(2-甲氧基苯基)膦(16mg、45μmol)及氯苯(8mL)，於130℃反應24小時。反應結束後，對於甲醇(45mL)加入反應液並濾取所析出之固體，將所獲得之固體進行索氏清洗(甲醇、丙酮、己烷)。繼而進行索氏萃取(氯仿)，結果獲得深藍色固體110.3mg(產率42%)。進行NMR光譜測定，結果所獲得之深藍色固體為P-Ac-CBTZ-HD-DPP(以下，有時稱為高分子型化合物1)。此時，以溶液之狀態進行所獲得之高分子型化合物1之紫外可見吸收光譜測定，該測定結果亦納入考慮。將紫外可見吸收光譜之測定結果以實線示於圖1。橫軸表示測定波長，縱軸表示吸光度(以下，關於紫外可見吸收光譜測定之結果亦相同)。 [Experiment 1] [Example 1] For a 20 mL flask add 2,5-bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bithiazole-7,2'-[1,3]diox Pentyl](Ac-CBTZ-SB, 217mg, 0.265mmol), 3,6-bis(5-bromo-2-thienyl)-2,5-bis(2-hexyldecyl)-2,5-bis Hydropyrrolo[3,4-c]pyrrole-1,4-dione (HD-DPP-DB, 242mg, 0.265mmol), tris(dibenzylideneacetone) dipalladium(0) chloroform adduct (10mg , 9.7 μmol), tris(2-methoxyphenyl)phosphine (16 mg, 45 μmol) and chlorobenzene (8 mL), reacted at 130° C. for 24 hours. After the reaction, methanol (45 mL) was added to the reaction solution, and the precipitated solid was collected by filtration, and the obtained solid was washed by Soxhlet (methanol, acetone, hexane). Then, Soxhlet extraction (chloroform) was performed, and as a result, 110.3 mg of a dark blue solid was obtained (yield 42%). As a result of NMR spectrum measurement, the obtained dark blue solid was P-Ac-CBTZ-HD-DPP (hereinafter, sometimes referred to as polymer compound 1). At this time, the ultraviolet-visible absorption spectrum measurement of the obtained polymer compound 1 was performed in the state of a solution, and the measurement result was also taken into consideration. The measurement results of the ultraviolet-visible absorption spectrum are shown in Fig. 1 by a solid line. The horizontal axis represents the measurement wavelength, and the vertical axis represents the absorbance (hereinafter, the same applies to the measurement results of the ultraviolet-visible absorption spectrum).

[化34] [chem 34]

[實施例2] 對於20mL燒瓶加入2,5-雙(三丁基錫烷基)螺[7H-環戊[1,2-d:4,3-d']雙噻唑-7,2'-[1,3]二氧戊環](Ac-CBTZ-SB、100mg、0.122mmol)、3,6-雙(5-溴-2-噻吩基)-2,5-雙(3,7-二甲基辛基)-2,5-二氫吡咯并[3,4-c]吡咯-1,4-二酮(DMO-DPP-DB、90.1mg、0.122mmol)、三(二亞苄基丙酮)二鈀(0)氯仿加成物(5mg、4.8μmol)、三(2-甲氧基苯基)膦(6.7mg、19μmol)及氯苯(4mL)，於130℃反應24小時。反應結束後，對於甲醇(30mL)加入反應液並濾取所析出之固體，將所獲得之固體進行索氏清洗(甲醇、丙酮、己烷)。繼而進行索氏萃取(氯仿)，結果獲得深藍色固體36.7mg(產率37%)。進行NMR光譜測定，結果所獲得之深藍色固體為P-Ac-CBTZ-DMO-DPP(以下，有時稱為高分子型化合物2)。此時，以溶液之狀態進行所獲得之高分子型化合物2之紫外可見吸收光譜測定，該測定結果亦納入考慮。將紫外可見吸收光譜之測定結果以實線示於圖2。 [Example 2] For a 20 mL flask add 2,5-bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bithiazole-7,2'-[1,3]diox Pentyl](Ac-CBTZ-SB, 100mg, 0.122mmol), 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 The adduct (5 mg, 4.8 μmol), tris(2-methoxyphenyl)phosphine (6.7 mg, 19 μmol) and chlorobenzene (4 mL) were reacted at 130° C. for 24 hours. After the reaction, methanol (30 mL) was added to the reaction solution, and the precipitated solid was collected by filtration, and the obtained solid was washed by Soxhlet (methanol, acetone, hexane). Then, Soxhlet extraction (chloroform) was performed to obtain 36.7 mg of a dark blue solid (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 compound 2). At this time, the ultraviolet-visible absorption spectrum measurement of the obtained polymer compound 2 was performed in the state of a solution, and the measurement result was also taken into consideration. The measurement results of the ultraviolet-visible absorption spectrum are shown in FIG. 2 by a solid line.

[化35] [chem 35]

[實施例3] 對於20mL燒瓶加入2,5-雙(三丁基錫烷基)螺[7H-環戊[1,2-d:4,3-d']雙噻唑-7,2'-[1,3]二氧戊環](Ac-CBTZ-SB、100mg、0.122mmol)、3,6-雙(5-溴-2-吡啶基)-2,5-二氫-2,5-雙(2-辛基十二烷基)吡咯并[3,4-c]吡咯-1,4-二酮(ODD-DPPDPy-DB、116mg、0.122mmol)、三(二亞苄基丙酮)二鈀(0)氯仿加成物(5mg、4.8μmol)、三(2-甲氧基苯基)膦(6.7mg、19μmol)及氯苯(4mL)，於130℃反應24小時。反應結束後，對於甲醇(30mL)加入反應液並濾取所析出之固體，將所獲得之固體進行索氏清洗(甲醇、丙酮、己烷)。繼而進行索氏萃取(氯仿)，結果獲得深藍色固體107.2mg(產率86%)。進行NMR光譜測定，結果所獲得之深藍色固體為P-Ac-CBTZ-ODD-DPPDPy(以下，有時稱為高分子型化合物3)。此時，以溶液之狀態進行所獲得之高分子型化合物3之紫外可見吸收光譜測定，該測定結果亦納入考慮。將紫外可見吸收光譜之測定結果以實線示於圖3。 [Example 3] For a 20 mL flask add 2,5-bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bithiazole-7,2'-[1,3]diox Pentacycline](Ac-CBTZ-SB, 100mg, 0.122mmol), 3,6-bis(5-bromo-2-pyridyl)-2,5-dihydro-2,5-bis(2-octyldeca Addition of dialkyl)pyrrolo[3,4-c]pyrrole-1,4-dione (ODD-DPPDPy-DB, 116 mg, 0.122 mmol), tris(dibenzylideneacetone) dipalladium(0) chloroform Compound (5mg, 4.8μmol), tris(2-methoxyphenyl)phosphine (6.7mg, 19μmol) and chlorobenzene (4mL), react at 130°C for 24 hours. After the reaction, methanol (30 mL) was added to the reaction solution, and the precipitated solid was collected by filtration, and the obtained solid was washed by Soxhlet (methanol, acetone, hexane). Then, Soxhlet extraction (chloroform) was carried out to obtain 107.2 mg of dark blue solid (yield 86%). As a result of NMR spectrum measurement, the obtained dark blue solid was P-Ac-CBTZ-ODD-DPPDPy (hereinafter, sometimes referred to as polymer compound 3). At this time, the ultraviolet-visible absorption spectrum measurement of the obtained polymer compound 3 was carried out in the state of a solution, and the measurement result was also taken into consideration. The measurement results of the ultraviolet-visible absorption spectrum are shown in FIG. 3 by a solid line.

[化36] [chem 36]

[實施例4] 對於20mL燒瓶加入2,5-雙(三丁基錫烷基)螺[7H-環戊[1,2-d:4,3-d']雙噻唑-7,2'-[1,3]二氧戊環](Ac-CBTZ-SB、100mg、0.122mmol)、5,13-二溴-2,9-雙(2-辛基十二烷基)蒽并[2,1,9-def:6,5,10-d'e'f']二異喹啉-1,3,8,10(2H,9H)-四酮(ODD-PDI-DB、135mg、0.122mmol)、三(二亞苄基丙酮)二鈀(0)氯仿加成物(5mg、4.8μmol)、三(2-甲氧基苯基)膦(6.7mg、19μmol)及氯苯(4mL)，於130℃反應24小時。反應結束後，對於甲醇(30mL)加入反應液並濾取所析出之固體，將所獲得之固體進行索氏清洗(甲醇、丙酮、己烷)。繼而進行索氏萃取(氯仿)，結果獲得褐色固體48.4mg(產率39%)。進行NMR光譜測定，結果所獲得之褐色固體為P-Ac-CBTZ-ODD-PDI(以下，有時稱為高分子型化合物4)。此時，以溶液之狀態進行所獲得之高分子型化合物4之紫外可見吸收光譜測定，該測定結果亦納入考慮。將紫外可見吸收光譜之測定結果以實線示於圖4。 [Example 4] For a 20 mL flask add 2,5-bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bithiazole-7,2'-[1,3]diox Pentyl](Ac-CBTZ-SB, 100mg, 0.122mmol), 5,13-dibromo-2,9-bis(2-octyldodecyl)anthracene[2,1,9-def:6 ,5,10-d'e'f']diisoquinoline-1,3,8,10(2H,9H)-tetraketone (ODD-PDI-DB, 135mg, 0.122mmol), tris(dibenzylidene Dipalladium(0) chloroform adduct (5 mg, 4.8 μmol), tris(2-methoxyphenyl)phosphine (6.7 mg, 19 μmol) and chlorobenzene (4 mL) were reacted at 130° C. for 24 hours. After the reaction, methanol (30 mL) was added to the reaction solution, and the precipitated solid was collected by filtration, and the obtained solid was washed by Soxhlet (methanol, acetone, hexane). Then, Soxhlet extraction (chloroform) was performed, and as a result, 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, may be referred to as polymer compound 4). At this time, the measurement of the ultraviolet-visible absorption spectrum of the obtained polymer compound 4 was performed in the state of a solution, and the measurement result was also taken into consideration. The measurement results of the ultraviolet-visible absorption spectrum are shown in Fig. 4 by a solid line.

[化37] [chem 37]

[實施例5] 對於20mL燒瓶加入2,5-雙(三丁基錫烷基)螺[7H-環戊[1,2-d:4,3-d']雙噻唑-7,2'-[1,3]二氧戊環](Ac-CBTZ-SB、100mg、0.122mmol)、1,3-二溴-5,7-雙(2-丁基辛基)-4H,8H-苯并[1,2-c:4,5-c']二噻吩-4,8-二酮(BO-BDT-DB、87.5mg、0.122mmol)、三(二亞苄基丙酮)二鈀(0)氯仿加成物(5mg、4.8μmol)、三(2-甲氧基苯基)膦(7.5mg、21μmol)及氯苯(4mL)，於130℃反應24小時。反應結束後，對於甲醇(30mL)加入反應液並濾取所析出之固體，將所獲得之固體進行索氏清洗(甲醇、丙酮、己烷)。繼而進行索氏萃取(氯仿)，結果獲得褐色固體22.9mg(產率29%)。進行NMR光譜測定，結果所獲得之褐色固體為P-Ac-CBTZ-BO-BDT(以下，有時稱為高分子型化合物5)。此時，以溶液之狀態進行所獲得之高分子型化合物5之紫外可見吸收光譜測定，該測定結果亦納入考慮。將紫外可見吸收光譜之測定結果以實線示於圖5。 [Example 5] For a 20 mL flask add 2,5-bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bithiazole-7,2'-[1,3]diox Pentyl] (Ac-CBTZ-SB, 100mg, 0.122mmol), 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, 4.8μmol), tris(2-methoxyphenyl)phosphine (7.5mg, 21μmol) and chlorobenzene (4mL), react at 130°C for 24 hours. After the reaction, methanol (30 mL) was added to the reaction solution, and the precipitated solid was collected by filtration, and the obtained solid was washed by Soxhlet (methanol, acetone, hexane). Then, Soxhlet extraction (chloroform) was carried out to obtain 22.9 mg of a brown solid (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 compound 5). At this time, the ultraviolet-visible absorption spectrum measurement of the obtained polymer compound 5 was performed in the state of a solution, and the measurement result was also taken into consideration. The measurement results of the ultraviolet-visible absorption spectrum are shown in Fig. 5 by a solid line.

[化38] [chem 38]

[實施例6] 對於20mL燒瓶加入2,5-雙(三丁基錫烷基)螺[7H-環戊[1,2-d:4,3-d']雙噻唑-7,2'-[1,3]二氧戊環](Ac-CBTZ-SB、100mg、0.122mmol)、4,9-二溴-2,7-雙(2-辛基十二烷基)苯并[lmn][3,8]啡啉-1,3,6,8(2H,7H)-四酮(ODD-NDI-DB、120mg、0.122mmol)、三(二亞苄基丙酮)二鈀(0)氯仿加成物(5mg、4.8μmol)、三(2-甲氧基苯基)膦(7.5mg、21μmol)及氯苯(4mL)，於130℃反應24小時。反應結束後，對於甲醇(30mL)加入反應液並濾取所析出之固體，將所獲得之固體進行索氏清洗(甲醇、丙酮、己烷)。繼而進行索氏萃取(氯仿)，結果獲得深藍色固體8.8mg(產率8%)。進行NMR光譜測定，結果所獲得之深藍色固體為P-Ac-CBTZ-ODD-NDI(以下，有時稱為高分子型化合物6)。此時，以溶液之狀態進行所獲得之高分子型化合物6之紫外可見吸收光譜測定，該測定結果亦納入考慮。將紫外可見吸收光譜之測定結果以實線示於圖6。 [Example 6] For a 20 mL flask add 2,5-bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bithiazole-7,2'-[1,3]diox Pentyl](Ac-CBTZ-SB, 100mg, 0.122mmol), 4,9-dibromo-2,7-bis(2-octyldodecyl)benzo[lmn][3,8]phenanthroline -1,3,6,8(2H,7H)-tetraketone (ODD-NDI-DB, 120mg, 0.122mmol), tris(dibenzylideneacetone) dipalladium(0) chloroform adduct (5mg, 4.8 μmol), tris(2-methoxyphenyl)phosphine (7.5mg, 21μmol) and chlorobenzene (4mL), react at 130°C for 24 hours. After the reaction, methanol (30 mL) was added to the reaction solution, and the precipitated solid was collected by filtration, and the obtained solid was washed by Soxhlet (methanol, acetone, hexane). Then, Soxhlet extraction (chloroform) was performed, and as a result, 8.8 mg of a dark blue solid was obtained (yield 8%). As a result of NMR spectrum measurement, the obtained dark blue solid was P-Ac-CBTZ-ODD-NDI (hereinafter, sometimes referred to as polymer compound 6). At this time, the measurement of the ultraviolet-visible absorption spectrum of the obtained polymer compound 6 was performed in a solution state, and the measurement results were also taken into consideration. The measurement results of the ultraviolet-visible absorption spectrum are shown in Fig. 6 by a solid line.

[化39] [chem 39]

[實施例7] 對於20mL燒瓶加入2,5-雙(三丁基錫烷基)螺[7H-環戊[1,2-d:4,3-d']雙噻唑-7,2'-[1,3]二氧戊環](Ac-CBTZ-SB、100mg、0.122mmol)、6-溴-3-(5-溴-2,3-二氫-3-側氧基-2-乙基己基-1H-異吲哚-1-亞基)-2,3-二氫-2-乙基己基-1H-異吲哚-1-酮(EH-IND-DB、78.6mg、0.122mmol)、三(二亞苄基丙酮)二鈀(0)氯仿加成物(5mg、4.8μmol)、三(2-甲氧基苯基)膦(6.7mg、19μmol)及氯苯(4mL)，於130℃反應24小時。反應結束後，對於甲醇(30mL)加入反應液並濾取所析出之固體，將所獲得之固體進行索氏清洗(甲醇、丙酮、己烷)。繼而進行索氏萃取(氯仿)，結果獲得深藍色固體23.4mg(產率34%)。進行NMR光譜測定，結果所獲得之深藍色固體為P-Ac-CBTZ-EH-IND(以下，有時稱為高分子型化合物7)。此時，以溶液之狀態進行所獲得之高分子型化合物7之紫外可見吸收光譜測定，該測定結果亦納入考慮。將紫外可見吸收光譜之測定結果以實線示於圖7。 [Example 7] For a 20 mL flask add 2,5-bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bithiazole-7,2'-[1,3]diox Pentyl](Ac-CBTZ-SB, 100mg, 0.122mmol), 6-bromo-3-(5-bromo-2,3-dihydro-3-oxo-2-ethylhexyl-1H-isoind Indol-1-ylidene)-2,3-dihydro-2-ethylhexyl-1H-isoindol-1-one (EH-IND-DB, 78.6mg, 0.122mmol), tris(dibenzylidene Acetone) dipalladium(0) chloroform adduct (5 mg, 4.8 μmol), tris(2-methoxyphenyl)phosphine (6.7 mg, 19 μmol) and chlorobenzene (4 mL), react at 130° C. for 24 hours. After the reaction, methanol (30 mL) was added to the reaction solution, and the precipitated solid was collected by filtration, and the obtained solid was washed by Soxhlet (methanol, acetone, hexane). Then, Soxhlet extraction (chloroform) was performed, and as a result, 23.4 mg of a dark blue solid was obtained (yield 34%). As a result of NMR spectrum measurement, the obtained dark blue solid was P-Ac-CBTZ-EH-IND (hereinafter, sometimes referred to as polymer compound 7). At this time, the ultraviolet-visible absorption spectrum measurement of the obtained polymer compound 7 was performed in the state of a solution, and the measurement result was also taken into consideration. The measurement results of the ultraviolet-visible absorption spectrum are shown by a solid line in FIG. 7 .

[化40] [chemical 40]

[實施例8] 對於20mL燒瓶加入2,5-雙(三丁基錫烷基)螺[7H-環戊[1,2-d:4,3-d']雙噻唑-7,2'-[1,3]二氧戊環](Ac-CBTZ-SB、100mg、0.122mmol)、4,9-二溴-2,7-雙(2-辛基十二烷基)苯并[lmn][3,8]啡啉-1,3,6,8(2H,7H)-四酮(ODD-NDI-DB、121.4mg、0.122mmol)、三(二亞苄基丙酮)二鈀(0)氯仿加成物(5mg、4.8μmol)、三(2-甲氧基苯基)膦(7.5mg、21μmol)及氯苯(4mL)，一邊確認溶解性，一邊自50℃階段性地升溫至100℃，於100℃反應15小時。自50℃至100℃之升溫係一邊確認溶解性，一邊於50℃保持1小時，升溫至65℃並保持1小時，升溫至75℃並保持1小時，升溫至85℃並保持1小時後，升溫至100℃。反應結束後，對於甲醇(30mL)加入反應液並濾取所析出之固體，將所獲得之固體進行索氏清洗(甲醇、丙酮、己烷)。繼而進行索氏萃取(氯仿)，結果獲得深藍色固體43.2mg(產率41%)。進行NMR光譜測定，結果所獲得之深藍色固體為P-Ac-CBTZ-ODD-NDI(以下，有時稱為高分子型化合物8)。此時，以溶液之狀態進行所獲得之高分子型化合物8之紫外可見吸收光譜測定，該測定結果亦納入考慮。將紫外可見吸收光譜之測定結果以實線示於圖8。 [Example 8] For a 20 mL flask add 2,5-bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bithiazole-7,2'-[1,3]diox Pentyl](Ac-CBTZ-SB, 100mg, 0.122mmol), 4,9-dibromo-2,7-bis(2-octyldodecyl)benzo[lmn][3,8]phenanthroline -1,3,6,8(2H,7H)-tetraketone (ODD-NDI-DB, 121.4mg, 0.122mmol), tris(dibenzylideneacetone) dipalladium(0) chloroform adduct (5mg, 4.8 μmol), tris(2-methoxyphenyl)phosphine (7.5 mg, 21 μmol) and chlorobenzene (4 mL), while confirming the solubility, the temperature was raised from 50°C to 100°C in stages, and the reaction was carried out at 100°C for 15 Hour. The temperature increase from 50°C to 100°C is to confirm the solubility while maintaining at 50°C for 1 hour, raising the temperature to 65°C and maintaining for 1 hour, raising the temperature to 75°C and maintaining for 1 hour, raising the temperature to 85°C and maintaining for 1 hour, The temperature was raised to 100°C. After the reaction, methanol (30 mL) was added to the reaction solution, and the precipitated solid was collected by filtration, and the obtained solid was washed by Soxhlet (methanol, acetone, hexane). Then, Soxhlet extraction (chloroform) was performed, and as a result, 43.2 mg of a dark blue solid was obtained (yield 41%). As a result of NMR spectrum measurement, the obtained dark blue solid was P-Ac-CBTZ-ODD-NDI (hereinafter, sometimes referred to as polymer compound 8). At this time, the ultraviolet-visible absorption spectrum measurement of the obtained polymer compound 8 was performed in the state of a solution, and the measurement result was also taken into consideration. The measurement results of the ultraviolet-visible absorption spectrum are shown in Fig. 8 by a solid line.

[化41] [chem 41]

[實施例9] 對於20mL燒瓶加入2,5-雙(三丁基錫烷基)螺[7H-環戊[1,2-d:4,3-d']雙噻唑-7,2'-[1,3]二氧戊環](Ac-CBTZ-SB、100mg、0.122mmol)、4,9-二溴-2,7-雙(2-癸基十四烷基)苯并[lmn][3,8]啡啉-1,3,6,8(2H,7H)-四酮(TD-NDI-DB、134mg、0.122mmol)、三(二亞苄基丙酮)二鈀(0)氯仿加成物(5mg、4.8μmol)、三(2-甲氧基苯基)膦(7.5mg、21μmol)及氯苯(4mL)，於130℃反應15小時。反應結束後，對於甲醇(30mL)加入反應液並濾取所析出之固體，將所獲得之固體進行索氏清洗(甲醇、丙酮、己烷)。繼而進行索氏萃取(氯仿)，結果獲得深藍色固體42.4mg(產率36%)。進行NMR光譜測定，結果所獲得之深藍色固體為P-Ac-CBTZ-TD-NDI(以下，有時稱為高分子型化合物9)。此時，以溶液之狀態進行所獲得之高分子型化合物9之紫外可見吸收光譜測定，該測定結果亦納入考慮。將紫外可見吸收光譜之測定結果以實線示於圖9。 [Example 9] For a 20 mL flask add 2,5-bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bithiazole-7,2'-[1,3]diox Pentyl](Ac-CBTZ-SB, 100mg, 0.122mmol), 4,9-dibromo-2,7-bis(2-decyltetradecyl)benzo[lmn][3,8]phenanthroline -1,3,6,8(2H,7H)-tetraketone (TD-NDI-DB, 134mg, 0.122mmol), tris(dibenzylideneacetone) dipalladium(0) chloroform adduct (5mg, 4.8 μmol), tris(2-methoxyphenyl)phosphine (7.5mg, 21μmol) and chlorobenzene (4mL), react at 130°C for 15 hours. After the reaction, methanol (30 mL) was added to the reaction solution, and the precipitated solid was collected by filtration, and the obtained solid was washed by Soxhlet (methanol, acetone, hexane). Then, Soxhlet extraction (chloroform) was performed, and as a result, 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 compound 9). At this time, the measurement of the ultraviolet-visible absorption spectrum of the obtained polymer compound 9 was performed in the state of the solution, and the measurement results were also taken into consideration. The measurement results of the ultraviolet-visible absorption spectrum are shown in Fig. 9 by a solid line.

[化42] [chem 42]

[實施例10] 對於20mL燒瓶加入2,5-雙(三丁基錫烷基)螺[7H-環戊[1,2-d:4,3-d']雙噻唑-7,2'-[1,3]二氧戊環](Ac-CBTZ-SB、217mg、0.265mmol)、3,6-雙(5-溴-2-噻吩基)-2,5-雙(2-己基癸基)-2,5-二氫吡咯并[3,4-c]吡咯-1,4-二酮(HD-DPP-DB、242mg、0.265mmol)、三(二亞苄基丙酮)二鈀(0)氯仿加成物(10mg、9.7μmol)、三(2-甲氧基苯基)膦(16mg、45μmol)及氯苯(8mL)，於130℃反應24小時。反應結束後，對於甲醇(45mL)加入反應液並濾取所析出之固體，將所獲得之固體進行索氏清洗(甲醇、丙酮、己烷)。繼而進行索氏萃取(氯仿)，結果獲得深藍色固體110.3mg(產率42%)。進行NMR光譜測定，結果所獲得之深藍色固體為P-Ac-CBTZ-HD-DPP。 [Example 10] For a 20 mL flask add 2,5-bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bithiazole-7,2'-[1,3]diox Pentyl](Ac-CBTZ-SB, 217mg, 0.265mmol), 3,6-bis(5-bromo-2-thienyl)-2,5-bis(2-hexyldecyl)-2,5-bis Hydropyrrolo[3,4-c]pyrrole-1,4-dione (HD-DPP-DB, 242mg, 0.265mmol), tris(dibenzylideneacetone) dipalladium(0) chloroform adduct (10mg , 9.7 μmol), tris(2-methoxyphenyl)phosphine (16 mg, 45 μmol) and chlorobenzene (8 mL), reacted at 130° C. for 24 hours. After the reaction, methanol (45 mL) was added to the reaction solution, and the precipitated solid was collected by filtration, and the obtained solid was washed by Soxhlet (methanol, acetone, hexane). Then, Soxhlet extraction (chloroform) was performed, and as a result, 110.3 mg of a dark blue solid was obtained (yield 42%). As a result of NMR spectrum measurement, the obtained dark blue solid was P-Ac-CBTZ-HD-DPP.

將所獲得之深藍色固體之一部分(41.2mg、41.9μmol)溶解於氯仿，遠遠過量地加入甲磺酸及水，於60℃攪拌15小時。攪拌後，進行濃縮，加入甲醇並進行濾取，結果獲得深藍色固體26.1mg(產率64%)。進行NMR光譜測定，結果所獲得之深藍色固體為P-Ac-CBTZ-HD-DPP/P-CBTZ-HD-DPP(50/50)(以下，有時稱為高分子型化合物10)。此時，以溶液之狀態進行所獲得之高分子型化合物10之紫外可見吸收光譜測定，該測定結果亦納入考慮。將紫外可見吸收光譜之測定結果以實線示於圖10。Part (41.2 mg, 41.9 μmol) of the obtained dark blue solid was dissolved in chloroform, methanesulfonic acid and water were added in large excess, and the mixture was stirred at 60° C. for 15 hours. After stirring, it was concentrated, methanol was added, and filtration was performed to obtain 26.1 mg of a dark blue solid (64% yield). NMR spectrum measurement revealed that the obtained dark blue solid was P-Ac-CBTZ-HD-DPP/P-CBTZ-HD-DPP (50/50) (hereinafter, may be referred to as polymer compound 10). At this time, the ultraviolet-visible absorption spectrum measurement of the obtained polymer compound 10 was performed in the state of a solution, and the measurement result was also taken into consideration. The measurement results of the ultraviolet-visible absorption spectrum are shown in FIG. 10 by a solid line.

[化43] [chem 43]

[實施例11] 作為微波反應裝置，使用Biotage製造之「Initiator＋Microwave System 356700」，對於5mL之微波(MW)用反應容器加入2,5-雙(三丁基錫烷基)螺[7H-環戊[1,2-d:4,3-d']雙噻唑-7,2'-[1,3]二氧戊環](Ac-CBTZ-SB、100mg、0.122mmol)、1,3-二溴-5-(2-癸基十四烷基)-4H-噻吩并[3,4-c]吡咯-4,6(5H)-二酮(TD-IMTH-DB、79.0mg、0.122mmol)、三(二亞苄基丙酮)二鈀(0)氯仿加成物(5mg、4.8μmol)、三(2-甲氧基苯基)膦(7.5mg、21μmol)及氯苯(4mL)，於180℃實施10分鐘MW反應。反應結束後，對於甲醇(30mL)加入反應液並濾取所析出之固體，將所獲得之固體進行索氏清洗(甲醇、丙酮、己烷)。繼而進行索氏萃取(氯仿)，結果獲得深藍色固體63.7mg(產率89%)。進行NMR光譜測定，結果所獲得之深藍色固體為P-Ac-CBTZ-TD-IMTH(以下，有時稱為高分子型化合物11)。此時，以溶液之狀態進行所獲得之高分子型化合物11之紫外可見吸收光譜測定，該測定結果亦納入考慮。將紫外可見吸收光譜之測定結果以實線示於圖11。 [Example 11] As a microwave reaction device, "Initiator+Microwave System 356700" manufactured by Biotage was used, and 2,5-bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d] was added to a 5 mL microwave (MW) reaction vessel: 4,3-d']bithiazole-7,2'-[1,3]dioxolane](Ac-CBTZ-SB, 100mg, 0.122mmol), 1,3-dibromo-5-(2- Decyltetradecyl)-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione (TD-IMTH-DB, 79.0mg, 0.122mmol), tris(dibenzylidene Acetone) dipalladium (0) chloroform adduct (5 mg, 4.8 μmol), tris(2-methoxyphenyl) phosphine (7.5 mg, 21 μmol) and chlorobenzene (4 mL), MW reaction at 180° C. for 10 minutes . After the reaction, methanol (30 mL) was added to the reaction solution, and the precipitated solid was collected by filtration, and the obtained solid was washed by Soxhlet (methanol, acetone, hexane). Then, Soxhlet extraction (chloroform) was performed, and as a result, 63.7 mg of a dark blue solid was obtained (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 compound 11). At this time, the measurement of the ultraviolet-visible absorption spectrum of the obtained polymer compound 11 was performed in the state of the solution, and the measurement results were also taken into consideration. The measurement results of the ultraviolet-visible absorption spectrum are shown in FIG. 11 by a solid line.

[化44] [chem 44]

[實施例12] 對於20mL燒瓶加入2,5-雙(三丁基錫烷基)螺[7H-環戊[1,2-d:4,3-d']雙噻唑-7,2'-[1,3]二氧戊環](Ac-CBTZ-SB、100mg、0.122mmol)、4,9-二溴-2,7-雙(2-癸基十四烷基)苯并[lmn][3,8]啡啉-1,3,6,8(2H,7H)-四酮(TD-NDI-DB、134mg、0.122mmol)、三(二亞苄基丙酮)二鈀(0)氯仿加成物(5mg、4.8μmol)、三(2-甲氧基苯基)膦(7.5mg、21μmol)及氯苯(4mL)，一邊確認溶解性，一邊自50℃階段性地升溫至100℃，於100℃反應15小時。自50℃至100℃之升溫係一邊確認溶解性，一邊於50℃保持1小時，升溫至70℃並保持1小時後，升溫至100℃。反應結束後，對於甲醇(30mL)加入反應液並濾取所析出之固體，將所獲得之固體進行索氏清洗(甲醇、丙酮、己烷)。繼而進行索氏萃取(氯仿)，結果獲得深藍色固體125mg(產率91%)。進行NMR光譜測定，結果所獲得之深藍色固體為P-Ac-CBTZ-TD-NDI(以下，有時稱為高分子型化合物12)。此時，以溶液之狀態進行所獲得之高分子型化合物12之紫外可見吸收光譜測定，該測定結果亦納入考慮。將紫外可見吸收光譜之測定結果以實線示於圖12。 [Example 12] For a 20 mL flask add 2,5-bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bithiazole-7,2'-[1,3]diox Pentyl](Ac-CBTZ-SB, 100mg, 0.122mmol), 4,9-dibromo-2,7-bis(2-decyltetradecyl)benzo[lmn][3,8]phenanthroline -1,3,6,8(2H,7H)-tetraketone (TD-NDI-DB, 134mg, 0.122mmol), tris(dibenzylideneacetone) dipalladium(0) chloroform adduct (5mg, 4.8 μmol), tris(2-methoxyphenyl)phosphine (7.5mg, 21μmol) and chlorobenzene (4mL), while confirming the solubility, the temperature was raised from 50°C to 100°C step by step, and the reaction was carried out at 100°C for 15 hours . The temperature rise from 50°C to 100°C was maintained at 50°C for 1 hour while checking the solubility, raised to 70°C and held for 1 hour, and then raised to 100°C. After the reaction, methanol (30 mL) was added to the reaction solution, and the precipitated solid was collected by filtration, and the obtained solid was washed by Soxhlet (methanol, acetone, hexane). Then, Soxhlet extraction (chloroform) was performed, and as a result, 125 mg of a dark blue solid was obtained (yield 91%). As a result of NMR spectrum measurement, the obtained dark blue solid was P-Ac-CBTZ-TD-NDI (hereinafter, sometimes referred to as polymer compound 12). At this time, the ultraviolet-visible absorption spectrum measurement of the obtained polymer compound 12 was performed in the state of a solution, and the measurement result was also taken into consideration. The measurement results of the ultraviolet-visible absorption spectrum are shown in FIG. 12 by a solid line.

[化45] [chem 45]

[實施例13] 對於20mL燒瓶加入2,5-雙(三丁基錫烷基)螺[7H-環戊[1,2-d:4,3-d']雙噻唑-7,2'-[1,3]二氧戊環](Ac-CBTZ-SB、300mg、0.367mmol)、4,9-二溴-2,7-雙(2-癸基十四烷基)苯并[lmn][3,8]啡啉-1,3,6,8(2H,7H)-四酮(TD-NDI-DB、402mg、0.367mmol)、三(二亞苄基丙酮)二鈀(0)氯仿加成物(15mg、14.7μmol)、三(2-甲氧基苯基)膦(22.0mg、62μmol)及氯苯(12mL)，於130℃反應24小時。反應結束後，對於甲醇(90mL)加入反應液並濾取所析出之固體，將所獲得之固體進行索氏清洗(甲醇、丙酮、己烷、氯仿)。繼而，取出索氏圓筒濾紙內部的固體，再次於氯仿中藉由超音波及攪拌操作進行溶解，結果獲得深藍色固體285.3mg(產率70%)。對可溶於氯仿之部分進行NMR光譜測定，結果所獲得之深藍色固體為P-Ac-CBTZ-TD-NDI(以下，有時稱為高分子型化合物13)。此時，以溶液之狀態進行所獲得之高分子型化合物13之紫外可見吸收光譜測定，該測定結果亦納入考慮。將紫外可見吸收光譜之測定結果以實線示於圖13。 [Example 13] For a 20 mL flask add 2,5-bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bithiazole-7,2'-[1,3]diox Pentyl](Ac-CBTZ-SB, 300mg, 0.367mmol), 4,9-dibromo-2,7-bis(2-decyltetradecyl)benzo[lmn][3,8]phenanthroline -1,3,6,8(2H,7H)-tetraketone (TD-NDI-DB, 402mg, 0.367mmol), tris(dibenzylideneacetone) dipalladium(0) chloroform adduct (15mg, 14.7 μmol), tris(2-methoxyphenyl)phosphine (22.0mg, 62μmol) and chlorobenzene (12mL), react at 130°C for 24 hours. After the reaction was completed, methanol (90 mL) was added to the reaction solution, and the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet cleaning (methanol, acetone, hexane, chloroform). Then, the solid inside the Soxhlet cylindrical filter paper was taken out, and dissolved again in chloroform by ultrasonic wave and stirring operation, and as a result, 285.3 mg of dark blue solid was obtained (yield 70%). As a result of NMR spectrum measurement of the chloroform-soluble fraction, the obtained dark blue solid was P-Ac-CBTZ-TD-NDI (hereinafter, sometimes referred to as polymer compound 13). At this time, the measurement of the ultraviolet-visible absorption spectrum of the obtained polymer compound 13 was performed in the state of a solution, and the measurement results were also taken into consideration. The measurement results of the ultraviolet-visible absorption spectrum are shown in FIG. 13 by a solid line.

[化46] [chem 46]

[實施例14] 對於20mL燒瓶添加4-溴-2,7-雙(2-癸基十四烷基)苯并[lmn][3,8]啡啉-1,3,6,8(2H,7H)-四酮(TD-NDI-DB、299.2mg、0.2727mmol)、2-(三丁基錫烷基)-***(Bu3Sn-Thz、299.1mg、0.799mmol)、四三苯基膦鈀(0)(34mg、30μmol)及甲苯(6.4mL)，於110℃反應16小時。反應結束後，實施鹽水清洗、甲苯萃取，並進行濃縮。進而，加入甲醇(10mL)，濾取所析出之固體，結果獲得黃色固體247.9mg(產率82.2%)。進行NMR光譜測定，結果所獲得之黃色固體為TD-NDI-2Thz(以下，有時稱為化合物14)。 ¹H NMR (400 MHz, CDCl ₃): 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 14] Add 4-bromo-2,7-bis(2-decyltetradecyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H ,7H)-tetraketone (TD-NDI-DB, 299.2mg, 0.2727mmol), 2-(tributylstannyl)-triazole (Bu3Sn-Thz, 299.1mg, 0.799mmol), tetrakistriphenylphosphine palladium ( 0) (34mg, 30μmol) and toluene (6.4mL), react at 110°C for 16 hours. After completion of the reaction, washing with brine, extraction with toluene, and concentration were performed. Furthermore, methanol (10 mL) was added, and the precipitated solid was collected by filtration to obtain 247.9 mg of a yellow solid (82.2% yield). As a result of NMR spectrum measurement, the obtained yellow solid was TD-NDI-2Thz (hereinafter, sometimes referred to as compound 14). ¹ H NMR (400 MHz, CDCl ₃ ): 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)

[化47] [chem 47]

[實施例15] 對於20mL燒瓶添加實施例14中所獲得之化合物14(TD-NDI-2Thz、18.1mg、0.02mmol)及四氫呋喃(0.25mL)、於-78℃冷卻後，添加正丁基鋰(1.6mol/L、0.05mL)而使之反應1小時。然後，添加1,3-二溴-5,5-二甲基乙內醯脲(DBH、15.51mg、0.06mmol)，於室溫下反應1小時。反應結束後，利用乙酸乙酯進行萃取，利用亞硫酸鈉實施水洗，將有機層利用硫酸鎂乾燥後進行濃縮。利用管柱層析法(氯仿/乙酸乙酯＝10)，加入甲醇(10mL)，濾取所析出之固體，結果獲得黃色固體15mg(產率72.5%)。進行NMR光譜測定，結果所獲得之黃色固體為TD-NDI-2Thz-Br(以下，有時稱為化合物15)。 ¹H NMR (400 MHz, CDCl ₃): 9.140 (s, 2H), 7.931 (s, 2H), 4.085 (d, 4H), 1.227-1.186 (bs, 80H), 0.855 (t, 12H) [Example 15] Compound 14 (TD-NDI-2Thz, 18.1mg, 0.02mmol) and tetrahydrofuran (0.25mL) obtained in Example 14 were added to a 20mL flask, and after cooling at -78°C, n-butyllithium was added (1.6 mol/L, 0.05 mL) and allowed to react for 1 hour. Then, 1,3-dibromo-5,5-dimethylhydantoin (DBH, 15.51 mg, 0.06 mmol) was added, and the mixture was reacted at room temperature for 1 hour. After completion of the reaction, extraction was performed with ethyl acetate, water washing was performed with sodium sulfite, and the organic layer was dried with magnesium sulfate and then concentrated. Using column chromatography (chloroform/ethyl acetate=10), methanol (10 mL) was added, and the precipitated solid was collected by filtration to obtain 15 mg of a yellow solid (yield 72.5%). As a result of NMR spectrum measurement, the obtained yellow solid was TD-NDI-2Thz-Br (hereinafter, sometimes referred to as compound 15). ¹ H NMR (400 MHz, CDCl ₃ ): 9.140 (s, 2H), 7.931 (s, 2H), 4.085 (d, 4H), 1.227-1.186 (bs, 80H), 0.855 (t, 12H)

[化48] [chem 48]

[實施例16] 於20mL燒瓶中，將2,5-雙(三丁基錫烷基)螺[7H-環戊[1,2-d:4,3-d']雙噻唑-7,2'-[1,3]二氧戊環](Ac-CBTZ-SB)、實施例15中所獲得之化合物15、觸媒量之三(二亞苄基丙酮)二鈀(0)氯仿加成物、及作為配位於觸媒之配位基之三(2-甲氧基苯基)膦於氯苯中進行加熱而使之反應。Ac-CBTZ-SB與化合物15之莫耳比設為1：1。自反應液中單離P-Ac-CBTZ-TD-NDI-2Thz(以下，有時稱為高分子化合物16)。 [Example 16] In a 20mL flask, 2,5-bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bithiazole-7,2'-[1,3] Dioxolane] (Ac-CBTZ-SB), compound 15 obtained in Example 15, tris(dibenzylideneacetone) dipalladium (0) chloroform adduct of catalytic amount, and as coordination in catalyst The tris(2-methoxyphenyl)phosphine of the intermediate ligand is heated in chlorobenzene to make it react. The molar ratio of Ac-CBTZ-SB to compound 15 was set as 1:1. P-Ac-CBTZ-TD-NDI-2Thz (hereinafter, sometimes referred to as polymer compound 16) was isolated from the reaction solution.

[化49] [chem 49]

由圖1至圖13可明顯看出，本發明之高分子型化合物1至高分子型化合物13能夠吸收長波長區域之光。It can be clearly seen from FIG. 1 to FIG. 13 that polymer compound 1 to polymer compound 13 of the present invention can absorb light in the long-wavelength region.

其次，測定所獲得之高分子型化合物1至高分子型化合物13的分子量。分子量之測定使用凝膠滲透層析法(GPC；Gel Permeation Chromatography)。測定時，將高分子型化合物以成為0.8g/L的濃度之方式溶解於流動相溶媒(氯仿)，於下述條件下進行測定，基於將聚苯乙烯作為標準試樣所製作之校準曲線進行換算，藉此算出高分子型化合物的重量平均分子量(Mw)及數量平均分子量(Mn)。測定中之GPC條件如下所述。裝置：高效液相層析儀 L-2420/L-2130(Hitachi High-Tech股份有限公司製造) 流動相：氯仿流速1mL/min 管柱：Shodex GPC K-803L(昭和電工股份有限公司製造) Next, the molecular weights of the obtained polymer compound 1 to polymer compound 13 were measured. The molecular weight was measured using gel permeation chromatography (GPC; Gel Permeation Chromatography). For the measurement, the polymer compound was dissolved in the mobile phase solvent (chloroform) so as to have a concentration of 0.8 g/L, and the measurement was performed under the following conditions, based on a calibration curve prepared using polystyrene as a standard sample By conversion, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of a polymer compound are calculated by this. The GPC conditions in the measurement are as follows. Apparatus: High performance liquid chromatography L-2420/L-2130 (manufactured by Hitachi High-Tech Co., Ltd.) Mobile phase: chloroform flow rate 1mL/min Column: Shodex GPC K-803L (manufactured by Showa Denko Co., Ltd.)

將分子量之測定結果示於下述表1。此外，於檢測到2個表示分子量之峰之情形時，將2個分子量示於下述表1。The measurement results of the molecular weight are shown in Table 1 below. In addition, when two peaks showing molecular weights were detected, the two molecular weights were shown in Table 1 below.

其次，對所獲得之高分子型化合物1至高分子型化合物13於溶媒中之溶解性進行評價。溶媒使用氯仿、氯苯、或甲苯。於使用氯仿之情形時，以高分子型化合物的濃度成為5質量%之方式添加氯仿，於60℃加熱30分鐘。於使用氯苯之情形時，以高分子型化合物1至高分子型化合物12成為1mg/mL之方式，於室溫下添加氯苯。對於高分子型化合物13，以成為1mg/mL之方式添加氯苯，於130℃加熱60分鐘。於使用甲苯之情形時，以高分子型化合物1至高分子型化合物9、高分子型化合物11、高分子型化合物12成為1mg/mL之方式，於室溫下添加甲苯。對於高分子型化合物13，以成為1mg/mL之方式添加甲苯，於100℃加熱60分鐘。此外，對於高分子型化合物10，未進行使用甲苯之評價。Next, the solubility in solvents of the obtained polymer compound 1 to polymer compound 13 was evaluated. As a solvent, chloroform, chlorobenzene, or toluene is used. When using chloroform, chloroform was added so that the density|concentration of a polymer type compound might become 5 mass %, and it heated at 60 degreeC for 30 minutes. When chlorobenzene was used, chlorobenzene was added at room temperature so that the polymer compound 1 to polymer compound 12 became 1 mg/mL. To polymer compound 13, chlorobenzene was added so that it might become 1 mg/mL, and it heated at 130 degreeC for 60 minutes. When using toluene, toluene was added at room temperature so that polymer compound 1 to polymer compound 9, polymer compound 11, and polymer compound 12 became 1 mg/mL. Toluene was added to polymer compound 13 so that it might become 1 mg/mL, and it heated at 100 degreeC for 60 minutes. In addition, for the polymer compound 10, the evaluation using toluene was not performed.

於添加溶媒後或加熱後，利用目視觀察高分子型化合物是否溶解，基於下述基準進行評價。將評價結果示於下述表1。 [評價基準] ○：溶解於溶媒。 △：高分子型化合物之一部分未溶解而殘留。 ×：未溶解於溶媒。 After adding the solvent or after heating, whether or not the polymer compound was dissolved was observed visually, and evaluated based on the following criteria. The evaluation results are shown in Table 1 below. [evaluation criteria] ◯: Dissolved in a solvent. Δ: A part of the polymer compound remains without being dissolved. ×: Not dissolved in the solvent.

其次，使用所獲得之高分子型化合物1至高分子型化合物13，測定游離能、帶隙、電子遷移率μe、閾值電壓、開/關比。另外，由游離能之值及帶隙之值求出LUMO之值。Next, using the obtained polymer compound 1 to polymer compound 13, free energy, band gap, electron mobility μe, threshold voltage, and on/off ratio were measured. In addition, the value of LUMO was obtained from the value of the ionization energy and the value of the band gap.

[游離能之測定] 以高分子型化合物的濃度成為8mg/mL之方式溶解於氯苯，將所獲得之溶液滴鑄於ITO(IndiumTin Oxide；氧化銦錫)基板上而進行成膜。針對該膜，於常溫、減壓下(0.1Pa以下)，藉由游離能測定裝置(分光計器股份有限公司製造，「BIP-KV202GD」)測定游離能(eV)。將所測定之游離能之值(eV)示於下述表1。 [Determination of dissociation energy] The polymer compound was dissolved in chlorobenzene so that the concentration of the polymer compound became 8 mg/mL, and the obtained solution was drop-cast on an ITO (Indium Tin Oxide; indium tin oxide) substrate to form a film. About this film, free energy (eV) was measured with the free energy measuring apparatus (manufactured by Spectrometer Co., Ltd., "BIP-KV202GD") at normal temperature and under reduced pressure (0.1 Pa or less). The values (eV) of the measured free energy are shown in Table 1 below.

[帶隙] 高分子型化合物之帶隙係進行包含高分子型化合物之薄膜之UV(紫外可見吸收光譜)測定，基於UV之上升而算出。亦即，以高分子型化合物的濃度成為8mg/mL之方式溶解於氯苯，將所獲得之溶液旋轉塗佈於玻璃基板(2.5cm×2.5cm見方、厚度0.8mm至1.0mm)上而形成薄膜。針對該薄膜，於常溫常壓下，藉由紫外-可見分光裝置(島津製作所公司製造，「UV-3600i Plus」)進行UV測定。將以薄膜之狀態所測定之UV測定之結果以虛線示於圖1至圖5、圖7至圖13。此外，對於實施例6，未進行以薄膜之狀態之UV測定。另外，基於UV之上升而算出帶隙(eV)。將所算出之帶隙之值(eV)示於下述表1。 [Bandgap] The band gap of the polymer compound was calculated based on the UV (ultraviolet-visible absorption spectrum) measurement of a thin film containing the polymer compound, based on the rise in UV. That is, the polymer compound was dissolved in chlorobenzene so that the concentration of the polymer compound became 8 mg/mL, and the obtained solution was spin-coated on a glass substrate (2.5 cm x 2.5 cm square, thickness 0.8 mm to 1.0 mm) to form film. With respect to this thin film, UV measurement was performed with the ultraviolet-visible spectrometer (manufactured by Shimadzu Corporation, "UV-3600i Plus") under normal temperature and normal pressure. The results of UV measurement measured in the film state are shown by dotted lines in FIGS. 1 to 5 and 7 to 13 . In addition, about Example 6, the UV measurement in the state of a thin film was not performed. In addition, the band gap (eV) was calculated based on the rise of UV. The calculated values (eV) of the band gap are shown in Table 1 below.

使用圖14對帶隙之算出方法進行說明。圖14係為了說明帶隙之算出方法而製作之示意圖，係對包含高分子型化合物9之薄膜進行UV測定所獲得之紫外可見吸收光譜畫出輔助線之示意圖。針對於200nm至1000nm之區域內所測定之紫外可見吸收光譜，如圖14所示，於來自化合物之峰之長波長側自峰頂附近畫出切線，由切線與橫軸(波長)之交點求出上升之波長λ。亦即，對顯示最大吸收之峰之曲線中自高波長側往低波長側之吸收變大之區域的曲線畫出切線作為輔助線，讀取該切線與吸光度顯示0之橫軸之交點處的波長，將該波長設為UV之上升波長λ。於圖14中所示之高分子型化合物9之情形時，上升波長λ成為841nm。A method of calculating the bandgap will be described using FIG. 14 . FIG. 14 is a schematic diagram prepared to illustrate the calculation method of the band gap, and it is a schematic diagram in which auxiliary lines are drawn in the ultraviolet-visible absorption spectrum obtained by UV measurement of a film containing polymer compound 9. For the ultraviolet-visible absorption spectrum measured in the region of 200nm to 1000nm, as shown in Figure 14, draw a tangent line from the vicinity of the peak top on the long wavelength side of the peak originating from the compound, and obtain it from the intersection point of the tangent line and the horizontal axis (wavelength) The rising wavelength λ. That is, draw a tangent to the curve of the curve showing the peak of maximum absorption in the region where the absorption increases from the high wavelength side to the low wavelength side as an auxiliary line, and read the wavelength at the intersection of the tangent line and the horizontal axis where the absorbance shows 0 , and set this wavelength as the rising wavelength λ of UV. In the case of the polymer compound 9 shown in FIG. 14 , the rising wavelength λ was 841 nm.

將HOMO-LUMO間之帶隙(能隙)設為E、普朗克常數設為h、真空中之光速設為c時，下式之關係成立。 E＝hc/λ When E is the band gap (energy gap) between HOMO-LUMO, Planck's constant is h, and the speed of light in vacuum is c, the relationship of the following formula holds. E=hc/λ

此處，普朗克常數h為6.626×10 ^-34、真空中之光速c為2.998×10 ⁸，因此若代入841作為上升波長λ，則帶隙E如下述式成為1.47eV。 E＝1239.8/841≒1.47(eV) Here, Planck's constant h is 6.626×10 ^-34 , and the speed of light c in vacuum is 2.998×10 ⁸ . Therefore, if 841 is substituted as 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)

另一方面，游離能之值(HOMO之值)為-5.96eV，因此LUMO之值如下述成為-4.49eV。 LUMO＝-5.96＋1.47＝-4.49(eV) On the other hand, the value of ionization energy (the value of HOMO) is -5.96eV, so the value of LUMO becomes -4.49eV as follows. LUMO＝-5.96＋1.47＝-4.49(eV)

將基於下述表1中所示之游離能及帶隙所算出之LUMO之值(eV)示於下述表1。The value (eV) of LUMO calculated based on the ionization energy and band gap shown in Table 1 below is shown in Table 1 below.

[電子遷移率、閾值電壓、開/關比之測定] 使用六甲基二矽氮烷(HMDS)或十八烷基三氯矽烷(ODTS)將經臭氧處理之矽基板上進行處理。將高分子型化合物的濃度為0.5質量%(7.4mg/mL)之氯仿溶液旋轉塗佈於處理後之基板表面，藉此製作有機場效型電晶體(OFET；organic field-effect transistor)元件。此外，對於實施例13，使用氯苯代替氯仿，旋轉塗佈高分子型化合物的濃度為0.5質量%之氯苯溶液。針對所製作之OFET元件，於100℃實施1小時之退火並放置冷卻，於150℃實施1小時之退火並放置冷卻，然後測定Id-Vg特性。Id-Vg特性係於氮氣氛圍下或真空下所測定。Id-Vg特性之測定使用Keithley Instruments(KEITHLEY)製造之「4200-SCS」，有機半導體元件的通道長度設為25μm，通道寬度設為294mm。進行Id-Vg特性之測定，求出電子遷移率μe(cm ²/Vs)、閾值電壓Vth(V)、開/關比(I _on/I _off)。將於150℃實施1小時退火後所測定之Id-Vg特性之結果示於下述表1。此外，下述表1中所示之游離能、帶隙、LUMO之值之欄中所記載之「-」表示未實施。 [Measurement of Electron Mobility, Threshold Voltage, On/Off Ratio] Ozone-treated silicon substrates were treated with hexamethyldisilazane (HMDS) or octadecyltrichlorosilane (ODTS). A chloroform solution with a polymer compound concentration of 0.5% by mass (7.4 mg/mL) was spin-coated on the surface of the treated substrate to fabricate an organic field-effect transistor (OFET; organic field-effect transistor) element. In addition, in Example 13, chlorobenzene was used instead of chloroform, and a chlorobenzene solution having a polymer compound concentration of 0.5% by mass was spin-coated. For the fabricated OFET element, annealing was performed at 100° C. for 1 hour and left to cool, and annealing was performed at 150° C. for 1 hour and left to cool, and then the Id-Vg characteristics were measured. The Id-Vg characteristics are measured under nitrogen atmosphere or vacuum. For the measurement of Id-Vg characteristics, "4200-SCS" manufactured by Keithley Instruments (KEITHLEY) was used, and the channel length of the organic semiconductor element was 25 μm, and the channel width was 294 mm. Id-Vg characteristics were measured to obtain electron mobility μe (cm ² /Vs), threshold voltage Vth (V), and on/off ratio (I _on /I _off ). The results of Id-Vg characteristics measured after annealing at 150° C. for 1 hour are shown in Table 1 below. In addition, "-" described in the columns of the value of ionization energy, band gap, and LUMO shown in Table 1 below indicates that it has not been implemented.

[表1-1] 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 Mw(重量平均分子量) 9000 2600 80000, 8300 30000 17000, 6900 96000 7100 Mn(數量平均分子量) 3800 1500 58000, 6500 16000 16000, 6700 62000 4300 溶解性氯仿〇〇〇〇〇〇〇氯苯〇〇〇〇〇〇〇甲苯 × 〇 △ × 〇〇 △ 游離能(eV) -5.45 -5.39 -5.69 -6.11 - - - 帶隙(eV) 1.38 1.32 1.63 1.64 1.65 - 1.63 LUMO(eV) -4.07 -4.07 -4.06 -4.47 - - - 表面處理 HMDS HMDS HMDS ODTS HMDS ODTS ODTS 測定氛圍 N ₂ N ₂ N ₂ N ₂ N ₂ N ₂ N ₂ 電子遷移率 μe(cm ²/Vs) 1.5×10 ^-5 6.8×10 ^-6 4.3×10 ^-5 1.7×10 ^-6 2.7×10 ^-7 1.1×10 ^-4 1.5×10 ^-7 閾值電壓 Vth(V) 40 50 40 15 55 14 46 開/關比 10 ⁴ 10 ⁵ 10 ³ 10 ³ 10 ² 10 ⁴ 10 ¹ [Table 1-1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Mw (weight average molecular weight) 9000 2600 80000, 8300 30000 17000, 6900 96000 7100 Mn (number average molecular weight) 3800 1500 58000, 6500 16000 16000, 6700 62000 4300 Solubility Chloroform 〇〇〇〇〇〇〇 chlorobenzene 〇〇〇〇〇〇〇 toluene x 〇 △ x 〇〇 △ Free energy (eV) -5.45 -5.39 -5.69 -6.11 - - - Bandgap (eV) 1.38 1.32 1.63 1.64 1.65 - 1.63 LUMO(eV) -4.07 -4.07 -4.06 -4.47 - - - surface treatment HMDS HMDS HMDS ODTS HMDS ODTS ODTS Measuring atmosphere N ₂ N ₂ N ₂ N ₂ N ₂ N ₂ N ₂ Electron mobility μe(cm ² /Vs) 1.5×10 ^-5 6.8×10 ^-6 4.3×10 ^-5 1.7×10 ^-6 2.7×10 ^-7 1.1×10 ^-4 1.5×10 ^-7 Threshold voltage Vth(V) 40 50 40 15 55 14 46 On/off ratio 10 ⁴ 10 ⁵ 10 ³ 10 ³ 10 ² 10 ⁴ 10 ¹

[表1-2] 實施例8 實施例9 實施例10 實施例11 實施例12 實施例13 Mw(重量平均分子量) 53000 67000 26000, 2500 30000 28000 69000 Mn(數量平均分子量) 29000 43000 22000, 1900 20000 26000 58000 溶解性氯仿〇〇〇〇〇〇氯苯〇〇〇〇〇〇甲苯〇〇 - △ 〇 △ 游離能(eV) -5.92 -5.96 -5.76 -5.80 - -5.98 帶隙(eV) 1.47 1.47 1.32 1.69 1.51 1.48 LUMO(eV) -4.45 -4.49 -4.44 -4.11 - -4.5 表面處理 ODTS ODTS HMDS HMDS HMDS ODTS 測定氛圍真空真空 N ₂ N ₂ N ₂ 真空電子遷移率 μe(cm ²/Vs) 6.8×10 ^-4 1.5×10 ^-3 1.7×10 ^-6 1.5×10 ^-5 1.7×10 ^-4 1.1×10 ^-2 閾值電壓 Vth(V) 30 17 38 56 12 24 開/關比 10 ⁶ 10 ⁵ 10 ³ 10 ⁵ 10 ⁴ 10 ⁷ [Table 1-2] Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Mw (weight average molecular weight) 53000 67000 26000, 2500 30000 28000 69000 Mn (number average molecular weight) 29000 43000 22000, 1900 20000 26000 58000 Solubility Chloroform 〇〇〇〇〇〇 chlorobenzene 〇〇〇〇〇〇 toluene 〇〇 - △ 〇 △ Free energy (eV) -5.92 -5.96 -5.76 -5.80 - -5.98 Bandgap (eV) 1.47 1.47 1.32 1.69 1.51 1.48 LUMO(eV) -4.45 -4.49 -4.44 -4.11 - -4.5 surface treatment ODTS ODTS HMDS HMDS HMDS ODTS Measuring atmosphere vacuum vacuum N ₂ N ₂ N ₂ vacuum Electron mobility μe(cm ² /Vs) 6.8×10 ^-4 1.5×10 ^-3 1.7×10 ^-6 1.5×10 ^-5 1.7×10 ^-4 1.1×10 ^-2 Threshold voltage Vth(V) 30 17 38 56 12 twenty four On/off ratio 10 ⁶ 10 ⁵ 10 ³ 10 ⁵ 10 ⁴ 10 ⁷

根據表1可探討如下。本發明之高分子型化合物1至高分子型化合物13係具有包含預定結構之供體性單元及受體性單元各1個以上且供體性單元與受體性單元相互連結之化合物，尤其是為具有供體性單元及受體性單元作為重複單位之化合物。本發明之高分子型化合物1至高分子型化合物13於溶媒中之溶解性、尤其是於鹵素系有機溶媒中之溶解性良好。另外，本發明之高分子型化合物1至高分子型化合物13可較佳地用作有機半導體材料。另外，本發明之高分子型化合物1至高分子型化合物13即便進行150℃之退火，亦顯示良好的電子遷移率。對於實施例16中所獲得之高分子化合物16，由於包含噻唑單元，故而供體性單元與受體性單元之間的應變變少，成為接***面之結構，分子彼此變得容易排列，從而可期待結晶性提升，電子遷移率提升。According to Table 1, it can be discussed as follows. Polymer compound 1 to polymer compound 13 of the present invention are compounds having one or more donor units and one acceptor unit each having a predetermined structure, and the donor unit and the acceptor unit are connected to each other, especially A compound having a donor unit and an acceptor unit as repeating units. The polymer compound 1 to the polymer compound 13 of the present invention have good solubility in solvents, especially in halogen-based organic solvents. In addition, the polymer compound 1 to the polymer compound 13 of the present invention can be preferably used as an organic semiconductor material. In addition, polymer compound 1 to polymer compound 13 of the present invention showed good electron mobility even after annealing at 150°C. For the polymer compound 16 obtained in Example 16, since the thiazole unit is included, the strain between the donor unit and the acceptor unit becomes less, and it becomes a structure close to a plane, and the molecules are easily arranged with each other, so that Improvement in crystallinity and improvement in electron mobility are expected.

[實驗2] [實施例21] 對於20mL燒瓶添加2,5-雙(三丁基錫烷基)螺[7H-環戊[1,2-d:4,3-d']雙噻唑-7,2'-[1,3]二氧戊環](Ac-CBTZ-SB、60mg、0.0735mmol)、4-溴-2,7-二丁基-苯并[lmn][3,8]啡啉-1,3,6,8(2H,7H)-四酮(BU-NDI-MB、67.3mg、0.147mmol)、三(二亞苄基丙酮)二鈀(0)氯仿加成物(6mg、5.9μmol)、三(2-甲氧基苯基)膦(8.9mg、25.0μmol)及氯苯(4mL)，於130℃反應16小時。反應結束後，實施矽藻土過濾並進行濃縮。進而，加入氯仿(3mL)、甲醇(7mL)，濾取所析出之固體，結果獲得深藍色固體52.7mg(產率72.3%)。進行NMR光譜測定，結果所獲得之深藍色固體為Ac-CBTZ-2(Bu-NDI)(以下，有時稱為低分子型化合物1)。以溶液之狀態進行所獲得之低分子型化合物1之紫外可見吸收光譜測定，將測定結果以實線示於圖15。 ¹H NMR (400 MHz, 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) [化50] [Experiment 2] [Example 21] 2,5-bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bithiazole-7,2 was added to a 20 mL flask '-[1,3]dioxolane](Ac-CBTZ-SB, 60mg, 0.0735mmol), 4-bromo-2,7-dibutyl-benzo[lmn][3,8]phenanthroline- 1,3,6,8(2H,7H)-tetraketone (BU-NDI-MB, 67.3mg, 0.147mmol), tris(dibenzylideneacetone) dipalladium(0) chloroform adduct (6mg, 5.9 μmol), tris(2-methoxyphenyl)phosphine (8.9mg, 25.0μmol) and chlorobenzene (4mL), react at 130°C for 16 hours. After completion of the reaction, Celite filtration and concentration were performed. Furthermore, chloroform (3 mL) and methanol (7 mL) were added, and the precipitated solid was collected by filtration to obtain 52.7 mg of a dark blue solid (yield 72.3%). As a result of NMR spectrum measurement, the obtained dark blue solid was Ac-CBTZ-2(Bu-NDI) (hereinafter, may be 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 results are shown in FIG. 15 by a solid line. ¹ H NMR (400 MHz, 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) [Chem. 50]

[實施例22] 對於20mL燒瓶添加2,5-雙(三丁基錫烷基)螺[7H-環戊[1,2-d:4,3-d']雙噻唑-7,2'-[1,3]二氧戊環](Ac-CBTZ-SB、60mg、0.0735mmol)、4-溴-2,7-雙(2-乙基己基)-苯并[lmn][3,8]啡啉-1,3,6,8(2H,7H)-四酮(EH-NDI-MB、84.3mg、0.147mmol)、三(二亞苄基丙酮)二鈀(0)氯仿加成物(6mg、5.9μmol)、三(2-甲氧基苯基)膦(8.9mg、25.0μmol)及氯苯(4mL)，於130℃反應16小時。反應結束後，實施矽藻土過濾並進行濃縮。進而，加入甲醇(10mL)，濾取所析出之固體，結果獲得深藍色固體40.1mg(產率44.2%)。進行NMR光譜測定，結果所獲得之深藍色固體為Ac-CBTZ-2(EH-NDI)(以下，有時稱為低分子型化合物2)。 ¹H NMR (400 MHz, CDCl ₃): 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) [化51] [Example 22] 2,5-bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bithiazole-7,2'-[1 ,3]dioxolane](Ac-CBTZ-SB, 60mg, 0.0735mmol), 4-bromo-2,7-bis(2-ethylhexyl)-benzo[lmn][3,8]phenanthroline -1,3,6,8(2H,7H)-tetraketone (EH-NDI-MB, 84.3mg, 0.147mmol), tris(dibenzylideneacetone) dipalladium(0) chloroform adduct (6mg, 5.9 μmol), tris(2-methoxyphenyl)phosphine (8.9 mg, 25.0 μmol) and chlorobenzene (4 mL), react at 130° C. for 16 hours. After completion of the reaction, Celite filtration and concentration were performed. Further, methanol (10 mL) was added, and the precipitated solid was collected by filtration to obtain 40.1 mg of a dark blue solid (44.2% yield). As a result of NMR spectrum measurement, the obtained dark blue solid was Ac-CBTZ-2(EH-NDI) (hereinafter, may be referred to as low-molecular-weight compound 2). ¹ H NMR (400 MHz, CDCl ₃ ): 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) [Chem. 51]

[實施例23] 對於20mL燒瓶添加2,5-雙(三丁基錫烷基)螺[7H-環戊[1,2-d:4,3-d']雙噻唑-7,2'-[1,3]二氧戊環](Ac-CBTZ-SB、60mg、0.0735mmol)、4-溴-2,7-二己基-苯并[lmn][3,8]啡啉-1,3,6,8(2H,7H)-四酮(Hex-NDI-MB、75.3mg、0.147mmol)、三(二亞苄基丙酮)二鈀(0)氯仿加成物(6mg、5.9μmol)、三(2-甲氧基苯基)膦(8.9mg、25.0μmol)及氯苯(4mL)，於130℃反應16小時。反應結束後，實施矽藻土過濾並進行濃縮。進而，加入甲醇(7mL)，濾取所析出之固體，結果獲得深藍色固體59.9mg(產率73.3%)。進行NMR光譜測定，結果所獲得之深藍色固體為Ac-CBTZ-2(Hex-NDI)(以下，有時稱為低分子型化合物3)。以溶液之狀態進行所獲得之低分子型化合物3之紫外可見吸收光譜測定，將測定結果以實線示於圖16。 ¹H NMR (400 MHz, CDCl ₃): 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) [化52] [Example 23] 2,5-bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bithiazole-7,2'-[1 ,3]dioxolane](Ac-CBTZ-SB, 60mg, 0.0735mmol), 4-bromo-2,7-dihexyl-benzo[lmn][3,8]phenanthroline-1,3,6 , 8(2H,7H)-tetraketone (Hex-NDI-MB, 75.3 mg, 0.147 mmol), tris(dibenzylideneacetone) dipalladium(0) chloroform adduct (6 mg, 5.9 μmol), tris( 2-Methoxyphenyl)phosphine (8.9mg, 25.0μmol) and chlorobenzene (4mL) were reacted at 130°C for 16 hours. After completion of the reaction, Celite filtration and concentration were performed. Furthermore, methanol (7 mL) was added, and the precipitated solid was collected by filtration to obtain 59.9 mg of a dark blue solid (yield 73.3%). As a result of NMR spectrum measurement, the obtained dark blue solid was Ac-CBTZ-2 (Hex-NDI) (hereinafter, may be 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 results are shown in FIG. 16 by a solid line. ¹ H NMR (400 MHz, CDCl ₃ ): 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) [Chem. 52]

[實施例24] 對於20mL燒瓶添加2,5-雙(三丁基錫烷基)螺[7H-環戊[1,2-d:4,3-d']雙噻唑-7,2'-[1,3]二氧戊環](Ac-CBTZ-SB、60mg、0.0735mmol)、4-溴-2,7-二辛基-苯并[lmn][3,8]啡啉-1,3,6,8(2H,7H)-四酮(n-o-NDI-MB、83.5mg、0.147mmol)、三(二亞苄基丙酮)二鈀(0)氯仿加成物(6mg、5.9μmol)、三(2-甲氧基苯基)膦(8.9mg、25.0μmol)及氯苯(4mL)，於130℃反應16小時。反應結束後，實施矽藻土過濾並進行濃縮。進而，加入甲醇(7mL)，濾取所析出之固體，結果獲得深藍色固體71.7mg(產率80%)。進行NMR光譜測定，結果所獲得之深藍色固體為Ac-CBTZ-2(n-o-NDI)(以下，有時稱為低分子型化合物4)。以溶液之狀態進行所獲得之低分子型化合物4之紫外可見吸收光譜測定，將測定結果以實線示於圖17。 ¹H NMR (400 MHz, 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) [化53] [Example 24] 2,5-bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bithiazole-7,2'-[1 ,3] dioxolane] (Ac-CBTZ-SB, 60mg, 0.0735mmol), 4-bromo-2,7-dioctyl-benzo[lmn][3,8]phenanthroline-1,3, 6,8(2H,7H)-tetraketone (no-NDI-MB, 83.5 mg, 0.147 mmol), tris(dibenzylideneacetone) dipalladium(0) chloroform adduct (6 mg, 5.9 μmol), tris(dibenzylideneacetone) (2-Methoxyphenyl)phosphine (8.9 mg, 25.0 μmol) and chlorobenzene (4 mL) were reacted at 130° C. for 16 hours. After completion of the reaction, Celite filtration and concentration were performed. Further, methanol (7 mL) was added, and the precipitated solid was collected by filtration to obtain 71.7 mg of a dark blue solid (80% yield). As a result of NMR spectrum measurement, the obtained dark blue solid was Ac-CBTZ-2 (no-NDI) (hereinafter, may be referred to as low-molecular-weight compound 4). The ultraviolet-visible absorption spectrum of the obtained low-molecular-weight compound 4 was measured in a solution state, and the measurement results are shown in FIG. 17 by a solid line. ¹ H NMR (400 MHz, 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) [Chem. 53]

[實施例25] 對於20mL燒瓶添加2,5-雙(三丁基錫烷基)螺[7H-環戊[1,2-d:4,3-d']雙噻唑-7,2'-[1,3]二氧戊環](Ac-CBTZ-SB、60mg、0.0735mmol)、4-溴-2,7-雙(2-癸基十四烷基)苯并[lmn][3,8]啡啉-1,3,6,8(2H,7H)-四酮(DMO-NDI-MB、91.2mg、0.147mmol)、三(二亞苄基丙酮)二鈀(0)氯仿加成物(6mg、5.9μmol)、三(2-甲氧基苯基)膦(8.9mg、25.0μmol)及氯苯(4mL)，於130℃反應16小時。反應結束後，實施矽藻土過濾並進行濃縮。進而，加入甲醇(7mL)，濾取所析出之固體，結果獲得深藍色固體85.9mg(產率95.5%)。進行NMR光譜測定，結果所獲得之深藍色固體為Ac-CBTZ-2(DMO-NDI)(以下，有時稱為低分子型化合物5)。以溶液之狀態進行所獲得之低分子型化合物5之紫外可見吸收光譜測定，將測定結果以實線示於圖18。 ¹H NMR (400 MHz, CDCl ₃): 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) [化54] [Example 25] 2,5-bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bithiazole-7,2'-[1 ,3]dioxolane](Ac-CBTZ-SB, 60mg, 0.0735mmol), 4-bromo-2,7-bis(2-decyltetradecyl)benzo[lmn][3,8] Phenanthroline-1,3,6,8(2H,7H)-tetraketone (DMO-NDI-MB, 91.2 mg, 0.147 mmol), tris(dibenzylideneacetone) dipalladium(0) chloroform adduct ( 6mg, 5.9μmol), tris(2-methoxyphenyl)phosphine (8.9mg, 25.0μmol) and chlorobenzene (4mL), react at 130°C for 16 hours. After completion of the reaction, Celite filtration and concentration were performed. Further, methanol (7 mL) was added, and the precipitated solid was collected by filtration to obtain 85.9 mg of a dark blue solid (95.5% yield). As a result of NMR spectrum measurement, the obtained dark blue solid was Ac-CBTZ-2(DMO-NDI) (hereinafter, sometimes referred to as low-molecular-weight compound 5). The ultraviolet-visible absorption spectrum of the obtained low-molecular-weight compound 5 was measured in a solution state, and the measurement results are shown in FIG. 18 by a solid line. ¹ H NMR (400 MHz, CDCl ₃ ): 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) [Chem. 54]

[實施例26] 對於20mL燒瓶添加2,5-雙(三丁基錫烷基)螺[7H-環戊[1,2-d:4,3-d']雙噻唑-7,2'-[1,3]二氧戊環](Ac-CBTZ-SB、60mg、0.0735mmol)、4-溴-2,7-二癸基苯并[lmn][3,8]啡啉-1,3,6,8(2H,7H)-四酮(DE-NDI-MB、92.5mg、0.147mmol)、三(二亞苄基丙酮)二鈀(0)氯仿加成物(6mg、5.9μmol)、三(2-甲氧基苯基)膦(8.9mg、25.0μmol)及氯苯(4mL)，於130℃反應16小時。反應結束後，實施矽藻土過濾並進行濃縮。進而，加入甲醇(7mL)，濾取所析出之固體，結果獲得深藍色固體57.5mg(產率71.0%)。進行NMR光譜測定，結果所獲得之深藍色固體為Ac-CBTZ-2(DE-NDI)(以下，有時稱為低分子型化合物6)。以溶液之狀態進行所獲得之低分子型化合物6之紫外可見吸收光譜測定，將測定結果以實線示於圖19。 ¹H NMR (400 MHz, CDCl ₃): 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) [化55] [Example 26] 2,5-bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bithiazole-7,2'-[1 ,3]dioxolane](Ac-CBTZ-SB, 60mg, 0.0735mmol), 4-bromo-2,7-didecylbenzo[lmn][3,8]phenanthroline-1,3,6 , 8(2H,7H)-tetraketone (DE-NDI-MB, 92.5 mg, 0.147 mmol), tris(dibenzylideneacetone) dipalladium(0) chloroform adduct (6 mg, 5.9 μmol), tris( 2-Methoxyphenyl)phosphine (8.9mg, 25.0μmol) and chlorobenzene (4mL) were reacted at 130°C for 16 hours. After completion of the reaction, Celite filtration and concentration were performed. Further, methanol (7 mL) was added, and the precipitated solid was collected by filtration to obtain 57.5 mg of a dark blue solid (yield 71.0%). As a result of NMR spectrum measurement, the obtained dark blue solid was Ac-CBTZ-2(DE-NDI) (hereinafter, sometimes referred to as low-molecular-weight compound 6). The ultraviolet-visible absorption spectrum of the obtained low-molecular-weight compound 6 was measured in a solution state, and the measurement results are shown in FIG. 19 by a solid line. ¹ H NMR (400 MHz, CDCl ₃ ): 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) [Chem. 55]

[實施例27] 對於20mL燒瓶添加2,5-雙(三丁基錫烷基)螺[7H-環戊[1,2-d:4,3-d']雙噻唑-7,2'-[1,3]二氧戊環](Ac-CBTZ-SB、60mg、0.0735mmol)、4-溴-2,7-雙(2-癸基十四烷基)苯并[lmn][3,8]啡啉-1,3,6,8(2H,7H)-四酮(TD-NDI-MB、183.4mg、0.147mmol)、三(二亞苄基丙酮)二鈀(0)氯仿加成物(6mg、5.9μmol)、三(2-甲氧基苯基)膦(8.9mg、25.0μmol)及氯苯(4mL)，於130℃反應16小時。反應結束後，實施矽藻土過濾並進行濃縮。進而，加入甲醇(7mL)，濾取所析出之固體，結果獲得深藍色固體58.3mg(產率38.3%)。進行NMR光譜測定，結果所獲得之深藍色固體為Ac-CBTZ-2(TD-NDI)(以下，有時稱為低分子型化合物7)。以溶液之狀態進行所獲得之低分子型化合物7之紫外可見吸收光譜測定，將測定結果以實線示於圖20。 ¹H NMR (400 MHz, CDCl ₃): 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), 0.818 (t, 12H) [化56] [Example 27] 2,5-bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bithiazole-7,2'-[1 ,3]dioxolane](Ac-CBTZ-SB, 60mg, 0.0735mmol), 4-bromo-2,7-bis(2-decyltetradecyl)benzo[lmn][3,8] Phenanthroline-1,3,6,8(2H,7H)-tetraketone (TD-NDI-MB, 183.4mg, 0.147mmol), tris(dibenzylideneacetone) dipalladium(0) chloroform adduct ( 6mg, 5.9μmol), tris(2-methoxyphenyl)phosphine (8.9mg, 25.0μmol) and chlorobenzene (4mL), react at 130°C for 16 hours. After completion of the reaction, Celite filtration and concentration were performed. Further, methanol (7 mL) was added, and the precipitated solid was collected by filtration to obtain 58.3 mg of a dark blue solid (38.3% yield). As a result of NMR spectrum measurement, the obtained dark blue solid was Ac-CBTZ-2(TD-NDI) (hereinafter, may be 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 results are shown in FIG. 20 by a solid line. ¹ H NMR (400 MHz, CDCl ₃ ): 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), 0.818 (t, 12H) [Chem. 56]

[實施例28] 對於20mL燒瓶添加2,5-雙(三丁基錫烷基)螺[7H-環戊[1,2-d:4,3-d']雙噻唑-7,2'-[1,3]二氧戊環](Ac-CBTZ-SB、60mg、0.0735mmol)、4-溴-2,7-雙(2-苯基乙基)苯并[lmn][3,8]啡啉-1,3,6,8(2H,7H)-四酮(PhEt-NDI-MB、81.8mg、0.147mmol)、三(二亞苄基丙酮)二鈀(0)氯仿加成物(6mg、5.9μmol)、三(2-甲氧基苯基)膦(8.9mg、25.0μmol)及氯苯(4mL)，於130℃反應16小時。反應結束後，實施矽藻土過濾並進行濃縮。進而，加入甲醇(7mL)，濾取所析出之固體，結果獲得深藍色固體68.3mg(產率84.2%)。進行NMR光譜測定，結果所獲得之深藍色固體為Ac-CBTZ-2(PhEt-NDI)(以下，有時稱為低分子型化合物8)。 ¹H NMR (400 MHz, 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) [化57] 由圖15至圖20可明顯看出，本發明之低分子型化合物1、低分子型化合物3至低分子型化合物7以溶液之狀態及薄膜之狀態均能夠吸收長波長區域之光。此外，低分子型化合物2由於試樣量少，故而無法測定紫外可見吸收光譜。低分子型化合物8幾乎不溶解於氯仿，因此無法測定紫外可見吸收光譜。 [Example 28] 2,5-bis(tributylstannyl)spiro[7H-cyclopenta[1,2-d:4,3-d']bithiazole-7,2'-[1 ,3]dioxolane](Ac-CBTZ-SB, 60mg, 0.0735mmol), 4-bromo-2,7-bis(2-phenylethyl)benzo[lmn][3,8]phenanthroline -1,3,6,8(2H,7H)-tetraketone (PhEt-NDI-MB, 81.8mg, 0.147mmol), tris(dibenzylideneacetone) dipalladium(0) chloroform adduct (6mg, 5.9 μmol), tris(2-methoxyphenyl)phosphine (8.9 mg, 25.0 μmol) and chlorobenzene (4 mL), react at 130° C. for 16 hours. After completion of the reaction, Celite filtration and concentration were performed. Further, methanol (7 mL) was added, and the precipitated solid was collected by filtration to obtain 68.3 mg of a dark blue solid (84.2% yield). As a result of NMR spectrum measurement, the obtained dark blue solid was Ac-CBTZ-2(PhEt-NDI) (hereinafter, may be referred to as low-molecular-weight compound 8). ¹ H NMR (400 MHz, 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) [Chemical 57] It can be clearly seen from Fig. 15 to Fig. 20 that low-molecular compound 1, low-molecular compound 3 to low-molecular compound 7 of the present invention can absorb light in the long-wavelength region both in the state of solution and in the state of film. In addition, the low-molecular-weight compound 2 could not measure the ultraviolet-visible absorption spectrum due to the small amount of the sample. Low-molecular-weight compound 8 was hardly soluble in chloroform, so the ultraviolet-visible absorption spectrum could not be measured.

其次，對所獲得之低分子型化合物1至低分子型化合物8於溶媒中之溶解性進行評價。溶媒使用氯仿、氯苯、甲苯、四氯乙烷、或1-甲基萘。於使用氯仿之情形時，以低分子型化合物的濃度成為1質量%之方式，於室溫下添加氯仿。於使用氯苯之情形時，以低分子型化合物成為1質量%之方式，於室溫下添加氯苯。於使用甲苯之情形時，以低分子型化合物成為1質量%之方式，於室溫下添加甲苯。於使用四氯乙烷之情形時，以低分子型化合物成為1質量%之方式，於室溫下添加四氯乙烷，然後加熱至110℃。於使用1-甲基萘之情形時，以低分子型化合物成為1質量%之方式，於室溫下添加1-甲基萘，然後加熱至110℃。此外，低分子型化合物1對於氯仿之溶解性係以低分子型化合物1的濃度成為1質量%之方式，於室溫下添加氯仿，然後加熱至50℃而進行評價。低分子型化合物1對於氯苯之溶解性係以低分子型化合物1的濃度成為1質量%之方式，於室溫下添加氯苯，然後加熱至110℃而進行評價。Next, the solubility of the obtained low-molecular compound 1 to low-molecular compound 8 in the solvent was evaluated. As a solvent, chloroform, chlorobenzene, toluene, tetrachloroethane, or 1-methylnaphthalene is used. In the case of using chloroform, chloroform was added at room temperature so that the concentration of the low-molecular-weight compound became 1% by mass. In the case of using chlorobenzene, chlorobenzene was added at room temperature so that the low-molecular-weight compound became 1% by mass. When using toluene, toluene was added at room temperature so that the low-molecular-weight compound became 1 mass %. When tetrachloroethane was used, tetrachloroethane was added at room temperature so that the low-molecular-weight compound became 1 mass %, and it heated to 110 degreeC after that. In the case of using 1-methylnaphthalene, after adding 1-methylnaphthalene at room temperature so that the low-molecular-weight compound becomes 1 mass %, it heats to 110 degreeC. In addition, the solubility of the low-molecular-weight compound 1 in chloroform was evaluated by adding chloroform at room temperature so that the concentration of the low-molecular-weight compound 1 became 1% by mass, and then heating to 50°C. The solubility of low-molecular-weight compound 1 to chlorobenzene was evaluated by adding chlorobenzene at room temperature so that the concentration of low-molecular-weight compound 1 became 1% by mass, and then heating to 110°C.

添加溶媒後，利用目視觀察低分子型化合物是否溶解，基於下述基準進行評價。將評價結果示於下述表2。下述表2中，「-」表示未進行評價。 [評價基準] ○：溶解於溶媒。 △：低分子型化合物之一部分未溶解而殘留。 ×：未溶解於溶媒。 After adding the solvent, whether or not the low-molecular-weight compound was dissolved was observed visually, and 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] ◯: Dissolved in a solvent. Δ: Part of the low-molecular-weight compound remained without being dissolved. ×: Not dissolved in the solvent.

其次，使用所獲得之低分子型化合物1、低分子型化合物3至低分子型化合物7，測定游離能、帶隙、電子遷移率μe、閾值電壓、及開/關比。游離能、帶隙、電子遷移率μe、閾值電壓、及開/關比之測定條件與使用上述高分子型化合物進行測定之情形相同。將測定結果示於下述表2。另外，將以薄膜之狀態所測定之UV測定之結果以虛線示於圖15至圖20。此外，製作用於測定電子遷移率μe、閾值電壓、及開/關比之有機場效型電晶體(OFET)元件時，作為旋轉塗佈之溶液之溶媒，使用氯仿、氯苯、或四氯乙烷。將所使用之溶媒一併示於下述表2。另外，由游離能及帶隙求出LUMO之值。Next, using the obtained low-molecular compound 1, low-molecular compound 3 to low-molecular compound 7, free energy, band gap, electron mobility μe, threshold voltage, and on/off ratio were measured. The measurement conditions of ionization energy, band gap, electron mobility μe, threshold voltage, and on/off ratio are the same as those in the case of measurement using the above-mentioned polymer compound. The measurement results are shown in Table 2 below. In addition, the results of UV measurement measured in the state of a thin film are shown by dotted lines in FIGS. 15 to 20 . In addition, when fabricating organic field-effect transistor (OFET) elements for measuring electron mobility μe, threshold voltage, and on/off ratio, chloroform, chlorobenzene, or tetrachloromethane are used as solvents for spin-coating solutions. ethane. The solvents used are collectively shown in Table 2 below. In addition, the value of LUMO was obtained from the ionization energy and the band gap.

其次，針對低分子型化合物2、低分子型化合物8，設計構成受體性單元之氮上所鍵結之取代基為甲基之三聚物型化合物，藉由DFT(Discrete Fourier Transform；離散傅立葉轉換)計算預測游離能之值(HOMO之值)及LUMO之值。將計算所使用之三聚物型化合物示於下述式。DFT計算係使用Gaussian 16作為計算軟體。將游離能之值及LUMO之值(eV)示於下述表2。另外，下述表2中亦表示由游離能之值及LUMO之值所算出之帶隙(eV)之值。另外，使用低分子型化合物2，測定電子遷移率μe、閾值電壓、及開/關比。電子遷移率μe、閾值電壓、及開/關比之測定條件與使用上述高分子型化合物進行測定之情形相同。將測定結果示於下述表2。此外，對於低分子型化合物8，未測定電子遷移率μe、閾值電壓、及開/關比。Secondly, for the low-molecular-weight compound 2 and the low-molecular-weight compound 8, a trimer compound in which the substituent bonded to the nitrogen constituting the acceptor unit is methyl is designed, and the DFT (Discrete Fourier Transform; Discrete Fourier Transform) Conversion) to calculate the value of the predicted ionization energy (the value of HOMO) and the value of LUMO. The terpolymer-type compound used for calculation is shown in the following formula. The DFT calculation system uses Gaussian 16 as the calculation software. The value of ionization energy and the value (eV) of LUMO are shown in Table 2 below. In addition, the following Table 2 also shows the value of the band gap (eV) calculated from the value of the ionization energy and the value of LUMO. In addition, using the low-molecular-weight compound 2, electron mobility μe, threshold voltage, and on/off ratio were measured. The measurement conditions of the electron mobility μe, the threshold voltage, and the on/off ratio are the same as the measurement using the above-mentioned polymer compound. The measurement results are shown in Table 2 below. In addition, for the low-molecular-weight compound 8, the electron mobility μe, threshold voltage, and on/off ratio were not measured.

[化58] [表2] 實施例21 實施例22 實施例23 實施例24 實施例25 實施例26 實施例27 實施例28 溶解性四氯乙烷 △ 〇〇〇〇〇〇 - 氯仿 ○ 〇〇〇〇〇〇 - 氯苯 △ 〇〇〇〇〇〇 - 甲苯 △ 〇〇〇〇〇〇 - 1-甲基萘 △ 〇〇〇〇〇〇〇游離能 (eV) -4.42 -5.74 -4.3 -4.76 -4.33 -4.51 -4.43 -5.74 帶隙 (eV) 1.6 2.12 1.77 1.84 1.6 1.72 1.77 2.12 LUMO (eV) -6.02 -3.62 -6.07 -6.6 -5.93 -6.23 -6.2 -3.62 表面處理 HMDS ODTS ODTS HMDS HMDS HMDS HMDS - 測定氛圍真空 N ₂ N ₂ N ₂ N ₂ N ₂ N ₂ - 旋轉塗佈溶媒氯仿氯苯氯苯四氯乙烷氯苯四氯乙烷四氯乙烷 - 電子遷移率 μe(cm ²/Vs) 2.7×10 ^-3 1.4×10 ^-4 6.8×10 ^-4 4.3×10 ^-3 6.8×10 ^-6 1.7×10 ^-4 6.8×10 ^-10 - 閾值電壓 Vth(V) 20 68 28 32 28 28 60 - 開/關比 10 ⁶ 10 ⁴ 10 ⁶ 10 ⁷ 10 ⁵ 10 ⁴ 10 ² - [Chemical 58] [Table 2] Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 Solubility Tetrachloroethane △ 〇〇〇〇〇〇 - Chloroform ○ 〇〇〇〇〇〇 - chlorobenzene △ 〇〇〇〇〇〇 - toluene △ 〇〇〇〇〇〇 - 1-Methylnaphthalene △ 〇〇〇〇〇〇〇 Free energy (eV) -4.42 -5.74 -4.3 -4.76 -4.33 -4.51 -4.43 -5.74 Bandgap (eV) 1.6 2.12 1.77 1.84 1.6 1.72 1.77 2.12 LUMO (eV) -6.02 -3.62 -6.07 -6.6 -5.93 -6.23 -6.2 -3.62 surface treatment HMDS ODTS ODTS HMDS HMDS HMDS HMDS - Measuring atmosphere vacuum N ₂ N ₂ N ₂ N ₂ N ₂ N ₂ - spin coating solvent Chloroform chlorobenzene chlorobenzene Tetrachloroethane chlorobenzene Tetrachloroethane Tetrachloroethane - Electron mobility μe(cm ² /Vs) 2.7×10 ^-3 1.4×10 ^-4 6.8×10 ^-4 4.3×10 ^-3 6.8×10 ^-6 1.7×10 ^-4 6.8× ^10-10 - Threshold voltage Vth(V) 20 68 28 32 28 28 60 - On/off ratio 10 ⁶ 10 ⁴ 10 ⁶ 10 ⁷ 10 ⁵ 10 ⁴ 10 ² -

根據表2可探討如下。本發明之低分子型化合物1至低分子型化合物8係具有包含預定結構之供體性單元及受體性單元各1個以上且供體性單元與受體性單元相互連結之化合物，尤其是為具有供體性單元及受體性單元合計3個之化合物(詳細而言，於供體性單元上連結有2個受體性單元之三聚物型化合物)。本發明之低分子型化合物1至低分子型化合物8於溶媒中之溶解性良好。另外，本發明之低分子型化合物1至低分子型化合物8可較佳地用作有機半導體材料。另外，本發明之低分子型化合物1至低分子型化合物7即便進行150℃之退火，亦顯示良好的電子遷移率。According to Table 2, it can be discussed as follows. Low-molecular-weight compound 1 to low-molecular-weight compound 8 of the present invention are compounds having one or more donor units and one acceptor unit each having a predetermined structure, and the donor unit and the acceptor unit are connected to each other, especially It is a compound having a total of three donor units and acceptor units (specifically, a trimer compound in which two acceptor units are linked to the donor unit). Low-molecular-weight compound 1 to low-molecular-weight compound 8 of the present invention have good solubility in solvents. In addition, low-molecular compound 1 to low-molecular compound 8 of the present invention can be preferably used as an organic semiconductor material. In addition, low-molecular compound 1 to low-molecular compound 7 of the present invention showed good electron mobility even after annealing at 150°C.

[圖1]表示高分子型化合物1之紫外可見吸收光譜。 [圖2]表示高分子型化合物2之紫外可見吸收光譜。 [圖3]表示高分子型化合物3之紫外可見吸收光譜。 [圖4]表示高分子型化合物4之紫外可見吸收光譜。 [圖5]表示高分子型化合物5之紫外可見吸收光譜。 [圖6]表示高分子型化合物6之紫外可見吸收光譜。 [圖7]表示高分子型化合物7之紫外可見吸收光譜。 [圖8]表示高分子型化合物8之紫外可見吸收光譜。 [圖9]表示高分子型化合物9之紫外可見吸收光譜。 [圖10]表示高分子型化合物10之紫外可見吸收光譜。 [圖11]表示高分子型化合物11之紫外可見吸收光譜。 [圖12]表示高分子型化合物12之紫外可見吸收光譜。 [圖13]表示高分子型化合物13之紫外可見吸收光譜。 [圖14]係用於說明帶隙之算出方法之示意圖，係對進行包含高分子型化合物9之薄膜之UV測定所獲得之紫外可見吸收光譜畫出輔助線之示意圖。 [圖15]表示低分子型化合物1之紫外可見吸收光譜。 [圖16]表示低分子型化合物3之紫外可見吸收光譜。 [圖17]表示低分子型化合物4之紫外可見吸收光譜。 [圖18]表示低分子型化合物5之紫外可見吸收光譜。 [圖19]表示低分子型化合物6之紫外可見吸收光譜。 [圖20]表示低分子型化合物7之紫外可見吸收光譜。 [ 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 polymer compound 10. [ Fig. 11 ] shows the ultraviolet-visible absorption spectrum of polymer compound 11. [ Fig. 12 ] shows the ultraviolet-visible absorption spectrum of polymer compound 12. [ Fig. 13 ] shows the ultraviolet-visible absorption spectrum of polymer compound 13. [ FIG. 14 ] is a schematic diagram for explaining the calculation method of the band gap, and is a schematic diagram in which auxiliary lines are drawn for the ultraviolet-visible absorption spectrum obtained by UV measurement of a thin film containing polymer compound 9 . [ Fig. 15 ] shows the ultraviolet-visible absorption spectrum of low-molecular-weight compound 1. [ Fig. 16 ] shows the ultraviolet-visible absorption spectrum of 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 low-molecular-weight compound 5. [ Fig. 19 ] shows the ultraviolet-visible absorption spectrum of low-molecular-weight compound 6. [ Fig. 20 ] shows the ultraviolet-visible absorption spectrum of low-molecular-weight compound 7.

Claims

一種化合物，具有包含下述式(Do-A)所表示之單位之供體性單元及受體性單元各1個以上，且供體性單元與受體性單元相互連結著； [化1] 式(Do-A)中，R ^a表示碳數2至10之伸烷基，*表示鍵結部位。 A compound having at least one donor unit and one acceptor unit each comprising a unit represented by the following formula (Do-A), and the donor unit and the acceptor unit are linked to each other; [Chem. 1] In the formula (Do-A), R ^a represents an alkylene group having 2 to 10 carbon atoms, and * represents a bonding site.

如請求項1所記載之化合物，其中前述受體性單元包含選自由下述(1)至(3)所組成之群組中的至少1種： (1) 雜芳香族縮環型單元，具有縮環結構，且環之至少1個為芳香族環，構成環之元素為碳原子及雜原子； (2) 芳香族縮環型單元，具有縮環結構，且環之至少1個為芳香族環，構成環之元素為碳原子；及 (3) 單環型單元，具有芳香族環且不具有縮環結構。 The compound as described in claim 1, wherein the above-mentioned receptivity unit includes at least one selected from the group consisting of the following (1) to (3): (1) Heteroaromatic condensed ring unit, which has a condensed ring structure, and at least one of the rings is an aromatic ring, and the elements constituting the ring are carbon atoms and heteroatoms; (2) An aromatic condensed ring unit, having a condensed ring structure, and at least one of the rings is an aromatic ring, and the elements constituting the ring are carbon atoms; and (3) A monocyclic unit having an aromatic ring and not having a condensed ring structure.

如請求項1所記載之化合物，其具有前述供體性單元及前述受體性單元作為重複單位。The compound according to claim 1, which has the aforementioned donating unit and the aforementioned accepting unit as repeating units.

如請求項3所記載之化合物，其中前述供體性單元與前述受體性單元交替地配置。The compound as described in claim 3, wherein the aforementioned donating units and the aforementioned accepting units are arranged alternately.

如請求項3所記載之化合物，其重量平均分子量(Mw)為1500以上。The compound described in claim 3 has a weight average molecular weight (Mw) of 1500 or more.

如請求項3所記載之化合物，其中前述高分子型化合物中所含之多個供體性單元進而包含下述式(Do-K)所表示之單位； [化2] 式(Do-K)中，*表示鍵結部位。 The compound as described in claim 3, wherein the plurality of donating units contained in the aforementioned polymer compound further include a unit represented by the following formula (Do-K); [Chemical 2] In the formula (Do-K), * represents a bonding site.

如請求項1所記載之化合物，其具有前述供體性單元及前述受體性單元合計2個或3個。The compound according to claim 1, which has two or three total of the aforementioned donating unit and the aforementioned accepting unit.

如請求項1所記載之化合物，其中於前述供體性單元上連結有2個前述受體性單元。The compound as described in Claim 1, wherein two of the above-mentioned acceptor units are linked to the above-mentioned donor unit.

一種有機半導體材料，包含如請求項1所記載之化合物。An organic semiconductor material, comprising the compound as described in claim 1.

一種有機電子器件，包含如請求項9所記載之有機半導體材料。An organic electronic device, comprising the organic semiconductor material as described in claim 9.