JP2024027112A - Organic semiconducting polymers and organic optoelectronic devices containing them - Google Patents

Abstract

An object of the present invention is to provide an organic semiconductor polymer and the like having a good absorption wavelength range and optical response performance. [Solution] An organic semiconductor polymer represented by the following formula. TIFF2024027112000069.tif15170X and Y are repeating units represented by formula I and formula II, respectively, A1 group and A2 group are electron-withdrawing groups, and D1 group and D2 group are electron-donating groups. TIFF2024027112000070.tif12170TIFF2024027112000071.tif13170A2 groups do not include the following. TIFF2024027112000072.tif44170 [Selection diagram] Figure 1A

Description

The present invention relates to semiconducting polymers and organic optoelectronic devices containing the same, and in particular to organic semiconducting polymers with good physical and chemical properties and organic optoelectronic devices containing the same. Organic semiconducting polymers can be processed by environmentally friendly organic solvents, are convenient to produce and have less environmental impact, and organic optoelectronic components containing them have excellent response in the infrared region.

In recent years, demand for organic semiconductor compounds has increased in order to manufacture more common electronic devices at lower costs. Compared to traditional semiconductor materials, organic semiconductor compounds have broader absorption bands, higher absorption coefficients, and tunable structures. Its absorption range, energy gap and solubility can also be adjusted according to the user's requirements. Additionally, organic materials have advantages in cost, flexibility, lower toxicity, and large area manufacturing. Organic optoelectronic materials have good competitiveness in various applications. Applications include components and assemblies of organic field effect transistors (OFETs), organic light emitting diodes (OLEDs), organic photodetectors (OPDs), organic photovoltaic (OPV) cells, transducers, memory components and logic circuits. included. In the components or assemblies for the above applications, the organic semiconductor material is in the form of a thin film with a thickness in the range of 50 nm to 1 μm.

In recent years, organic photodetectors (OPDs) are one of the new and developing fields in organic optoelectronics in detecting light with different wavelengths in the environment. It can be applied to medical care, health care, intelligent drives, drones or digital home. There are different material needs depending on the corresponding application. Additionally, the use of organic materials makes the device flexible. Under developments in materials science, OPDs can operate as thin films with specific wavelength responsiveness. Commercially available products have different operating needs with respect to various materials with corresponding wavelengths. Organic materials have good flexibility to meet different requirements for each application, while structural changes allow the optical absorption range of organic materials to be tuned. Specific wavelength absorption of organic materials is effective in reducing noise. The high attenuation coefficient of organic materials also improves responsiveness. Detectability is a figure of merit for evaluating the quality of a photodetector. Good detectability is closely related to high responsivity and low dark current.

Furthermore, the response range of OPD has been gradually red-shifted from UV-VIS to near-infrared (NIR) in recent years. NIR light is characterized by low dispersion and high transmittance, and has been applied as intelligent drives, drones, and night vision devices. OPD with detection above wavelength 1300 nm has attracted great attention due to long-range detection, low optical loss, and better transmission, which is actively used in optical communications.

In OPD, the material of the active layer (ATL), which directly addresses the performance, plays an important role in the device. These substances are divided into donors and acceptors. Donors can be organic polymers, oligomers, or small molecules with limited molecular weight. Here, DA type conjugated polymer is one of the most common donor materials. The energy levels and energy gaps of D-A type polymers are controllable due to the interaction between electron-rich (D) and electron-deficient (A) units in the polymer and the resulting push-pull electron effects. It is. Acceptors used in ATL include fullerene derivatives, graphene, metal oxides, quantum dots, and the like, which have absorption between 400 and 600 nm. Regarding recent market needs, the demand for NIR materials is increasing. In particular, conjugated polymers with longer wavelength absorption and good responsivity are the most viable donor materials. To be practical above 1300 nm, the optical bandgap (E _g ^opt ) of a material must be less than 0.9 eV. Furthermore, in the operation of the OPD, a bias voltage is applied. However, currently available organic polymers as donor materials suffer from high dark currents under biases above −2 V, which is detrimental to optoelectronic applications.

Due to national environmental regulations and the need for good processability, materials that can be processed with environmentally friendly solvents are essential and beneficial for wet processes. In particular, the use of halogenated organic solvents in solution processes should be avoided. In conclusion, there is a need for new organic semiconducting polymers. It should have a better absorption range in the infrared region. Devices based on organic semiconducting polymers should be operable and durable under bias voltage. Additionally, device fabrication should be processed in non-halogenated organic solvents.

According to the drawbacks of the available materials mentioned above, the main object of the present invention is to provide an organic semiconducting polymer, which is a p-type semiconducting polymer, capable of overcoming the drawbacks of conventional materials, and having at least the above-mentioned characteristics. The goal is to provide one. It can be synthesized in mass production. It has a photoresponse at wavelengths above 1300 nm. The polymers exhibit good processability and solubility in environmentally friendly solvents during device fabrication, which is beneficial for solution processing in large-scale manufacturing.

Another object of the invention is that optoelectronic devices comprising the organic semiconducting polymers of the invention provide optical responsivity at wavelengths of 1300 nm and above and excellent external quantum efficiency.

式中、Ｘは、式Ｉで表される第１の繰返し単位であり；

Ｙは、式ＩＩで表される第２の繰返し単位であり；

Ａ^１基およびＡ^２基は、互いに独立した電子吸引基であり、前記Ａ^１基は前記Ａ^２基とは異なり、前記Ａ^２基は、

を含まず；
Ｄ^１基およびＤ^２基は、互いに独立した電子供与基であり；
ｓｐ^１～ｓｐ^４は、非置換アリーレン基、置換アリーレン基、非置換ヘテロアリーレン基、および置換ヘテロアリーレン基からなる群から独立して選択され；
ａおよびｂは実数であり、０＜ａ＜１、０＜ｂ＜１、ａ＋ｂ＝１であり；
ｃ、ｄ、ｅ、およびｆは、それぞれ、０～５から選択される整数であり、互いに独立しており；ならびに
前記第１の繰返し単位Ｘの吸収波長は１０００ｎｍより長く、前記第２の繰返し単位Ｙの吸収波長は１０００ｎｍ未満である。 In order to achieve the above object, the organic semiconductor polymer according to the present invention is represented by the following formula:

where X is the first repeating unit of formula I;

Y is a second repeating unit represented by formula II;

A ¹ group and A ² group are mutually independent electron-withdrawing groups, the A ¹ group is different from the A ² group, and the A ² group is

Does not include;
D ¹ and D ² groups are mutually independent electron donating groups;
sp ¹ -sp ⁴ are independently selected from the group consisting of unsubstituted arylene groups, substituted arylene groups, unsubstituted heteroarylene groups, and substituted heteroarylene groups;
a and b are real numbers, 0<a<1, 0<b<1, a+b=1;
c, d, e, and f are each an integer selected from 0 to 5 and are independent of each other; and the absorption wavelength of the first repeating unit X is longer than 1000 nm, and the absorption wavelength of the second repeating unit The absorption wavelength of unit Y is less than 1000 nm.

To achieve the above object, an organic optoelectronic device according to the present invention includes a substrate, a first electrode disposed on the substrate, and an organic semiconductor polymer disposed on the first electrode. and a second electrode disposed on the active layer. At least one of the two electrodes, the first electrode and the second electrode, is transparent or translucent.

1 is a schematic diagram illustrating the structure of an embodiment of an organic optoelectronic device according to the present invention; FIG. 1 is a schematic diagram illustrating the structure of an embodiment of an organic optoelectronic device according to the present invention; FIG. 1 is a schematic diagram illustrating the structure of an embodiment of an organic optoelectronic device according to the present invention; FIG. 1 is a schematic diagram illustrating the structure of an embodiment of an organic optoelectronic device according to the present invention; FIG. 1 is a schematic diagram illustrating the structure of an embodiment of an organic optoelectronic device according to the present invention; FIG. 1 is a schematic diagram illustrating the structure of an embodiment of an organic optoelectronic device according to the present invention; FIG. 1 is a graph showing light absorption characteristics of an organic semiconductor polymer according to the present invention. 1 is a graph showing light absorption characteristics of an organic semiconductor polymer according to the present invention. 1 is a graph showing test results of an embodiment of an organic optoelectronic device according to the present invention. 1 is a graph showing test results of an embodiment of an organic optoelectronic device according to the present invention. 1 is a graph showing test results of an embodiment of an organic optoelectronic device according to the present invention.

[Detailed description of the invention]
The organic semiconductor polymer according to the present invention is a random copolymer synthesized by copolymerization of a donor unit and two acceptor units having different electron-withdrawing abilities. Organic semiconducting polymers with expected energy gaps, energy levels, and solubility can be obtained by modifying the structure of acceptors in the polymer.

The term "random copolymer" in the present invention is to be understood as a copolymer comprising two or more repeating units, said two or more repeating units appearing in the copolymer in a random order.

The term "donor" in the present invention is to be understood as an electron donor, which is a chemical entity that donates electrons to another compound or group of atoms in a compound. The term "acceptor" is to be understood as an electron acceptor, a chemical entity that accepts electrons transferred to it from another compound or group of atoms in a compound.

The organic semiconductor polymer according to the present invention has the following characteristics.

1. Organic semiconducting polymers are formed by polymerization of a donor unit and two acceptor units with different electron-withdrawing capacities, forming a first repeat unit and a second repeat unit, respectively. The first repeating unit and the second repeating unit each have an absorption maximum wavelength greater than 1000 nm and an absorption maximum wavelength less than 1000 nm.

2. The optical bandgap of the organic semiconductor polymer is less than 0.9 eV, and the organic semiconductor polymer has an optical response at a wavelength of 1300 nm or more.

3. Organic semiconducting polymers have lower LUMOs and are compatible with fullerene-based and non-fullerene-based materials.

4. The energy level of organic semiconducting polymers can be effectively adjusted by changing the second repeat unit. This shows great potential for use in combination with different n-type non-fullerene materials.

5. High dark current and low detection performance are the main challenges for materials with E _g ^opt less than 0.9 eV in OPD. The second repeating unit in the present invention can effectively suppress dark current and improve detectability.

6. Organic semiconducting polymers are practical in wet processes using environmentally friendly non-halogenated solvents.

The organic semiconducting polymer according to the invention can be prepared by a person skilled in the art using methods already described in known literature. The preparation of organic semiconducting polymers is further described in the embodiments below.

式中、Ｘは、式Ｉで表される第１の繰返し単位であり；

Ｙは、式ＩＩで表される第２の繰返し単位であり；

Ａ^１基およびＡ^２基は電子吸引基であり、前記Ａ^１基は前記Ａ^２基とは異なり、前記Ａ^２基は、

を含まず；
Ｄ^１基およびＤ^２基は、互いに独立した電子供与基であり；
ｓｐ^１～ｓｐ^４は、非置換アリーレン基、置換アリーレン基、非置換ヘテロアリーレン基、および置換ヘテロアリーレン基からなる群から独立して選択され；
ａおよびｂは実数であり、０＜ａ＜１、０＜ｂ＜１、ａ＋ｂ＝１であり；
ｃ、ｄ、ｅ、およびｆは、それぞれ、０～５から選択される整数であり、互いに独立しており；ならびに
前記第１の繰返し単位Ｘの吸収波長は１０００ｎｍより長く、前記第２の繰返し単位Ｙの吸収波長は１０００ｎｍ未満である。 The organic semiconductor polymer according to the present invention is represented by the following formula:

where X is the first repeating unit of formula I;

Y is a second repeating unit of formula II;

A ¹ group and A ² group are electron-withdrawing groups, the A ¹ group is different from the A ² group, and the A ² group is

Does not include;
D ¹ and D ² groups are mutually independent electron-donating groups;
sp ¹ -sp ⁴ are independently selected from the group consisting of unsubstituted arylene groups, substituted arylene groups, unsubstituted heteroarylene groups, and substituted heteroarylene groups;
a and b are real numbers, 0<a<1, 0<b<1, a+b=1;
c, d, e, and f are each an integer selected from 0 to 5 and are independent of each other; and the absorption wavelength of the first repeating unit X is longer than 1000 nm, and the absorption wavelength of the second repeating unit The absorption wavelength of unit Y is less than 1000 nm.

An asterisk (*) in a polymer or repeating unit mentioned in the context of the present invention is to be understood as a chemical bond between the polymer backbone and the neighboring unit or end group.

The term "repeat unit" used in the context of the present invention is to be understood as a constituent repeat unit (CRU) of a compound. A CRU is the smallest building block of a compound. Repeating CRUs form regular macromolecules, regular oligomeric molecules, regular blocks or regular chains. The term "unit" is to be understood as a building block that can be used as a repeating unit or in combination with other units to form a CRU.

式中、Ｒ^１～Ｒ^４は、水素原子、ハロゲン、シアノ基、Ｃ１～Ｃ３０直鎖アルキル基、Ｃ３～Ｃ３０分岐アルキル基、Ｃ１～Ｃ３０シリル基、Ｃ２～Ｃ３０エステル基、Ｃ１～Ｃ３０アルコキシ基、Ｃ１～Ｃ３０チオアルキル基、Ｃ１～Ｃ３０ハロアルキル基、Ｃ２～Ｃ３０アルケン基、Ｃ２～Ｃ３０アルキン基、Ｃ２～Ｃ３０シアン基含有炭化水素基、Ｃ１～Ｃ３０ニトロ基含有炭化水素基、Ｃ１～Ｃ３０ヒドロキシ基含有炭化水素基、Ｃ３～Ｃ３０ケト基含有炭化水素基、およびＣ５～Ｃ２０環式炭化水素基、Ｃ５～Ｃ２０ヘテロ環式炭化水素基、Ｃ５～Ｃ２０アリール基、およびＣ５～Ｃ２０ヘテロアリール基からなる群から独立して選択され、前記環式炭化水素基、前記ヘテロ環式炭化水素基、前記アリール基、および前記ヘテロアリール基は、非置換であるかもしくはＲ^５～Ｒ^９のうちの少なくとも１つで置換されており、且つ単環式、多環式、または縮合環であり；ならびに
Ｒ^５～Ｒ^９は、水素原子、ハロゲン、シアノ基、Ｃ１～Ｃ３０直鎖アルキル基、Ｃ３～Ｃ３０分岐アルキル基、Ｃ１～Ｃ３０シリル基、Ｃ２～Ｃ３０エステル基、Ｃ１～Ｃ３０アルコキシ基、Ｃ１～Ｃ３０チオアルキル基、Ｃ１～Ｃ３０ハロアルキル基、Ｃ２～Ｃ３０アルケン基、Ｃ２～Ｃ３０アルキン基、Ｃ２～Ｃ３０シアノ基含有炭化水素基、Ｃ１～Ｃ３０ニトロ基含有炭化水素基、Ｃ１～Ｃ３０ヒドロキシ基含有炭化水素基、およびＣ３～Ｃ３０ケト基含有炭化水素基からなる群から独立して選択される。 In a preferred embodiment, the D ¹ and D ² groups of the organic semiconducting polymer are independently selected from the group consisting of:

In the formula, R ¹ to R ⁴ are a hydrogen atom, a halogen, a cyano group, a C1 to C30 straight chain alkyl group, a C3 to C30 branched alkyl group, a C1 to C30 silyl group, a C2 to C30 ester group, a C1 to C30 alkoxy group , C1-C30 thioalkyl group, C1-C30 haloalkyl group, C2-C30 alkene group, C2-C30 alkyne group, C2-C30 cyan group-containing hydrocarbon group, C1-C30 nitro group-containing hydrocarbon group, C1-C30 hydroxy group consisting of a containing hydrocarbon group, a C3-C30 keto group-containing hydrocarbon group, a C5-C20 cyclic hydrocarbon group, a C5-C20 heterocyclic hydrocarbon group, a C5-C20 aryl group, and a C5-C20 heteroaryl group. independently selected from the group, said cyclic hydrocarbon group, said heterocyclic hydrocarbon group, said aryl group, and said heteroaryl group are unsubstituted or at least one of R ⁵ -R ⁹ and is monocyclic, polycyclic, or fused ring; and R ⁵ to R ⁹ are a hydrogen atom, a halogen, a cyano group, a C1 to C30 straight chain alkyl group, a C3 to C30 branched Alkyl group, C1-C30 silyl group, C2-C30 ester group, C1-C30 alkoxy group, C1-C30 thioalkyl group, C1-C30 haloalkyl group, C2-C30 alkene group, C2-C30 alkyne group, C2-C30 cyano group independently selected from the group consisting of C1-C30 nitro-containing hydrocarbon groups, C1-C30 hydroxy-containing hydrocarbon groups, and C3-C30 keto-containing hydrocarbon groups.

The term "hydrocarbon radical" used in the context of the present invention is to be understood as an organic radical containing carbon and hydrogen, including alkyl, alkene, alkyne and aromatic hydrocarbon radicals.

The term "heteroatom" as used in the context of the present invention means boron (B), nitrogen (N), oxygen (O), sulfur (S), phosphorus (P), silicon (Si), selenium (Se), It is to be understood as any atom that is not hydrogen (H) or carbon (C) in organic compounds, such as arsenic (As), tellurium (Te), and germanium (Ge).

式中、Ｘは、酸素（Ｏ）、硫黄（Ｓ）、またはセレン（Ｓｅ）から選択され；
Ｒ^１０およびＲ^１１は、水素原子、Ｃ１～Ｃ３０直鎖アルキル基、Ｃ３～Ｃ３０分岐アルキル基、Ｃ１～Ｃ３０シリル基、Ｃ２～Ｃ３０エステル基、Ｃ１～Ｃ３０アルコキシ基、Ｃ１～Ｃ３０チオアルキル基、Ｃ１～Ｃ３０ハロアルキル基、Ｃ２～Ｃ３０アルケン基、Ｃ２～Ｃ３０アルキン基、Ｃ２～Ｃ３０シアノ基含有炭化水素基、Ｃ１～Ｃ３０ニトロ基含有炭化水素基、Ｃ１～Ｃ３０ヒドロキシ基含有炭化水素基、Ｃ３～Ｃ３０ケト基含有炭化水素基、およびＣ５～Ｃ２０環式炭化水素基、Ｃ５～Ｃ２０ヘテロ環式炭化水素基、Ｃ５～Ｃ２０アリール基、およびＣ５～Ｃ２０ヘテロアリール基からなる群から独立して選択され、前記環式炭化水素基、前記ヘテロ環式炭化水素基、前記アリール基、および前記ヘテロアリール基は、非置換であるかもしくはＲ^１３～Ｒ^１７のうちの少なくとも１つで置換されており、且つ単環式、多環式、または縮合環であり；ならびにＲ^１３～Ｒ^１７は、水素原子、ハロゲン、シアノ基、Ｃ１～Ｃ３０直鎖アルキル基、Ｃ３～Ｃ３０分岐アルキル基、Ｃ１～Ｃ３０シリル基、Ｃ２～Ｃ３０エステル基、Ｃ１～Ｃ３０アルコキシ基、Ｃ１～Ｃ３０チオアルキル基、Ｃ１～Ｃ３０ハロアルキル基、Ｃ２～Ｃ３０アルケン基、Ｃ２～Ｃ３０アルキン基、Ｃ２～Ｃ３０シアノ基含有炭化水素基、Ｃ１～Ｃ３０ニトロ基含有炭化水素基、Ｃ１～Ｃ３０ヒドロキシ基含有炭化水素基、およびＣ３～Ｃ３０ケト基含有炭化水素基からなる群から独立して選択される。 In a preferred embodiment, the A ¹ group of the organic semiconducting polymer is selected from the group consisting of:

where X is selected from oxygen (O), sulfur (S), or selenium (Se);
R ¹⁰ and R ¹¹ are hydrogen atom, C1 to C30 straight chain alkyl group, C3 to C30 branched alkyl group, C1 to C30 silyl group, C2 to C30 ester group, C1 to C30 alkoxy group, C1 to C30 thioalkyl group, C1 ~C30 haloalkyl group, C2-C30 alkene group, C2-C30 alkyne group, C2-C30 cyano group-containing hydrocarbon group, C1-C30 nitro group-containing hydrocarbon group, C1-C30 hydroxy group-containing hydrocarbon group, C3-C30 independently selected from the group consisting of a keto group-containing hydrocarbon group, and a C5-C20 cyclic hydrocarbon group, a C5-C20 heterocyclic hydrocarbon group, a C5-C20 aryl group, and a C5-C20 heteroaryl group; The cyclic hydrocarbon group, the heterocyclic hydrocarbon group, the aryl group, and the heteroaryl group are unsubstituted or substituted with at least one of R ¹³ to R ¹⁷ , and is a monocyclic, polycyclic, or fused ring; and R ¹³ to R ¹⁷ are a hydrogen atom, a halogen, a cyano group, a C1 to C30 straight chain alkyl group, a C3 to C30 branched alkyl group, a C1 to C30 silyl group , C2-C30 ester group, C1-C30 alkoxy group, C1-C30 thioalkyl group, C1-C30 haloalkyl group, C2-C30 alkene group, C2-C30 alkyne group, C2-C30 cyano group-containing hydrocarbon group, C1-C30 independently selected from the group consisting of nitro group-containing hydrocarbon groups, C1-C30 hydroxy group-containing hydrocarbon groups, and C3-C30 keto group-containing hydrocarbon groups.

式中、Ｘは、酸素（Ｏ）、硫黄（Ｓ）、またはセレン（Ｓｅ）から選択され；
Ｒ^１８およびＲ^１９は、水素原子、ハロゲン、シアノ基、Ｃ１～Ｃ３０直鎖アルキル基、Ｃ３～Ｃ３０分岐アルキル基、Ｃ１～Ｃ３０シリル基、Ｃ２～Ｃ３０エステル基、Ｃ１～Ｃ３０アルコキシ基、Ｃ１～Ｃ３０チオアルキル基、Ｃ１～Ｃ３０ハロアルキル基、Ｃ２～Ｃ３０アルケン基、Ｃ２～Ｃ３０アルキン基、Ｃ２～Ｃ３０シアノ基含有炭化水素基、Ｃ１～Ｃ３０ニトロ基含有炭化水素基、Ｃ１～Ｃ３０ヒドロキシ基含有炭化水素基、およびＣ３～Ｃ３０ケト基含有炭化水素基からなる群から独立して選択され；
Ｒ^２０およびＲ^２１は、水素原子、ハロゲン、シアノ基、Ｃ１～Ｃ３０直鎖アルキル基、Ｃ３～Ｃ３０分岐アルキル基、Ｃ１～Ｃ３０シリル基、Ｃ２～Ｃ３０エステル基、Ｃ１～Ｃ３０アルコキシ基、Ｃ１～Ｃ３０チオアルキル基、Ｃ１～Ｃ３０ハロアルキル基、Ｃ２～Ｃ３０アルケン基、Ｃ２～Ｃ３０アルキン基、Ｃ２～Ｃ３０シアノ基含有炭化水素基、Ｃ１～Ｃ３０ニトロ基含有炭化水素基、Ｃ１～Ｃ３０ヒドロキシ基含有炭化水素基、Ｃ３～Ｃ３０ケト基含有炭化水素基、およびＣ５～Ｃ２０環式炭化水素基、Ｃ５～Ｃ２０ヘテロ環式炭化水素基、Ｃ５～Ｃ２０アリール基、およびＣ５～Ｃ２０ヘテロアリール基からなる群から独立して選択され、前記環式炭化水素基、前記ヘテロ環式炭化水素基、前記アリール基、および前記ヘテロアリール基は、非置換であるかもしくはＲ^２２～Ｒ^２６のうちの少なくとも１つで置換されており、且つ単環式、多環式、または縮合環であり；ならびに
Ｒ^２２～Ｒ^２６は、水素原子、ハロゲン、シアノ基、Ｃ１～Ｃ３０直鎖アルキル基、Ｃ３～Ｃ３０分岐アルキル基、Ｃ１～Ｃ３０シリル基、Ｃ２～Ｃ３０エステル基、Ｃ１～Ｃ３０アルコキシ基、Ｃ１～Ｃ３０チオアルキル基、Ｃ１～Ｃ３０ハロアルキル基、Ｃ２～Ｃ３０アルケン基、Ｃ２～Ｃ３０アルキン基、Ｃ２～Ｃ３０シアノ基含有炭化水素基、Ｃ１～Ｃ３０ニトロ基含有炭化水素基、Ｃ１～Ｃ３０ヒドロキシ基含有炭化水素基、およびＣ３～Ｃ３０ケト基含有炭化水素基からなる群から独立して選択される。 In a preferred embodiment, the A ² group is selected from the group consisting of:

where X is selected from oxygen (O), sulfur (S), or selenium (Se);
R ¹⁸ and R ¹⁹ are hydrogen atom, halogen, cyano group, C1 to C30 straight chain alkyl group, C3 to C30 branched alkyl group, C1 to C30 silyl group, C2 to C30 ester group, C1 to C30 alkoxy group, C1 to C30 thioalkyl group, C1-C30 haloalkyl group, C2-C30 alkene group, C2-C30 alkyne group, C2-C30 cyano group-containing hydrocarbon group, C1-C30 nitro group-containing hydrocarbon group, C1-C30 hydroxy group-containing hydrocarbon group independently selected from the group consisting of C3-C30 keto group-containing hydrocarbon groups;
R ²⁰ and R ²¹ are hydrogen atom, halogen, cyano group, C1 to C30 straight chain alkyl group, C3 to C30 branched alkyl group, C1 to C30 silyl group, C2 to C30 ester group, C1 to C30 alkoxy group, C1 to C30 thioalkyl group, C1-C30 haloalkyl group, C2-C30 alkene group, C2-C30 alkyne group, C2-C30 cyano group-containing hydrocarbon group, C1-C30 nitro group-containing hydrocarbon group, C1-C30 hydroxy group-containing hydrocarbon group C3-C30 keto group-containing hydrocarbon groups, and independent from the group consisting of C5-C20 cyclic hydrocarbon groups, C5-C20 heterocyclic hydrocarbon groups, C5-C20 aryl groups, and C5-C20 heteroaryl groups and the cyclic hydrocarbon group, the heterocyclic hydrocarbon group, the aryl group, and the heteroaryl group are unsubstituted or substituted with at least one of R ²² to R ²⁶ and is monocyclic, polycyclic, or fused ring; and R ²² to R ²⁶ are hydrogen atoms, halogens, cyano groups, C1 to C30 straight chain alkyl groups, C3 to C30 branched alkyl groups, C1-C30 silyl group, C2-C30 ester group, C1-C30 alkoxy group, C1-C30 thioalkyl group, C1-C30 haloalkyl group, C2-C30 alkene group, C2-C30 alkyne group, C2-C30 cyano group-containing hydrocarbon C1-C30 nitro-containing hydrocarbon groups, C1-C30 hydroxy-containing hydrocarbon groups, and C3-C30 keto-containing hydrocarbon groups.

式中、Ｘは、酸素（Ｏ）、硫黄（Ｓ）、またはセレン（Ｓｅ）から選択され；
Ｒ^２７～^２８は、水素原子、ハロゲン、シアノ基、Ｃ１～Ｃ３０直鎖アルキル基、Ｃ３～Ｃ３０分岐アルキル基、Ｃ１～Ｃ３０シリル基、Ｃ２～Ｃ３０エステル基、Ｃ１～Ｃ３０アルコキシ基、Ｃ１～Ｃ３０チオアルキル基、Ｃ１～Ｃ３０ハロアルキル基、Ｃ２～Ｃ３０アルケン基、Ｃ２～Ｃ３０アルキン基、Ｃ２～Ｃ３０シアノ基含有炭化水素基、Ｃ１～Ｃ３０ニトロ基含有炭化水素基、Ｃ１～Ｃ３０ヒドロキシ基含有炭化水素基、およびＣ３～Ｃ３０ケト基含有炭化水素基からなる群から独立して選択される。 In a preferred embodiment, sp ¹ -sp ⁴ are independently selected from the group consisting of:

where X is selected from oxygen (O), sulfur (S), or selenium (Se);
R ²⁷ to ²⁸ are a hydrogen atom, halogen, cyano group, C1 to C30 straight chain alkyl group, C3 to C30 branched alkyl group, C1 to C30 silyl group, C2 to C30 ester group, C1 to C30 alkoxy group, C1 to C30 Thioalkyl group, C1-C30 haloalkyl group, C2-C30 alkene group, C2-C30 alkyne group, C2-C30 cyano group-containing hydrocarbon group, C1-C30 nitro group-containing hydrocarbon group, C1-C30 hydroxy group-containing hydrocarbon group , and C3-C30 keto group-containing hydrocarbon groups.

In the following embodiments, a method for synthesizing an organic semiconductor polymer according to the present invention is provided.

２５０ｍＬの三つ口丸ビン中で、Ｃ１（２０．０ｇ、１６９ｍｍｏｌ）を１００ｍＬの無水テトラヒドロフラン（ＴＨＦ）に溶解し、窒素下で１５℃に冷却した。ｎ－ブチルリチウム（ヘキサン中２．５Ｍ）（４５．０ｍＬ、１１３ｍｍｏｌ）を溶液中にゆっくりと滴下した。溶液を１時間撹拌した。次いで、Ｃ３（３９．８ｇ、１１３ｍｍｏｌ）を、１５℃で、溶液中に滴下した。反応物を室温まで温め、２０時間撹拌した。その後、５０ｍＬの水を添加して反応を停止させ、有機溶媒を回転濃縮して除去した。ヘプタンを添加し、有機層を水で３回洗浄した。有機層をＭｇＳＯ_４で乾燥させ、回転濃縮によって溶媒を除去して、粗生成物（約６０ｇ）を得た。真空蒸留（０．２５ｔｏｒｒ、１７０～２００℃）を利用して、粗生成物中の出発物質および不純物を除去した。残留物を回収し、溶離剤としてヘプタンを用いてフラッシュシリカゲルカラムによって精製した。化合物Ｃ５を黄色油状物として得た（１６ｇ、収率４１．３％）。¹H NMR (500 MHz, CDCl₃): δ 7.09 (d, J = 6.5 Hz, 1H), 6.85 (d, J = 6.5 Hz, 1H), 2.72 (d, J = 7.0 Hz, 2H), 1.68 (m, 1H), 1.27 (m, 24H), 0.88 (m, 6H)。 Preparation of monomer C13

In a 250 mL three-necked round bottle, C1 (20.0 g, 169 mmol) was dissolved in 100 mL of anhydrous tetrahydrofuran (THF) and cooled to 15° C. under nitrogen. n-Butyllithium (2.5M in hexanes) (45.0 mL, 113 mmol) was slowly added dropwise into the solution. The solution was stirred for 1 hour. C3 (39.8 g, 113 mmol) was then added dropwise into the solution at 15°C. The reaction was allowed to warm to room temperature and stirred for 20 hours. Thereafter, 50 mL of water was added to stop the reaction, and the organic solvent was removed by rotary evaporation. Heptane was added and the organic layer was washed three times with water. The organic layer was dried with MgSO ₄ and the solvent was removed by rotary concentration to give the crude product (approximately 60 g). Vacuum distillation (0.25 torr, 170-200° C.) was used to remove starting materials and impurities in the crude product. The residue was collected and purified by flash silica gel column using heptane as eluent. Compound C5 was obtained as a yellow oil (16 g, yield 41.3%). ¹ H NMR (500 MHz, CDCl ₃ ): δ 7.09 (d, J = 6.5 Hz, 1H), 6.85 (d, J = 6.5 Hz, 1H), 2.72 (d, J = 7.0 Hz, 2H), 1.68 ( m, 1H), 1.27 (m, 24H), 0.88 (m, 6H).

５００ｍＬの三つ口丸ビン中で、Ｃ５（２１．２ｇ、６１．８ｍｍｏｌ）を１６０ｍＬの無水ＴＨＦに溶解し、アルゴン下で１０℃に冷却した。ｎ－ブチルリチウム（ヘキサン中２．５Ｍ）（２４．７ｍＬ、６１．８ｍｍｏｌ）を溶液中にゆっくりと滴下した。溶液を１時間撹拌した。臭化銅（Ｉ）（ＣｕＢｒ）（８．９ｇ、６１．８ｍｍｏｌ）、臭化リチウム（ＬｉＢｒ）（５．４ｇ、６１．８ｍｍｏｌ）、および１６０ｍＬの無水ＴＨＦを、アルゴン下で、第２の５００ｍＬの三つ口丸ビンに充填した。その後、第１の三つ口丸ビン中の溶液を、１０℃で、二重先端針を通して、第２の三つ口丸ビン中の混合物に添加した。混合物をさらに１時間撹拌した。次いで、二塩化オキサリル（３．６ｇ、２８．１ｍｍｏｌ）を、１０℃で、上述の混合物に添加した。反応物を室温まで温め、２０時間撹拌した。その後、水を添加して反応を停止させ、有機溶媒を回転濃縮して除去した。次いで、ヘプタンを添加し、有機層を水で３回洗浄した。有機層をＭｇＳＯ_４で乾燥させ、回転濃縮によって溶媒を除去して、粗生成物を得た。得られた粗生成物を、溶離剤としてヘプタン（Ｈｅｐ）／ジクロロメタン（ＤＣＭ）（ｖ／ｖ ９／１）を用いたシリカゲルカラムクロマトグラフィーで精製した。化合物Ｃ７を黄色油状物として得た（１６．３ｇ、収率８１．４％）。¹H NMR (500 MHz, CDCl₃): δ 7.88 (s, 2H), 2.80 (d, J = 7.0 Hz, 4H), 1.76 (m, 2H), 1.29 (m, 48H), 0.88 (m, 12H)。

In a 500 mL three-necked round bottle, C5 (21.2 g, 61.8 mmol) was dissolved in 160 mL of anhydrous THF and cooled to 10° C. under argon. n-Butyllithium (2.5M in hexanes) (24.7 mL, 61.8 mmol) was slowly added dropwise into the solution. The solution was stirred for 1 hour. Copper(I) bromide (CuBr) (8.9 g, 61.8 mmol), lithium bromide (LiBr) (5.4 g, 61.8 mmol), and 160 mL of anhydrous THF were combined in a second 500 mL under argon. It was filled into a three-necked round bottle. The solution in the first three-necked bottle was then added to the mixture in the second three-necked bottle through a double-tipped needle at 10°C. The mixture was stirred for an additional hour. Oxalyl dichloride (3.6 g, 28.1 mmol) was then added to the above mixture at 10°C. The reaction was allowed to warm to room temperature and stirred for 20 hours. Thereafter, water was added to stop the reaction, and the organic solvent was removed by rotary concentration. Heptane was then added and the organic layer was washed three times with water. The organic layer was dried with MgSO ₄ and the solvent was removed by rotary concentration to give the crude product. The obtained crude product was purified by silica gel column chromatography using heptane (Hep)/dichloromethane (DCM) (v/v 9/1) as eluent. Compound C7 was obtained as a yellow oil (16.3 g, yield 81.4%). ¹ H NMR (500 MHz, CDCl ₃ ): δ 7.88 (s, 2H), 2.80 (d, J = 7.0 Hz, 4H), 1.76 (m, 2H), 1.29 (m, 48H), 0.88 (m, 12H) ).

１００ｍＬの二つ口丸ビン中で、Ｃ８（２．０ｇ、５．２ｍｍｏｌ）および４０ｍＬの酢酸（ＡｃＯＨ）を混合し、室温で撹拌した。窒素下で、５．８ｇの鉄粉末を溶液に添加した。次いで、混合物を８０℃に加熱し、一晩撹拌した。反応が完了すると、混合物を室温に冷却した。次に、１５０ｍＬの氷水を混合物に注いで、反応を停止させた。不溶物をろ過し、水で洗浄し、カーキ色の固体として回収した。その後、カーキ色の固体を、１５０ｍＬのＴＨＦに溶解し、次いで、灰色の残留物をろ過によって除去した。ろ液を回収し、回転濃縮し、真空下で乾燥させた。化合物Ｃ９を褐色がかった緑色固体として得た（１．４４ｇ、収率８６％）。２５０ｍＬの一つ口丸ビン中で、Ｃ９（１．１当量、１．０３ｇ、３．２ｍｍｏｌ）、Ｃ７（１．０当量、２．１ｇ、２．９ｍｍｏｌ）および３０ｍＬの酢酸を混合した。混合物を、窒素下で１２０℃まで加熱し、窒素下で一晩撹拌した。その後、混合物を室温に冷却した。混合物を１００ｍＬの氷水に注いで、反応を停止させた。次いで、生成物をＤＣＭで３回抽出した。有機層を水で３回洗浄して、酢酸を除去した。有機溶媒をＭｇＳＯ_４で乾燥させ、回転濃縮によって溶媒を除去して、粗生成物を得た。得られた粗生成物を、溶離剤としてヘプタン／ＤＣＭ（ｖ／ｖ ４／１）を用いたシリカゲルカラムクロマトグラフィーで精製した。化合物Ｃ１０を赤色固体として得た（１．９８ｇ、収率６６．９％）。¹H NMR (500 MHz, CDCl₃): δ 7.45 (s, 2H), 2.83 (d, J = 7.0 Hz, 4H), 1.83 (m, 2H), 1.30 (m, 48H), 0.89 (m, 12H)。

C8 (2.0 g, 5.2 mmol) and 40 mL of acetic acid (AcOH) were mixed in a 100 mL two-necked round bottle and stirred at room temperature. Under nitrogen, 5.8 g of iron powder was added to the solution. The mixture was then heated to 80°C and stirred overnight. Once the reaction was completed, the mixture was cooled to room temperature. Next, 150 mL of ice water was poured into the mixture to stop the reaction. Insoluble matter was filtered, washed with water, and collected as a khaki solid. The khaki solid was then dissolved in 150 mL of THF and the gray residue was then removed by filtration. The filtrate was collected, rotary concentrated and dried under vacuum. Compound C9 was obtained as a brownish green solid (1.44 g, 86% yield). In a 250 mL single-necked round bottle, C9 (1.1 eq., 1.03 g, 3.2 mmol), C7 (1.0 eq., 2.1 g, 2.9 mmol) and 30 mL of acetic acid were mixed. The mixture was heated to 120° C. under nitrogen and stirred under nitrogen overnight. The mixture was then cooled to room temperature. The reaction was stopped by pouring the mixture into 100 mL of ice water. The product was then extracted three times with DCM. The organic layer was washed three times with water to remove acetic acid. The organic solvent was dried with MgSO ₄ and the solvent was removed by rotary concentration to obtain the crude product. The crude product obtained was purified by silica gel column chromatography using heptane/DCM (v/v 4/1) as eluent. Compound C10 was obtained as a red solid (1.98 g, yield 66.9%). ¹ H NMR (500 MHz, CDCl ₃ ): δ 7.45 (s, 2H), 2.83 (d, J = 7.0 Hz, 4H), 1.83 (m, 2H), 1.30 (m, 48H), 0.89 (m, 12H) ).

１００ｍＬの二つ口丸ビン中で、Ｃ１０（２．０ｇ、１．９５ｍｍｏｌ）およびＣ１１（１．６ｇ、４．２８ｍｍｏｌ）を４０ｍＬのＴＨＦに溶解した。溶液をアルゴンで１５分間パージした。次いで、Ｐｄ_２ｄｂａ_３（７１．２ｍｇ、０．０７７８ｍｍｏｌ）およびＰ（ｏ－ｔｏｌ）_３（９４．８ｍｇ、０．３１１３ｍｍｏｌ）を溶液に添加した。混合物を６６℃まで加熱し、２時間撹拌した。反応が終了すると、混合物を冷却し、セライトパッドを通してろ過し、パッドをヘプタンで洗浄した。その後、ろ液を回収し、回転濃縮した。得られた粗生成物を、溶離剤としてヘプタン／ＤＣＭ（ｖ／ｖ ５／１）を用いたシリカゲルカラムクロマトグラフィーで精製した。化合物Ｃ１２を暗褐色の固体として得た（１．８５ｇ、収率９１．９％）。¹H NMR (600 MHz, CDCl₃): δ 8.88 (d, J = 4.8 Hz, 2H), 7.71 (d, J = 4.8 Hz, 2H), 7.43 (s, 2H), 7.34 (t, J = 6.0 Hz, 2H), 2.85 (d, J = 8.4 Hz, 4H), 1.83 (m, 2H), 1.30 (m, 48H), 0.88 (m, 12H)。

In a 100 mL two-necked round bottle, C10 (2.0 g, 1.95 mmol) and C11 (1.6 g, 4.28 mmol) were dissolved in 40 mL of THF. The solution was purged with argon for 15 minutes. Pd ₂ dba ₃ (71.2 mg, 0.0778 mmol) and P(o-tol) ₃ (94.8 mg, 0.3113 mmol) were then added to the solution. The mixture was heated to 66°C and stirred for 2 hours. Once the reaction was complete, the mixture was cooled and filtered through a pad of Celite, and the pad was washed with heptane. The filtrate was then collected and rotary concentrated. The crude product obtained was purified by silica gel column chromatography using heptane/DCM (v/v 5/1) as eluent. Compound C12 was obtained as a dark brown solid (1.85 g, 91.9% yield). ¹ H NMR (600 MHz, CDCl ₃ ): δ 8.88 (d, J = 4.8 Hz, 2H), 7.71 (d, J = 4.8 Hz, 2H), 7.43 (s, 2H), 7.34 (t, J = 6.0 Hz, 2H), 2.85 (d, J = 8.4 Hz, 4H), 1.83 (m, 2H), 1.30 (m, 48H), 0.88 (m, 12H).

２５０ｍＬの一つ口丸ビン中で、Ｃ１２（１．８５ｇ、１．７８８ｍｍｏｌ）を５０ｍＬのＴＨＦに溶解した。次いで、Ｎ－ブロモスクシンイミド（ＮＢＳ）（６５３ｍｇ、３．６６６ｍｍｏｌ）を氷浴中の溶液に添加した。混合物を室温まで温め、２０時間撹拌した。反応が完了した後に、ヘプタンおよび水を添加して、生成物を抽出した。有機層を回収し、水で２回洗浄した。有機溶媒をＭｇＳＯ_４で乾燥させ、回転濃縮によって溶媒を除去して、粗生成物を得た。その後、得られた粗生成物を、溶離剤としてヘプタン／ＤＣＭ（ｖ／ｖ ９５／５）を用いたシリカゲルカラムクロマトグラフィーで精製した。化合物Ｃ１３を黒色の粘稠液として得た（１．９６ｇ、収率９２．１％）。¹H NMR (600 MHz, CDCl₃): δ 8.73 (d, J = 5.4 Hz, 2H), 7.38 (s, 2H), 7.21 (t, J = 4.8 Hz, 2H), 2.88 (d, J = 8.4 Hz, 4H), 1.87 (m, 2H), 1.29 (m, 48H), 0.85 (m, 12H)。

C12 (1.85 g, 1.788 mmol) was dissolved in 50 mL of THF in a 250 mL single-necked round bottle. N-bromosuccinimide (NBS) (653 mg, 3.666 mmol) was then added to the solution in the ice bath. The mixture was allowed to warm to room temperature and stirred for 20 hours. After the reaction was completed, heptane and water were added to extract the product. The organic layer was collected and washed twice with water. The organic solvent was dried with MgSO ₄ and the solvent was removed by rotary concentration to obtain the crude product. The crude product obtained was then purified by silica gel column chromatography using heptane/DCM (v/v 95/5) as eluent. Compound C13 was obtained as a black viscous liquid (1.96 g, yield 92.1%). ¹ H NMR (600 MHz, CDCl ₃ ): δ 8.73 (d, J = 5.4 Hz, 2H), 7.38 (s, 2H), 7.21 (t, J = 4.8 Hz, 2H), 2.88 (d, J = 8.4 Hz, 4H), 1.87 (m, 2H), 1.29 (m, 48H), 0.85 (m, 12H).

５００ｍＬの三つ口丸ビン中で、Ｃ１５（５．０ｇ、１３．７ｍｍｏｌ）を１５０ｍＬの無水ＴＨＦに溶解し、窒素下で－６０℃に冷却した。ｎ－ブチルリチウム（ヘキサン中２．５Ｍ）（５．７６ｍＬ、１４．４ｍｍｏｌ）を溶液中にゆっくりと滴下した。反応物を－６０℃で１時間撹拌した。その後、Ｃ１７（２．９ｇ、１４．４ｍｍｏｌ）を５ｍＬの無水ＴＨＦに溶解した。次いで、Ｃ１７溶液を、－６０℃でゆっくりとＣ１５リチオ化溶液中に滴下した。次いで、反応物を室温までゆっくりと温め、さらに２０時間撹拌した。その後、水を添加して反応を停止させ、有機溶媒を回転濃縮によって除去した。ヘプタンを添加し、有機層をブラインで３回洗浄した。有機溶剤をＭｇＳＯ_４で乾燥させた。生成物は、さらに精製することなく、真空下で有機溶媒を除去した後に得られた。化合物Ｃ１９を淡黄色液体として得た（１９６．７ｇ、収率９２．５％）。¹H NMR (600 MHz, CDCl₃) C19: δ 7.23 (s, 1H), 7.05 (s, 1H), 2.68 (m, 2H), 1.69 (m, 1H), 1.35 (m, 32H), 0.98 (m, 6H), and 0.44 (m, 9H)。 Preparation of monomer C30

In a 500 mL three-necked round bottle, C15 (5.0 g, 13.7 mmol) was dissolved in 150 mL of anhydrous THF and cooled to −60° C. under nitrogen. n-Butyllithium (2.5M in hexane) (5.76 mL, 14.4 mmol) was slowly added dropwise into the solution. The reaction was stirred at -60°C for 1 hour. C17 (2.9 g, 14.4 mmol) was then dissolved in 5 mL of anhydrous THF. The C17 solution was then slowly added dropwise into the C15 lithiation solution at -60°C. The reaction was then slowly warmed to room temperature and stirred for an additional 20 hours. The reaction was then quenched by the addition of water and the organic solvent was removed by rotary concentration. Heptane was added and the organic layer was washed three times with brine. The organic solvent was dried with _MgSO4 . The product was obtained after removing the organic solvent under vacuum without further purification. Compound C19 was obtained as a pale yellow liquid (196.7 g, yield 92.5%). ¹ H NMR (600 MHz, CDCl ₃ ) C19: δ 7.23 (s, 1H), 7.05 (s, 1H), 2.68 (m, 2H), 1.69 (m, 1H), 1.35 (m, 32H), 0.98 ( m, 6H), and 0.44 (m, 9H).

５００ｍＬの三つ口丸ビン中で、Ｃ２６（５ｇ、１５．２２ｍｍｏｌ）を７５ｍＬのエタノール（ＥｔＯＨ）および１２５ｍＬのＴＨＦの混合物に溶解し、氷浴中で冷却した。次いで、水素化ホウ素ナトリウム（ＮａＢＨ_４）（１１．５ｇ、３０４ｍｍｏｌ）を氷浴中で少しずつゆっくりと反応物に添加した。混合物を氷浴中でさらに３０分間撹拌し、次いで室温まで温め、１時間撹拌した。反応が完了した後に、混合物を吸引ろ過して、固体を除去した。ろ液を回収し、回転濃縮した。得られた粗生成物を酢酸エチル（ＥＡ）に溶解し、水で３回洗浄した。有機層を回収し、ＭｇＳＯ_４で水分を除去し、回転濃縮した。真空で溶媒を除去した後に、化合物Ｃ２７をさらに精製することなく白色固体として得た（４．５ｇ、収率９８％）。¹H NMR (500 MHz, CDCl₃) of the 化合物 C27: δ 7.12 (s, 1H), 4.11 (m, 2H), 3.83 (m, 2H)。

In a 500 mL three-necked round bottle, C26 (5 g, 15.22 mmol) was dissolved in a mixture of 75 mL ethanol (EtOH) and 125 mL THF and cooled in an ice bath. Sodium borohydride (NaBH ₄ ) (11.5 g, 304 mmol) was then slowly added to the reaction in portions in an ice bath. The mixture was stirred in the ice bath for a further 30 minutes, then warmed to room temperature and stirred for 1 hour. After the reaction was completed, the mixture was filtered with suction to remove solids. The filtrate was collected and rotary concentrated. The obtained crude product was dissolved in ethyl acetate (EA) and washed three times with water. The organic layer was collected, dried with MgSO ₄ and rotary concentrated. After removing the solvent in vacuo, compound C27 was obtained as a white solid without further purification (4.5 g, 98% yield). ^1H NMR (500 MHz, _CDCl3 ) of the compound C27: δ 7.12 (s, 1H), 4.11 (m, 2H), 3.83 (m, 2H).

２５０ｍＬ三つ口丸ビン中で、Ｃ２７（４．５ｇ、１４．９８ｍｍｏｌ）およびＳｅＯ_２（２ｇ、１７．９８ｍｍｏｌ）を１３５ｍＬエタノールと混合した。混合物を７５℃まで温め、２０時間撹拌した。反応が完了した後に、混合物を冷却した。生成物を氷浴中でゆっくりと沈殿させた。沈殿物、白色固体、を吸引ろ過によって回収し、エタノールで洗浄し、真空で溶媒を除去した。化合物Ｃ２８を白色固体として得た（４．９ｇ、収率８７％）。¹H NMR (500 MHz, CDCl₃): δ 7.89 (s, 1H)。

In a 250 mL three-necked round bottle, C27 (4.5 g, 14.98 mmol) and SeO ₂ (2 g, 17.98 mmol) were mixed with 135 mL ethanol. The mixture was warmed to 75°C and stirred for 20 hours. After the reaction was completed, the mixture was cooled. The product was slowly precipitated in an ice bath. The precipitate, a white solid, was collected by suction filtration, washed with ethanol and the solvent removed in vacuo. Compound C28 was obtained as a white solid (4.9 g, yield 87%). ^1H NMR (500 MHz, _CDCl3 ): δ 7.89 (s, 1H).

１００ｍＬの三つ口丸ビン中で、Ｃ２８（１．０ｇ、２．６６ｍｍｏｌ）およびＣ１９（３．１ｇ、５．８６ｍｍｏｌ）を３０ｍＬのＴＨＦに溶解した。溶液をアルゴンでパージした。次いで、Ｐｄ_２ｄｂａ_３（１９６ｍｇ、０．２１４ｍｍｏｌ）およびＰ（ｏ－ｔｏｌ）_３（２６０ｍｇ、０．８５２ｍｍｏｌ）をアルゴン下で溶液に添加した。混合物を６６℃まで加熱し、２４時間撹拌した。反応が終了すると、混合物をシリカゲルおよびセライトパッドを通してろ過し、パッドをＴＨＦで洗浄した。その後、ろ液を回収し、回転濃縮した。得られた粗生成物を、溶離剤としてヘプタン／ＤＣＭ（ｖ／ｖ ２／１）を用いたシリカゲルカラムクロマトグラフィーで精製した。化合物Ｃ２９を淡橙色固体として得た（０．５ｇ、収率１９％）。¹H NMR (500 MHz, CDCl₃): δ 7.86 (s, 1H), 7.84 (d, J = 1.0 Hz, 1H), 7.42 (d, J = 1.5 Hz, 1H), 7.13 (J = 1.0 Hz, 1H), 7.07 (d, J = 1.0 Hz, 1H), 2.63 (d, J = 7.5 Hz, 2H), 2.62 (d, J = 8.0 Hz, 2H), 1.67 (m, 2H), 1.31-1.25 (m, 64 Hz), 0.88-0.85 (m, 12 Hz)。

In a 100 mL three-necked round bottle, C28 (1.0 g, 2.66 mmol) and C19 (3.1 g, 5.86 mmol) were dissolved in 30 mL of THF. The solution was purged with argon. Pd ₂ dba ₃ (196 mg, 0.214 mmol) and P(o-tol) ₃ (260 mg, 0.852 mmol) were then added to the solution under argon. The mixture was heated to 66°C and stirred for 24 hours. Once the reaction was complete, the mixture was filtered through a pad of silica gel and Celite, and the pad was washed with THF. The filtrate was then collected and rotary concentrated. The crude product obtained was purified by silica gel column chromatography using heptane/DCM (v/v 2/1) as eluent. Compound C29 was obtained as a pale orange solid (0.5 g, 19% yield). ¹ H NMR (500 MHz, CDCl ₃ ): δ 7.86 (s, 1H), 7.84 (d, J = 1.0 Hz, 1H), 7.42 (d, J = 1.5 Hz, 1H), 7.13 (J = 1.0 Hz, 1H), 7.07 (d, J = 1.0 Hz, 1H), 2.63 (d, J = 7.5 Hz, 2H), 2.62 (d, J = 8.0 Hz, 2H), 1.67 (m, 2H), 1.31-1.25 ( m, 64 Hz), 0.88-0.85 (m, 12 Hz).

１００ｍＬの二つ口丸ビン中で、Ｃ２９（１．９ｇ、２．０２ｍｍｏｌ）を５７ｍＬのＴＨＦに溶解した。次いで、ＮＢＳ（８９７ｍｇ、５．０４ｍｍｏｌ）を室温で溶液に添加した。混合物を室温で２時間攪拌した。反応が完了した後に、生成物を水／ヘプタンで３回抽出した。有機層を回収し、水を除去し、回転濃縮した。その後、得られた粗生成物を、溶離剤としてヘプタン／ＤＣＭ（ｖ／ｖ ９／１）を用いたシリカゲルカラムクロマトグラフィーで精製した。化合物Ｃ３０を淡橙色固体として得た（１．７０ｇ、収率７７％）。¹H NMR (500 MHz, CDCl₃): δ 7.80 (s, 1H), 7.62 (s, 1H), 7.39 (s, 1H), 2.57 (d, J = 7.0 Hz, 2H), 2.56 (d, J = 6.5 Hz, 2H), 1.72 (m, 2H), 1.25 (m, 64H), 0.86 (m, 12H)。

C29 (1.9 g, 2.02 mmol) was dissolved in 57 mL of THF in a 100 mL two-necked round bottle. NBS (897 mg, 5.04 mmol) was then added to the solution at room temperature. The mixture was stirred at room temperature for 2 hours. After the reaction was completed, the product was extracted three times with water/heptane. The organic layer was collected, water removed and rotary concentrated. The obtained crude product was then purified by silica gel column chromatography using heptane/DCM (v/v 9/1) as eluent. Compound C30 was obtained as a pale orange solid (1.70 g, 77% yield). ¹ H NMR (500 MHz, CDCl ₃ ): δ 7.80 (s, 1H), 7.62 (s, 1H), 7.39 (s, 1H), 2.57 (d, J = 7.0 Hz, 2H), 2.56 (d, J = 6.5 Hz, 2H), 1.72 (m, 2H), 1.25 (m, 64H), 0.86 (m, 12H).

２５０ｍＬの三つ口丸ビン中で、Ｃ４０（３ｇ、９．０９ｍｍｏｌ）を４５ｍＬのＥｔＯＨおよび４５ｍＬのＴＨＦの混合物に溶解し、氷浴中で冷却した。次いで、ＮａＢＨ_４（６．９ｇ、１８２ｍｍｏｌ）を、氷浴中で、反応物に少しずつゆっくりと添加した。混合物を氷浴中でさらに３０分間撹拌し、次いで室温まで温め、１時間撹拌した。反応が完了した後に、混合物を吸引ろ過して固体を除去した。ろ液を回収し、回転濃縮して粗生成物を得た。得られた粗生成物を酢酸エチルに溶解し、水で３回洗浄した。有機層は、ＭｇＳＯ_４で水分を除去し、回転濃縮した。真空で溶媒を除去した後、化合物Ｃ４１をさらに精製することなく白色固体として得た（２．１ｇ、収率７６％）。 Preparation of monomer C44

In a 250 mL three-necked round bottle, C40 (3 g, 9.09 mmol) was dissolved in a mixture of 45 mL EtOH and 45 mL THF and cooled in an ice bath. NaBH ₄ (6.9 g, 182 mmol) was then slowly added to the reaction in portions in an ice bath. The mixture was stirred in the ice bath for an additional 30 minutes, then warmed to room temperature and stirred for 1 hour. After the reaction was completed, the mixture was filtered with suction to remove solids. The filtrate was collected and rotary concentrated to obtain the crude product. The obtained crude product was dissolved in ethyl acetate and washed three times with water. The organic layer was dried with MgSO ₄ and rotary concentrated. After removing the solvent in vacuo, compound C41 was obtained as a white solid without further purification (2.1 g, 76% yield).

２５０ｍＬの三つ口丸ビン中で、Ｃ１（２０．０ｇ、１６９ｍｍｏｌ）を１００ｍＬの無水テトラヒドロフラン（ＴＨＦ）に溶解し、窒素下で１５℃に冷却した。ｎ－ブチルリチウム（ヘキサン中２．５Ｍ）（４５．０ｍＬ、１１３ｍｍｏｌ）を溶液中にゆっくりと滴下した。溶液を１時間撹拌した。次いで、１５℃で、Ｃ２（３３．３ｇ、１１２ｍｍｏｌ）を溶液中に滴下した。反応物を室温まで温め、２０時間撹拌した。その後、水を加えて反応を停止させ、有機溶媒を回転濃縮によって除去した。ヘプタンを添加し、有機層を水で３回洗浄した。有機層をＭｇＳＯ_４で乾燥させ、回転濃縮によって溶媒を除去して粗生成物を得た。真空蒸留（０．２５ｔｏｒｒ、１５０℃）を利用して、粗生成物中の出発物質および不純物を除去した。残留物を回収し、溶離剤としてヘプタンを用いたフラッシュシリカゲルカラムによって精製した。化合物Ｃ４を淡黄色油状物として得た（１７．５ｇ、収率５４．３％）。

In a 250 mL three-necked round bottle, C1 (20.0 g, 169 mmol) was dissolved in 100 mL of anhydrous tetrahydrofuran (THF) and cooled to 15° C. under nitrogen. n-Butyllithium (2.5M in hexanes) (45.0 mL, 113 mmol) was slowly added dropwise into the solution. The solution was stirred for 1 hour. C2 (33.3 g, 112 mmol) was then added dropwise into the solution at 15°C. The reaction was allowed to warm to room temperature and stirred for 20 hours. The reaction was then quenched by adding water and the organic solvent was removed by rotary concentration. Heptane was added and the organic layer was washed three times with water. The organic layer was dried with MgSO ₄ and the solvent was removed by rotary concentration to obtain the crude product. Vacuum distillation (0.25 torr, 150° C.) was utilized to remove starting materials and impurities in the crude product. The residue was collected and purified by flash silica gel column using heptane as eluent. Compound C4 was obtained as a pale yellow oil (17.5 g, yield 54.3%).

５００ｍＬの三つ口丸ビン中で、Ｃ４（１７．４ｇ、６０．７ｍｍｏｌ）を１４０ｍＬの無水ＴＨＦに溶解し、アルゴン下で１０℃に冷却した。ｎ－ブチルリチウム（ヘキサン中２．５Ｍ）（２４．３ｍＬ、６０．７ｍｍｏｌ）を溶液中にゆっくりと滴下した。溶液を１時間撹拌した。臭化銅（Ｉ）（ＣｕＢｒ）（８．７ｇ、６０．７ｍｍｏｌ）、臭化リチウム（ＬｉＢｒ）（５．３ｇ、６０．７ｍｍｏｌ）、および１４０ｍＬの無水ＴＨＦを、アルゴン下で、第２の５００ｍＬの三つ口丸ビンに充填した。その後、第１の三つ口丸ビン中の溶液を、１０℃で、二重先端針を通して、第２の三つ口丸ビン中の混合物中に添加した。混合物をさらに１時間撹拌した。次いで、１０℃で、二塩化オキサリル（３．５ｇ、２７．６ｍｍｏｌ）を混合物中に添加した。反応物を室温まで温め、２０時間撹拌した。その後、水を添加して反応を停止させ、有機溶媒を回転濃縮によって除去した。ヘプタンを添加し、有機層を水で３回洗浄した。有機層をＭｇＳＯ_４で乾燥させ、回転濃縮によって溶媒を除去して、粗生成物を得た。得られた粗生成物を、溶離剤としてヘプタン／ＤＣＭ（ｖ／ｖ ９／１）を用いたシリカゲルカラムクロマトグラフィーで精製した。化合物Ｃ６を黄色油状物として得た（１３．３ｇ、収率７６．６％）。

In a 500 mL three-necked round bottle, C4 (17.4 g, 60.7 mmol) was dissolved in 140 mL of anhydrous THF and cooled to 10° C. under argon. n-Butyllithium (2.5M in hexane) (24.3 mL, 60.7 mmol) was slowly added dropwise into the solution. The solution was stirred for 1 hour. Copper(I) bromide (CuBr) (8.7 g, 60.7 mmol), lithium bromide (LiBr) (5.3 g, 60.7 mmol), and 140 mL of anhydrous THF were added to a second 500 mL under argon. It was filled into a three-necked round bottle. The solution in the first three-necked bottle was then added through a double-tipped needle into the mixture in the second three-necked bottle at 10°C. The mixture was stirred for an additional hour. Then, at 10° C., oxalyl dichloride (3.5 g, 27.6 mmol) was added into the mixture. The reaction was allowed to warm to room temperature and stirred for 20 hours. The reaction was then quenched by the addition of water and the organic solvent was removed by rotary concentration. Heptane was added and the organic layer was washed three times with water. The organic layer was dried with MgSO ₄ and the solvent was removed by rotary concentration to give the crude product. The crude product obtained was purified by silica gel column chromatography using heptane/DCM (v/v 9/1) as eluent. Compound C6 was obtained as a yellow oil (13.3 g, 76.6% yield).

２５０ｍＬ丸ビン中で、Ｃ４１（２．１ｇ、６．９６ｍｍｏｌ）、Ｃ６（４．６ｇ、７．６５ｍｍｏｌ）および６３ｍＬの酢酸を混合した。反応物を１２０℃まで加熱し、窒素下で１８時間撹拌した。反応が完了すると、混合物を室温に冷却し、次いで生成物をＤＣＭ／水で３回抽出した。有機層をＭｇＳＯ_４で乾燥させ、溶媒を回転濃縮によって除去した。得られた粗生成物を、溶離剤としてヘプタン／ＤＣＭ（ｖ／ｖ ２／１）を用いたシリカゲルカラムクロマトグラフィーで精製した。化合物Ｃ４２を赤色固体として得た（３．２ｇ、収率５１％）。¹H NMR (500 MHz, CDCl₃): δ 7.35 (m, 2H), 2.18 (d, J = 7.2 Hz, 4H), 1.78 (m, 2H), 1.36-1.28 (m, 32H), 0.91-0.86 (m, 12H)。

In a 250 mL round bottle, C41 (2.1 g, 6.96 mmol), C6 (4.6 g, 7.65 mmol) and 63 mL of acetic acid were mixed. The reaction was heated to 120° C. and stirred under nitrogen for 18 hours. Once the reaction was completed, the mixture was cooled to room temperature and then the product was extracted with DCM/water three times. The organic layer was dried with MgSO ₄ and the solvent was removed by rotary evaporation. The crude product obtained was purified by silica gel column chromatography using heptane/DCM (v/v 2/1) as eluent. Compound C42 was obtained as a red solid (3.2 g, 51% yield). ¹ H NMR (500 MHz, CDCl ₃ ): δ 7.35 (m, 2H), 2.18 (d, J = 7.2 Hz, 4H), 1.78 (m, 2H), 1.36-1.28 (m, 32H), 0.91-0.86 (m, 12H).

１００ｍＬの三つ口丸ビン中で、Ｃ４２（２．４ｇ、２．６７ｍｍｏｌ）およびＣ１１（２．５ｇ、６．７２ｍｍｏｌ）を７２ｍＬのＴＨＦに溶解した。溶液をアルゴンで３０分間パージした。次いで、Ｐｄ_２ｄｂａ_３（９８ｍｇ、０．１０７ｍｍｏｌ）およびＰ（ｏ－ｔｏｌ）_３（１３０ｍｇ、０．４２６ｍｍｏｌ）をアルゴン下で溶液に添加した。混合物を６６℃まで加熱し、２４時間撹拌した。反応が終了すると、混合物をシリカゲルおよびセライトパッドを通してろ過し、パッドをＴＨＦで洗浄した。その後、ろ液を回収し、回転濃縮によって溶媒を除去した。得られた粗生成物を、溶離剤としてヘプタン／トルエン（ｖ／ｖ ７／１）を用いたシリカゲルカラムクロマトグラフィーで精製した。化合物Ｃ４３を赤色油状物として得た（１．４ｇ、収率５８％）。¹H NMR (600 MHz, CDCl₃): δ 7.99 (d, J = 4.8 Hz, 2H), 7.65 (d, J = 6.6 Hz, 2H), 7.35 (s, 1H), 7.25 (m, 2H), 2.82 (d, J = 8.4 Hz, 4H), 1.79 (m, 2H), 1.38-1.24 (m, 32H), 0.94-0.88 (m, 12H)。

In a 100 mL three-necked round bottle, C42 (2.4 g, 2.67 mmol) and C11 (2.5 g, 6.72 mmol) were dissolved in 72 mL of THF. The solution was purged with argon for 30 minutes. Pd ₂ dba ₃ (98 mg, 0.107 mmol) and P(o-tol) ₃ (130 mg, 0.426 mmol) were then added to the solution under argon. The mixture was heated to 66°C and stirred for 24 hours. Once the reaction was complete, the mixture was filtered through a pad of silica gel and Celite, and the pad was washed with THF. The filtrate was then collected and the solvent removed by rotary concentration. The obtained crude product was purified by silica gel column chromatography using heptane/toluene (v/v 7/1) as eluent. Compound C43 was obtained as a red oil (1.4 g, 58% yield). ¹ H NMR (600 MHz, CDCl ₃ ): δ 7.99 (d, J = 4.8 Hz, 2H), 7.65 (d, J = 6.6 Hz, 2H), 7.35 (s, 1H), 7.25 (m, 2H), 2.82 (d, J = 8.4 Hz, 4H), 1.79 (m, 2H), 1.38-1.24 (m, 32H), 0.94-0.88 (m, 12H).

１００ｍＬの二つ口丸ビン中で、Ｃ４３（１．３ｇ、１．４４ｍｍｏｌ）を３９ｍＬのＴＨＦに溶解した。次いで、ＮＢＳ（５６５ｍｇ、３．１８ｍｍｏｌ）を溶液に添加した。混合物を４０℃まで加熱し、１８時間撹拌した。反応が完了した後に、生成物をヘプタン／水で３回抽出した。有機層をＭｇＳＯ_４で乾燥させ、回転濃縮によって溶媒を除去した。その後、得られた粗生成物を、溶離剤としてヘプタン／ＤＣＭ（ｖ／ｖ ３／１）を用いたシリカゲルカラムクロマトグラフィーで精製した。化合物Ｃ４４を赤色油状物として得た（１．４ｇ、収率９２％）。¹H NMR (600 MHz, CDCl₃): δ 7.75 (d, J = 4.2 Hz, 2H), 7.34 (s, 2H), 7.18 (d, J = 4.2 Hz, 2H), 2.84 (d, J = 6.6 Hz, 4H), 1.83 (m, 2H), 1.40-1.26 (m, 32H), 0.91 (t, J = 6.6 Hz, 6H), 0.87 (t, J = 6.6 Hz, 6H)。

C43 (1.3 g, 1.44 mmol) was dissolved in 39 mL of THF in a 100 mL two-necked round bottle. NBS (565 mg, 3.18 mmol) was then added to the solution. The mixture was heated to 40°C and stirred for 18 hours. After the reaction was completed, the product was extracted with heptane/water three times. The organic layer was dried with MgSO ₄ and the solvent was removed by rotary concentration. The obtained crude product was then purified by silica gel column chromatography using heptane/DCM (v/v 3/1) as eluent. Compound C44 was obtained as a red oil (1.4 g, 92% yield). ¹ H NMR (600 MHz, CDCl ₃ ): δ 7.75 (d, J = 4.2 Hz, 2H), 7.34 (s, 2H), 7.18 (d, J = 4.2 Hz, 2H), 2.84 (d, J = 6.6 Hz, 4H), 1.83 (m, 2H), 1.40-1.26 (m, 32H), 0.91 (t, J = 6.6 Hz, 6H), 0.87 (t, J = 6.6 Hz, 6H).

２５０ｍＬの三つ口丸ビン中で、Ｃ３７（２．０ｇ、６．８０ｍｍｏｌ）およびＣ１９（９．０ｇ、１７．０１ｍｍｏｌ）を６０ｍＬのＴＨＦに溶解した。溶液をアルゴンでパージした。次いで、Ｐｄ_２ｄｂａ_３（２４９ｍｇ、０．２７２ｍｍｏｌ）およびＰ（ｏ－ｔｏｌ）_３（３３１ｍｇ、１．０８９ｍｍｏｌ）をアルゴン下で溶液に添加した。混合物を６６℃まで加熱し、１８時間撹拌した。反応が終了すると、混合物をシリカゲルおよびセライトパッドを通してろ過し、パッドをＴＨＦで洗浄した。その後、ろ液を回収し、回転濃縮によって溶媒を除去した。得られた粗生成物を、溶離剤としてヘプタン／ＤＣＭ（ｖ／ｖ ３／１）を用いたシリカゲルカラムクロマトグラフィーで精製した。化合物Ｃ５０を淡橙色固体として得た（４．５ｇ、収率７７％）。¹H NMR (500 MHz, CDCl₃): δ 8.10 (d, J = 1.5 Hz, 1H) 7.87 (d, J = 8.0 Hz, 1H), 7.82 (d, J = 8.0 Hz, 1H), 7.28 (s, 1H), 7.08 (d, J = 1.0 Hz, 1H), 7.01 (d, J = 1.0 Hz, 1H), 2.63 (m, 4H), 1.68 (m, 2H), 1.38-1.21 (m, 64H), 0.87 (m, 12H)。 Preparation of monomer C51

In a 250 mL three-necked round bottle, C37 (2.0 g, 6.80 mmol) and C19 (9.0 g, 17.01 mmol) were dissolved in 60 mL of THF. The solution was purged with argon. Pd ₂ dba ₃ (249 mg, 0.272 mmol) and P(o-tol) ₃ (331 mg, 1.089 mmol) were then added to the solution under argon. The mixture was heated to 66°C and stirred for 18 hours. Once the reaction was complete, the mixture was filtered through a pad of silica gel and Celite, and the pad was washed with THF. The filtrate was then collected and the solvent removed by rotary concentration. The crude product obtained was purified by silica gel column chromatography using heptane/DCM (v/v 3/1) as eluent. Compound C50 was obtained as a pale orange solid (4.5 g, 77% yield). ¹ H NMR (500 MHz, CDCl ₃ ): δ 8.10 (d, J = 1.5 Hz, 1H) 7.87 (d, J = 8.0 Hz, 1H), 7.82 (d, J = 8.0 Hz, 1H), 7.28 (s , 1H), 7.08 (d, J = 1.0 Hz, 1H), 7.01 (d, J = 1.0 Hz, 1H), 2.63 (m, 4H), 1.68 (m, 2H), 1.38-1.21 (m, 64H) , 0.87 (m, 12H).

２５０ｍＬの二つ口丸ビン中で、Ｃ５０（４．５ｇ、５．２２ｍｍｏｌ）を１３５ｍＬのＴＨＦに溶解した。次いで、ＮＢＳ（２．０５ｇ、１１．４９ｍｍｏｌ）を室温で前記溶液に添加した。混合物を２時間攪拌した。反応が完了した後に、生成物をヘプタン／水で３回抽出した。水を有機層から除去し、溶媒を回転蒸発によって除去した。その後、得られた粗生成物を、溶離剤としてヘプタンを用いたシリカゲルカラムクロマトグラフィーで精製した。化合物Ｃ５１を淡橙色固体として得た（４．８ｇ、収率８７％）。¹H NMR (500 MHz, CDCl₃) of the 化合物 C51: δ 7.85 (s, 1H), 7.80 (d, J = 8.0 Hz, 1H), 7.75 (d, J = 8.0 Hz, 1H), 7.12 (s, 1H), 2.57 (m, 4H), 1.73 (m, 2H), 1.38-1.21 (m, 64H), 0.87 (m, 12H)。

C50 (4.5 g, 5.22 mmol) was dissolved in 135 mL of THF in a 250 mL two-necked round bottle. NBS (2.05 g, 11.49 mmol) was then added to the solution at room temperature. The mixture was stirred for 2 hours. After the reaction was completed, the product was extracted with heptane/water three times. Water was removed from the organic layer and the solvent was removed by rotary evaporation. Thereafter, the obtained crude product was purified by silica gel column chromatography using heptane as eluent. Compound C51 was obtained as a pale orange solid (4.8 g, 87% yield). ¹ H NMR (500 MHz, CDCl ₃ ) of the compound C51: δ 7.85 (s, 1H), 7.80 (d, J = 8.0 Hz, 1H), 7.75 (d, J = 8.0 Hz, 1H), 7.12 (s , 1H), 2.57 (m, 4H), 1.73 (m, 2H), 1.38-1.21 (m, 64H), 0.87 (m, 12H).

１００ｍＬの三つ口丸ビン中で、Ｃ４２（１．５ｇ、１．６８ｍｍｏｌ）およびＣ５２（１．５ｇ、３．６９ｍｍｏｌ）を４５ｍＬのＴＨＦに溶解した。溶液をアルゴンでパージした。次いで、Ｐｄ_２ｄｂａ_３（６１ｍｇ、０．０６７ｍｍｏｌ）およびＰ（ｏ－ｔｏｌ）_３（８２ｍｇ、０．２６９ｍｍｏｌ）をアルゴン下で溶液に添加した。混合物を６６℃まで加熱し、３時間撹拌した。反応が終了すると、混合物をシリカゲルおよびセライトパッドを通してろ過し、パッドをＴＨＦで洗浄した。その後、ろ液を回収し、回転濃縮によって溶媒を除去した。得られた粗生成物を、溶離剤としてヘプタンを用いたシリカゲルカラムクロマトグラフィーで精製した。化合物Ｃ５３を赤色油状物として得た（１．９ｇ、収率９２％）。¹H NMR (600 MHz, CDCl₃): δ 7.85 (s, 2H), 7.35 (s, 2H), 7.24 (s, 2H), 2.81 (d, J = 7.2 Hz, 4H), 2.71 (t, J = 7.8 Hz, 4H), 1.79 (m, 2H), 1.71 (m, 4H), 1.42-1.26 (m, 68H), 0.91 (t, J = 6.6 Hz, 6H), 0.89-0.86 (m, 12H)。 Preparation of monomer C54

In a 100 mL three-necked round bottle, C42 (1.5 g, 1.68 mmol) and C52 (1.5 g, 3.69 mmol) were dissolved in 45 mL of THF. The solution was purged with argon. Pd ₂ dba ₃ (61 mg, 0.067 mmol) and P(o-tol) ₃ (82 mg, 0.269 mmol) were then added to the solution under argon. The mixture was heated to 66°C and stirred for 3 hours. Once the reaction was complete, the mixture was filtered through a pad of silica gel and Celite, and the pad was washed with THF. The filtrate was then collected and the solvent removed by rotary concentration. The obtained crude product was purified by silica gel column chromatography using heptane as eluent. Compound C53 was obtained as a red oil (1.9 g, 92% yield). ¹ H NMR (600 MHz, CDCl ₃ ): δ 7.85 (s, 2H), 7.35 (s, 2H), 7.24 (s, 2H), 2.81 (d, J = 7.2 Hz, 4H), 2.71 (t, J = 7.8 Hz, 4H), 1.79 (m, 2H), 1.71 (m, 4H), 1.42-1.26 (m, 68H), 0.91 (t, J = 6.6 Hz, 6H), 0.89-0.86 (m, 12H) .

１００ｍＬの二つ口丸ビン中で、Ｃ５３（１．９ｇ、１．５４ｍｍｏｌ）を５７ｍＬのＴＨＦに溶解した。次いで、ＮＢＳ（６０１ｍｇ、３．７４ｍｍｏｌ）を溶液に添加した。混合物を室温で２．５時間撹拌した。反応が完了した後に、生成物をヘプタン／水で３回抽出した。有機層をＭｇＳＯ_４で乾燥させ、回転濃縮によって溶媒を除去した。その後、得られた粗生成物を溶離剤としてヘプタンを用いたシリカゲルカラムクロマトグラフィーで精製した。化合物Ｃ５４を赤色油状物として得た（１．８ｇ、収率８４％）。¹H NMR (500 MHz, CDCl₃): δ 7.70 (s, 2H), 7.34 (s, 2H), 2.83 (d, J = 7.0 Hz, 4H), 2.65 (t, J = 7.5 Hz, 4H), 1.82 (m, 2H), 1.65 (m, 4H), 1.38-1.26 (m, 68H), 0.91-0.85 (m, 18H)。

C53 (1.9 g, 1.54 mmol) was dissolved in 57 mL of THF in a 100 mL two-necked round bottle. NBS (601 mg, 3.74 mmol) was then added to the solution. The mixture was stirred at room temperature for 2.5 hours. After the reaction was completed, the product was extracted with heptane/water three times. The organic layer was dried with MgSO ₄ and the solvent was removed by rotary concentration. Thereafter, the obtained crude product was purified by silica gel column chromatography using heptane as an eluent. Compound C54 was obtained as a red oil (1.8 g, 84% yield). ¹ H NMR (500 MHz, CDCl ₃ ): δ 7.70 (s, 2H), 7.34 (s, 2H), 2.83 (d, J = 7.0 Hz, 4H), 2.65 (t, J = 7.5 Hz, 4H), 1.82 (m, 2H), 1.65 (m, 4H), 1.38-1.26 (m, 68H), 0.91-0.85 (m, 18H).

Ｃ４９（１６２．６ｍｇ、０．２６３ｍｍｏｌ）、Ｃ１３（１５６．８ｍｇ、０．１３２ｍｍｏｌ）、Ｃ３０（１４５．０ｍｇ、０．１３２ｍｍｏｌ）、Ｐｄ_２ｄｂａ_３（２．４１ｍｇ、０．００２６ｍｍｏｌ）、およびＰ（ｏ－ｔｏｌ）_３（３．２１ｍｇ、０．０１０５ｍｍｏｌ）を、１００ｍＬの二つ口丸ビン中で混合した。系を３０分間真空にし、アルゴンで埋め戻した。１１．４ｍＬのクロロベンゼンをアルゴンでパージし、次いで、混合物に添加した。混合物を１３０℃まで加熱し、２．５時間撹拌した。反応が完了した後に、ポリマーをメタノール中で沈殿させ、ろ過した。固体をアセトンで洗浄し、真空下で乾燥させた。次いで、ポリマーを、メタノールおよびジクロロメタンを順に用いたソックスレー抽出によって精製した（各ステップは１８時間）。その後、残留固体を回収した。残留固体をクロロベンゼンに溶解し、１２０℃で１時間撹拌し、ＭｅＯＨ中で沈殿させ、ろ過した。固体を回収し、アセトンで洗浄し、真空で溶媒を除去した。ポリマー１を黒色固体として得た（２８５ｍｇ、収率８５％）。 The synthesis of Polymer 1 is represented by the following formula:

C49 (162.6 mg, 0.263 mmol), C13 (156.8 mg, 0.132 mmol), C30 (145.0 mg, 0.132 mmol), _Pd2dba3 ( _2.41 mg, 0.0026 mmol), and P( o-tol) ₃ (3.21 mg, 0.0105 mmol) were mixed in a 100 mL two-necked round bottle. The system was evacuated for 30 minutes and backfilled with argon. 11.4 mL of chlorobenzene was purged with argon and then added to the mixture. The mixture was heated to 130°C and stirred for 2.5 hours. After the reaction was completed, the polymer was precipitated in methanol and filtered. The solid was washed with acetone and dried under vacuum. The polymer was then purified by Soxhlet extraction with methanol and dichloromethane sequentially (18 hours each step). The remaining solids were then collected. The remaining solid was dissolved in chlorobenzene, stirred at 120° C. for 1 hour, precipitated in MeOH and filtered. The solid was collected, washed with acetone and the solvent removed in vacuo. Polymer 1 was obtained as a black solid (285 mg, yield 85%).

ポリマー３の合成は、以下の式で表される：

Ｃ４９（１４７．５ｍｇ、０．２３９ｍｍｏｌ）、Ｃ１３（１４２．２ｍｇ、０．１２０ｍｍｏｌ）、Ｃ３３（１０８．５ｍｇ、０．１２０ｍｍｏｌ）、Ｐｄ_２ｄｂａ_３（８．７５ｍｇ、０．００９６ｍｍｏｌ）、およびＰ（ｏ－ｔｏｌ）_３（１１．６４ｍｇ、０．０３８２ｍｍｏｌ）を、１００ｍＬの二つ口丸ビン中で混合した。系を３０分間真空にし、アルゴンで埋め戻した。１０．３ｍＬのトルエンをアルゴンでパージし、次いで、混合物に添加した。混合物を９０℃まで加熱し、４５分間撹拌した。反応が完了した後に、ポリマーをメタノール中で沈殿させ、ろ過した。固体をアセトンで洗浄し、真空下で乾燥させた。次いで、ポリマーを、メタノールおよびジクロロメタンを順に用いたソックスレー抽出によって精製した（各ステップは１８時間）。その後、残留固体を回収した。残留固体をクロロベンゼンに溶解し、１２０℃で１時間撹拌し、ＭｅＯＨ中で沈殿させ、ろ過した。固体を回収し、アセトンで洗浄し、真空で溶媒を除去した。ポリマー３を黒色固体として得た（２５０ｍｇ、収率７２％）。 The synthesis of polymer 2 is represented by the following formula:

The synthesis of polymer 3 is represented by the following formula:

C49 (147.5 mg, 0.239 mmol), C13 (142.2 mg, 0.120 mmol), C33 (108.5 mg, 0.120 mmol), _Pd2dba3 ( _8.75 mg, 0.0096 mmol), and P( o-tol) ₃ (11.64 mg, 0.0382 mmol) were mixed in a 100 mL two-necked round bottle. The system was evacuated for 30 minutes and backfilled with argon. 10.3 mL of toluene was purged with argon and then added to the mixture. The mixture was heated to 90°C and stirred for 45 minutes. After the reaction was completed, the polymer was precipitated in methanol and filtered. The solid was washed with acetone and dried under vacuum. The polymer was then purified by Soxhlet extraction with methanol and dichloromethane sequentially (18 hours each step). The remaining solids were then collected. The remaining solid was dissolved in chlorobenzene, stirred at 120° C. for 1 hour, precipitated in MeOH and filtered. The solid was collected, washed with acetone and the solvent removed in vacuo. Polymer 3 was obtained as a black solid (250 mg, 72% yield).

Ｃ４９（１５２．７ｍｇ、０．２４７ｍｍｏｌ）、Ｃ１３（１４７．３ｍｇ、０．１２４ｍｍｏｌ）、Ｃ３６（１４６．５ｍｇ、０．１２４ｍｍｏｌ）、Ｐｄ_２ｄｂａ_３（２．２７ｍｇ、０．００２５ｍｍｏｌ）、およびＰ（ｏ－ｔｏｌ）_３（３．０１ｍｇ、０．００９９ｍｍｏｌ）を、１００ｍＬの二つ口丸ビン中で混合した。系を３０分間真空にし、アルゴンで埋め戻した。１０．７ｍＬのクロロベンゼンをアルゴンでパージし、次いで、混合物に添加した。混合物を１３０℃まで加熱し、２．５時間撹拌した。反応が完了した後に、ポリマーをメタノール中で沈殿させ、ろ過した。固体をアセトンで洗浄し、真空下で乾燥させた。次いで、ポリマーを、メタノールおよびジクロロメタンを順に用いたソックスレー抽出によって精製した（各ステップは１８時間）。その後、残留固体を回収した。残留固体をクロロベンゼンに溶解し、１２０℃で１時間撹拌し、ＭｅＯＨ中で沈殿させ、ろ過した。固体を回収し、アセトンで洗浄し、真空で溶媒を除去した。ポリマー４を黒色固体として得た（２４０ｍｇ、収率７３％）。 The synthesis of polymer 4 is represented by the following formula:

C49 (152.7 mg, 0.247 mmol), C13 (147.3 mg, 0.124 mmol), C36 (146.5 mg, 0.124 mmol), _Pd2dba3 ( _2.27 mg, 0.0025 mmol), and P( o-tol) ₃ (3.01 mg, 0.0099 mmol) were mixed in a 100 mL two-necked round bottle. The system was evacuated for 30 minutes and backfilled with argon. 10.7 mL of chlorobenzene was purged with argon and then added to the mixture. The mixture was heated to 130°C and stirred for 2.5 hours. After the reaction was completed, the polymer was precipitated in methanol and filtered. The solid was washed with acetone and dried under vacuum. The polymer was then purified by Soxhlet extraction with methanol and dichloromethane sequentially (18 hours each step). The remaining solids were then collected. The remaining solid was dissolved in chlorobenzene, stirred at 120° C. for 1 hour, precipitated in MeOH and filtered. The solid was collected, washed with acetone and the solvent removed in vacuo. Polymer 4 was obtained as a black solid (240 mg, yield 73%).

ポリマー６の合成は、以下の式で表される：

Ｃ４９（１５０．０ｍｇ、０．２４３ｍｍｏｌ）、Ｃ１３（１４４．５ｍｇ、０．１２２ｍｍｏｌ）、Ｃ４４（１２０．１ｍｇ、０．１２２ｍｍｏｌ）、Ｐｄ_２ｄｂａ_３（２．２３ｍｇ、０．００２４ｍｍｏｌ）、およびＰ（ｏ－ｔｏｌ）_３（２．９６ｍｇ、０．００９７ｍｍｏｌ）を、１００ｍＬの二つ口丸ビン中で混合した。系を３０分間真空にし、アルゴンで埋め戻した。１０．５ｍＬのクロロベンゼンをアルゴンでパージし、次いで、混合物に添加した。混合物を１３０℃まで加熱し、２２分間撹拌した。反応が完了した後に、ポリマーをメタノール中で沈殿させ、ろ過した。固体をアセトンで洗浄し、真空下で乾燥させた。次いで、ポリマーを、メタノールおよびジクロロメタンを順に用いたソックスレー抽出によって精製した（各ステップは１８時間）。その後、残留固体を回収した。残留固体をクロロベンゼンに溶解し、１２０℃で１時間撹拌し、ＭｅＯＨ中で沈殿させ、ろ過した。固体を回収し、アセトンで洗浄し、真空で溶媒を除去した。ポリマー６を黒色固体として得た（２６０ｍｇ、収率８５％）。 The synthesis of polymer 5 is represented by the following formula:

The synthesis of polymer 6 is represented by the following formula:

C49 (150.0 mg, 0.243 mmol), C13 (144.5 mg, 0.122 mmol), C44 (120.1 mg, 0.122 mmol), _Pd2dba3 ( _2.23 mg, 0.0024 mmol), and P( o-tol) ₃ (2.96 mg, 0.0097 mmol) were mixed in a 100 mL two-necked round bottle. The system was evacuated for 30 minutes and backfilled with argon. 10.5 mL of chlorobenzene was purged with argon and then added to the mixture. The mixture was heated to 130°C and stirred for 22 minutes. After the reaction was completed, the polymer was precipitated in methanol and filtered. The solid was washed with acetone and dried under vacuum. The polymer was then purified by Soxhlet extraction with methanol and dichloromethane sequentially (18 hours each step). The remaining solids were then collected. The remaining solid was dissolved in chlorobenzene, stirred at 120° C. for 1 hour, precipitated in MeOH and filtered. The solid was collected, washed with acetone and the solvent removed in vacuo. Polymer 6 was obtained as a black solid (260 mg, 85% yield).

ポリマー８の合成は、以下の式で表される：

１００ｍＬの二つ口丸ビン中で、Ｃ４９（１５０．３ｍｇ、０．２４５ｍｍｏｌ）、Ｃ１３（１７３．９ｍｇ、０．１４６ｍｍｏｌ）、Ｃ５１（１０２．６ｍｇ、０．０９７ｍｍｏｌ）、Ｐｄ_２ｄｂａ_３（８．９２ｍｇ、０．００９７ｍｍｏｌ）、およびＰ（ｏ－ｔｏｌ）_３（１１．８６ｍｇ、０．０３９０ｍｍｏｌ）を１００ｍＬの二つ口丸ビン中で混合した。系を３０分間真空にし、アルゴンで埋め戻した。１０．５ｍＬのトルエンをアルゴンでパージし、次いで、混合物に添加した。混合物を９０℃まで加熱し、２時間撹拌した。反応が完了した後に、ポリマーをメタノール中で沈殿させ、ろ過した。固体をアセトンで洗浄し、真空下で乾燥させた。次いで、ポリマーを、メタノールおよびジクロロメタンを順に用いたソックスレー抽出によって精製した（各ステップは１８時間）。その後、残留固体を回収した。残留固体をトルエンに溶解し、１２０℃で１時間撹拌し、ＭｅＯＨ中で沈殿させ、ろ過した。固体を回収し、アセトンで洗浄し、真空で溶媒を除去した。ポリマー８を黒色固体として得た（２４０ｍｇ、収率７９％）。 The synthesis of polymer 7 is represented by the following formula:

The synthesis of polymer 8 is represented by the following formula:

In a 100 mL two-necked round bottle, C49 (150.3 mg, 0.245 mmol), C13 (173.9 mg, 0.146 mmol), C51 (102.6 mg, 0.097 mmol), Pd ₂ dba ₃ (8. 92 mg, 0.0097 mmol) and P(o-tol) ₃ (11.86 mg, 0.0390 mmol) were mixed in a 100 mL two-neck round bottle. The system was evacuated for 30 minutes and backfilled with argon. 10.5 mL of toluene was purged with argon and then added to the mixture. The mixture was heated to 90°C and stirred for 2 hours. After the reaction was completed, the polymer was precipitated in methanol and filtered. The solid was washed with acetone and dried under vacuum. The polymer was then purified by Soxhlet extraction with methanol and dichloromethane sequentially (18 hours each step). The remaining solids were then collected. The residual solid was dissolved in toluene, stirred at 120° C. for 1 hour, precipitated in MeOH and filtered. The solid was collected, washed with acetone and the solvent removed in vacuo. Polymer 8 was obtained as a black solid (240 mg, 79% yield).

Ｃ４９（１４７．４ｍｇ、０．２３９ｍｍｏｌ）、Ｃ１３（１４２．２ｍｇ、０．１１９ｍｍｏｌ）、Ｃ５４（１６６．６ｍｇ、０．１１９ｍｍｏｌ）、Ｐｄ_２ｄｂａ_３（２．１９ｍｇ、０．００２４ｍｍｏｌ）、およびＰ（ｏ－ｔｏｌ）_３（２．９１ｍｇ、０．００９６ｍｍｏｌ）を、１００ｍＬの二つ口丸ビン中で混合した。系を３０分間真空にし、アルゴンで埋め戻した。１０．３ｍＬのクロロベンゼンをアルゴンでパージし、次いで、混合物に添加した。混合物を１３０℃まで加熱し、１８時間撹拌した。反応が完了した後に、ポリマーをメタノール中で沈殿させ、ろ過した。固体をアセトンで洗浄し、真空下で乾燥させた。次いで、ポリマーを、メタノールおよびジクロロメタンを順に用いたソックスレー抽出によって精製した（各ステップは１８時間）。その後、残留固体を回収した。残留固体をクロロベンゼンに溶解し、１２０℃で１時間撹拌し、ＭｅＯＨ中で沈殿させ、ろ過した。固体を回収し、アセトンで洗浄し、真空で溶媒を除去した。ポリマー９を黒色固体として得た（２８５ｍｇ、収率８４％）。 The synthesis of polymer 9 is represented by the following formula:

C49 (147.4 mg, 0.239 mmol), C13 (142.2 mg, 0.119 mmol), C54 (166.6 mg, 0.119 mmol), _Pd2dba3 ( _2.19 mg, 0.0024 mmol), and P( o-tol) ₃ (2.91 mg, 0.0096 mmol) were mixed in a 100 mL two-necked round bottle. The system was evacuated for 30 minutes and backfilled with argon. 10.3 mL of chlorobenzene was purged with argon and then added to the mixture. The mixture was heated to 130°C and stirred for 18 hours. After the reaction was completed, the polymer was precipitated in methanol and filtered. The solid was washed with acetone and dried under vacuum. The polymer was then purified by Soxhlet extraction with methanol and dichloromethane sequentially (18 hours each step). The remaining solids were then collected. The remaining solid was dissolved in chlorobenzene, stirred at 120° C. for 1 hour, precipitated in MeOH and filtered. The solid was collected, washed with acetone and the solvent removed in vacuo. Polymer 9 was obtained as a black solid (285 mg, yield 84%).

Ｃ４９（１５０ｍｇ、０．２４３ｍｍｏｌ）、Ｃ１３（２９０ｍｇ、０．２４３ｍｍｏｌ）、Ｐｄ_２ｄｂａ_３（２．２３ｍｇ、０．００２４３ｍｍｏｌ）、およびＰ（ｏ－ｔｏｌ）_３（２．９９ｍｇ、０．００９７２ｍｍｏｌ）を、１００ｍＬの二つ口丸ビン中で混合した。系を３０分間真空にし、アルゴンで埋め戻した。２１．０ｍＬのクロロベンゼンをアルゴンでパージし、次いで、混合物に添加した。混合物を１３０℃まで加熱し、１５分間撹拌した。反応が完了した後に、ポリマーをメタノール中で沈殿させ、ろ過した。固体をアセトンで洗浄し、真空下で乾燥させた。次いで、ポリマーを、メタノールおよびジクロロメタンを順に用いたソックスレー抽出によって精製した（各ステップは１８時間）。その後、残留固体を回収した。残留固体をクロロベンゼンに溶解し、１２０℃で１時間撹拌し、ＭｅＯＨ中で沈殿させ、ろ過した。固体を回収し、アセトンで洗浄し、真空で溶媒を除去した。比較ポリマーＰＣ１を黒色固体として得た（１０３ｍｇ、収率３１％）。 The synthesis of polymer PC1 is represented by the following formula:

C49 (150 mg, 0.243 mmol), C13 (290 mg, 0.243 mmol), _Pd2dba3 ( _2.23 mg, 0.00243 mmol), and P(o-tol) ₃ (2.99 mg, 0.00972 mmol). , mixed in a 100 mL two-necked round bottle. The system was evacuated for 30 minutes and backfilled with argon. 21.0 mL of chlorobenzene was purged with argon and then added to the mixture. The mixture was heated to 130°C and stirred for 15 minutes. After the reaction was completed, the polymer was precipitated in methanol and filtered. The solid was washed with acetone and dried under vacuum. The polymer was then purified by Soxhlet extraction with methanol and dichloromethane sequentially (18 hours each step). The remaining solids were then collected. The remaining solid was dissolved in chlorobenzene, stirred at 120° C. for 1 hour, precipitated in MeOH and filtered. The solid was collected, washed with acetone and the solvent removed in vacuo. Comparative polymer PC1 was obtained as a black solid (103 mg, 31% yield).

The term "n" in the formulas of the present invention means an integer and n>1.

Table 1 shows embodiments of the organic semiconductor polymer according to the present invention.

Furthermore, the organic semiconducting polymers of the present invention have charge transport, semiconducting, conductive, optically conductive properties in optical devices or systems, optoelectronic devices or systems, electronic devices or systems, electroluminescent devices or systems, or optoelectronic devices or systems. Or it can be a luminescent material. The organic semiconducting polymers of the present invention are typically manipulated in the form of thin layers or films in the devices.

The organic semiconducting polymer according to the present invention can be applied as an electron donor or a p-type semiconductor in organic optoelectronic devices. It can be realized in the formation of n-type and p-type organic semiconductor blends in organic photodetectors. The term n-type or n-type organic semiconductor is understood as an extrinsic semiconductor with a conduction electron density greater than the hole density, while the term p-type or p-type organic semiconductor is understood as an extrinsic semiconductor with a conduction hole density greater than the electron density. It is understood as an extrinsic semiconductor with density (also shown in J. Thewlis, Concise Dictionary of Physics, Pergamon Press, Oxford, 1973).

In organic optoelectronic applications, the organic semiconducting polymers of the present invention may have at least one of the following characteristics to prepare components: charge transport, semiconducting, electrical conductivity, optical conductivity, hole blocking, and electron blocking. One or more small molecule compounds or polymers having one or more components are selectively added.

Furthermore, in organic optoelectronic device applications, organic semiconducting polymers of the present invention and/or compounds such as charge transporting, semiconducting, electrical conductivity, optical conductivity, hole blocking, and electron blocking may be used to mix and prepare components. one or more small molecule compounds or polymers having properties and one or more organic solvents (preferably, the solvent is, for example, toluene, o-xylene, p-xylene, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3, aliphatic hydrocarbons, chlorinated hydrocarbons, aromatic hydrocarbons, ketones, ethers, and mixtures thereof, such as 5-trimethylbenzene or 1,2,4-trimethylbenzene.

The organic semiconducting polymer according to the invention can be used in the active layer of the above-mentioned devices. For microelectronic applications, there is a need to fabricate small or patterned structures to reduce cost (more devices per unit area) and power consumption. For processing as thin layers or thin films in electronic or optoelectronic devices, components composed of the organic semiconducting polymers of the invention may be deposited in any suitable manner. In said devices, solution processing technology is superior to vacuum deposition.

Preferred deposition methods include, but are not limited to, dip coating, spin coating, inkjet printing, nozzle printing, relief printing, screen printing, gravure printing, blade coating, roller printing, reverse roll coating, lithography, dry offset printing, flexography, Including web printing, spray coating, curtain coating, brush coating, slot die coating or pad printing.

The present invention embodies a component composed of an organic semiconducting polymer of the present invention or an optoelectronic device comprising said component composed of an organic semiconducting polymer of the present invention.

In a first embodiment of the invention, referring to FIG. 1A, an organic optoelectronic device 10 includes a substrate 100, an electrode module 110, and an active layer 120. An electrode module 110 is disposed on the substrate 100, the electrode module 110 includes a first electrode 112 and a second electrode 114, and an active layer 120 is formed between the first electrode 112 and the second electrode 114. will be placed in First electrode 112 is disposed between substrate 100 and active layer 120. Second electrode 114 is located above active layer 120.

In this embodiment, the active layer 120 comprises at least one organic semiconducting polymer according to the invention. At least one of the first electrode 112 and the second electrode 114 is transparent or semitransparent.

In a second embodiment of the invention, referring to FIG. 1B, an organic optoelectronic device 10 includes a substrate 100, an electrode module 110, and an active layer 120. An electrode module 110 is disposed on the substrate 100, the electrode module 110 includes a first electrode 112 and a second electrode 114, and an active layer 120 is formed between the first electrode 112 and the second electrode 114. will be placed in The second electrode 114 is disposed between the substrate 100 and the active layer 120, and the first electrode 112 is located above the active layer 120.

The substrate 100 is preferably a glass substrate or a transparent flexible substrate that has mechanical strength, thermal strength, and transparency. Transparent soft base materials include polyethylene, ethylene vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polypropylene, polystyrene, poly(methyl methacrylate), polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone, polysulfone, poly Ether sulfone, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyvinyl fluoride, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, polyvinylidene difluoride, polyester, polycarbonate, polyurethane, Contains polyimide, etc.

The first electrode 112 is preferably a transparent metal oxide such as indium oxide, tin oxide, and fluorine-doped tin oxide (FTO), or a composite metal oxide such as indium tin oxide (ITO), indium zinc oxide (IZO), etc. It is a thing.

The second electrode 114 is selected from metal oxides, metals (silver, aluminum, gold), conductive polymers, carbon-based conductors, metal compounds, or conductive films composed of two or more of the above-mentioned materials. can be done.

In a preferred embodiment, active layer 120 of organic optoelectronic device 10 includes at least one p-type organic semiconductor polymer (eg, the organic semiconductor polymer of the present invention described above) and at least one n-type organic semiconductor compound.

図１Ｃに示される第３の実施形態において、有機光電子デバイス１０のコンポーネントは、前記第１の実施形態と同じ順序で配置されるが、有機光電子デバイス１０は、第１の電極１１２と活性層１２０との間に配置された第１のキャリア輸送層１３０と、第２の電極１１４と活性層１２０との間に配置された第２のキャリア輸送層１４０とをさらに含む。 In a preferred embodiment, the n-type organic semiconductor compound of organic optoelectronic device 10 is selected from the group consisting of:

In a third embodiment shown in FIG. 1C, the components of the organic optoelectronic device 10 are arranged in the same order as in the first embodiment, but the organic optoelectronic device 10 includes a first electrode 112 and an active layer 120. The active layer 120 further includes a first carrier transport layer 130 disposed between the second electrode 114 and the active layer 120 .

In a fourth embodiment shown in FIG. 1D, the components of the organic optoelectronic device 10 are arranged in the same order as in the first embodiment, but the organic optoelectronic device 10 has a second electrode 114 and an active layer 120. The active layer 120 further includes a first carrier transport layer 130 disposed between the first electrode 112 and the active layer 120 .

In a fifth embodiment shown in FIG. 1E, the components of the organic optoelectronic device 10 are arranged in the same order as in the second embodiment, but the organic optoelectronic device 10 has a second electrode 114 and an active layer 120. The active layer 120 further includes a first carrier transport layer 130 disposed between the first electrode 112 and the active layer 120 .

In a sixth embodiment shown in FIG. 1F, the components of the organic optoelectronic device 10 are arranged in the same order as in the second embodiment, but the organic optoelectronic device 10 includes a first electrode 112 and an active layer 120. The active layer 120 further includes a first carrier transport layer 130 disposed between the second electrode 114 and the active layer 120 .

In the third to sixth embodiments described above, the material for the first carrier transport layer 130 is selected from: conjugated polymer electrolyte (e.g. PEDOT:PSS), polymeric acid (e.g. polyacrylate) , conjugated polymers (e.g. poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA)), insulating polymers (e.g. Nafion film, polyethyleneimine and polystyrene sulfonate), MoOx, NiOx, Polymers doped with metal oxides including WOx, SnOx, metal oxides (e.g. MoOx, NiOx, WOx, SnOx), small organic compounds (e.g. N,N'-diphenyl-N,N'-bis- (1-naphthyl)(1,1'-biphenyl)-4,4'-diamine (NPB), N,N'-diphenyl-N,N'-(3-methylphenyl)-1,1'-biphenyl- 4,4'-diamine (TPD)), or combinations thereof.

In the third to sixth embodiments described above, the material for the second carrier transport layer 140 is selected from: a conjugated polymer electrolyte (eg, polyethyleneimine), a conjugated polymer (eg, poly[3- (6-trimethylammoniumhexyl)thiophene], poly[9,9-bis(2-ethylhexyl)fluorene]-b-poly[3-(6-trimethylammoniumhexyl)thiophene], or poly[(9,9-bis (3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)]), organic small molecule compounds (for example, tris(8- hydroxyquinoline) aluminum(III) (Alq ₃ ), 4,7-diphenyl-1,10-phenanthroline), metal oxides (e.g. ZnOx, aluminum-doped zinc oxide (AZO), TiOx and their nanoparticles), salts (e.g., LiF, NaF, CsF, and _CsCO3 ), and amines (e.g., primary amines, secondary amines, and tertiary amines).

In order to exhibit the beneficial effects of the organic semiconducting polymer in the present invention in organic optoelectronic devices, optoelectronic devices containing the present organic semiconducting polymer were fabricated, and the corresponding performance was tested and collected. The results are shown below:
UV-VIS Absorption Characteristics of Organic Semiconductor Polymer The absorption spectrum of the organic semiconductor polymer was measured using a UV-VIS spectrophotometer. For solution UV-VIS absorption measurements, all of the samples were dissolved in chlorobenzene and then measured. For solid state UV-VIS absorption measurements, samples were prepared in the form of thin films. Film samples were prepared on glass plates by spin coating their solutions in o-xylene with a solids concentration of 7-14 mg/mL and then measured. The absorption spectra are shown in FIGS. 2A and 2B, and the measurement results are shown in Table 2.

The absorption spectra of the present organic semiconductor polymers P1 to P9 and comparative polymer PC1 in solution and film form are shown in FIGS. 2A and 2B. Comparative polymer PC1 is an alternating copolymer. Apart from the absorption peak at 500 nm in all polymers of the invention, which is due to the π-π* orbital transition, polymer PC1 lacks absorption peaks between 600 and 900 nm and has only absorption peaks above 1000 nm. On the other hand, the absorption spectra of polymers 1 to 9 have two absorption peaks, less than 1000 nm and more than 1000 nm, respectively. All polymers 1-9 showed good absorption in the 1000 nm to 1400 nm region.

Determination of the electrochemical properties of the materials The oxidation properties were determined by cyclic voltammetry (CV). The highest occupied orbital (HOMO) was calculated according to the formula HOMO=−|4.71+E ^ox −E ^ferroncene |. The optical absorption onset (λ _onset ) was measured by film ultraviolet-visible-near-infrared (UV-Vis-NIR) absorption spectra. The optical energy gap was then calculated according to the formula E _g =1240/λ _onset . The lowest unoccupied molecular orbital (LUMO) was calculated according to the formula LUMO=HOMO+E _g ^opt . The energy levels are shown in Table 2. It is clear that the energy levels of polymers 1 to 9 can be adjusted by copolymerization with different second repeat units. The results suggested that the polymers of the present invention have the potential to be compatible with various non-fullerene acceptors (NFAs) by providing sufficient driving force for the dissociation of electron-hole pairs.

Fabrication of OPD Device The substrate was patterned ITO (indium tin oxide) coated glass with a sheet resistance of about 15 Ω/sq. The substrate was cleaned by sequential sonication in an aqueous surfactant solution, deionized water, methanol, acetone, and isopropanol (15 minutes each step). The ITO substrate was then further treated with a UV/ozone cleaner for 30 minutes. The ITO substrate was spin-coated with AZO (aluminum-doped zinc oxide) solution at 3000 rpm for 40 seconds and annealed in air at 120 °C for 5 minutes. An active layer solution was prepared by dissolving the above N-type and P-type organic semiconductor materials in o-xylene and stirring at 100° C. for 4 hours. After cooling to room temperature, the solution was filtered through a 1.0 μm pore size membrane. Thereafter, the solution was spin-coated onto the substrate to form an active layer. The active layer was annealed at 100° C. for 5 minutes and then transferred to a thermal evaporation coater. An active layer solution of PC1 is prepared in o-xylene at a weight ratio of polymer:N1=1:1. Active layer solutions of P1, P4, P6 and P8 are prepared in o-xylene in a weight ratio of polymer:N1=1:1.5. Finally, 8 nm of MoO ₃ as a hole transport layer and 100 nm of Ag as an electrode were sequentially deposited by evaporation at 3 × 10 ⁻⁶ Torr, and the device was assembled using epoxy resin in a glove box. Enclosed. The above-mentioned organic optoelectronic devices were investigated using the glass/ITO/AZO/active layer/MoO ₃ /Ag structure.

Measurement of OPD Performance Current density-voltage (JV) characteristics under dark conditions (J _d , bias -8V) were measured using a Keithley ^TM 2400 source meter. The photocurrent (I _ph ) characteristics of the device were measured by a solar simulator (with an AM1.5G filtered xenon lamp) under AM1.5G (100 mW cm ⁻² ) at room temperature in air. Here, a standard silicon diode with a KG5 filter was used as a reference cell to calibrate the light intensity and match the mismatched parts of the spectrum. External quantum efficiency (EQE) was measured using an external quantum efficiency measuring device, and the measurement range was 300 to 1800 nm (bias 0 approximately -4 V). Light source calibration uses silicon (300-1100 nm) and germanium (1100-1800 nm). Responsiveness (R) and detectability (D) were calculated according to the following formulas:

Here, λ is the wavelength, q is the electron charge, h is Planck's constant, c is the speed of light, and J _d is the dark current.

The current-voltage characteristics of the corresponding OPD under dark conditions are shown in FIG. 3A. The detection capability of the corresponding OPD device is shown in Figure 3B. The EQE curve of the corresponding OPD device is shown in FIG. 3C. The performances of the corresponding OPD devices and comparative examples are shown in Tables 3 and 4.

表３によれば、Ｐ１、Ｐ４、Ｐ６、およびＰ８ならびにＮ１のＨＯＭＯおよびＬＵＭＯオフセットは、電子－正孔対に解離した励起子を動作させるのに十分であった。Ｐ１、Ｐ４、Ｐ６、およびＰ８に基づくデバイスは、－２Ｖバイアス電圧下で、１６００ｎｍまで光電応答（ＥＱＥ検出を伴う）を示し、１３００ｎｍでのそれらの検出能はすべて１×１０^１０Ｊｏｎｅｓを上回った。
Here, the comparative example in the literature is selected from Small 2022, 2200580, where the compound structure used is as follows:

According to Table 3, the HOMO and LUMO offsets of P1, P4, P6, and P8 and N1 were sufficient to drive excitons dissociated into electron-hole pairs. Devices based on P1, P4, P6, and P8 showed photoelectric response (with EQE detection) up to 1600 nm under −2 V bias voltage, and their detectability at 1300 nm all exceeded 1 × ¹⁰ Jones. .

Comparison of dark current performance: Under different biases, devices based on the presented organic semiconductor polymers P1, P4, P6, and P8 have better dark current performance than comparative example PC1 with only one repeating unit. . A reduction of 10,000 to 10,000 times in dark current density was achieved. Among the devices, the lowest dark current density was 1×10 ⁻⁶ A/cm ² . As shown in Figure 3A, the device based on PC1 is more sensitive to bias changes, and the dark current leakage is more severe than P1, P4, P6, and P8 as the bias increases. . The results showed that the second repeat unit of the present organic semiconducting polymer effectively suppresses device dark current.

Comparison of EQE performance: Devices based on P4 and P6 showed better EQE than PC1. P4 and P6 devices have EQE greater than 5% from 1300-1400 nm. In particular, P6 devices in embodiments have an EQE of up to 20% at 1300 nm. These results showed that the second repeat unit of the polymer suppresses dark current while not sacrificing the EQE performance of the corresponding devices.

Comparison of detection performance: The devices based on the presented organic semiconducting polymers P1, P4, P6, and P8 have a 100-fold increase in detection power compared to comparative example PC1. The good detection performance was the result of suppressing dark current without sacrificing EQE by adding a second repeating unit into the semiconducting polymer.

In conclusion, when the optical bandgap is less than 0.8 eV, the organic semiconducting polymer in the present invention has better corresponding device performance in both dark current and detectability under −2 V compared to the alternating copolymer PC1. has.

Additionally, as shown in Table 4, the components comprised of P4 and P6 in embodiments were treated with non-halogenated o-xylene for spin-coating active layers. OPD devices based on P4 and P6 showed better responsivity and detectability at 1200 nm than Comparative Examples 1 and 2 in the literature. In particular, the responsiveness and detectability of Comparative Examples 1 and 2 in the literature decreased from 1200 nm to 1400 nm, while the performance of the present invention was maintained.

Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and representative devices shown and described herein. Accordingly, various changes may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.

In summary, the organic semiconducting polymers of the present invention have good solubility in environmentally friendly solvents, which is beneficial for solution processing in mass production. Moreover, the organic optoelectronic devices based on the organic semiconducting polymers of the present invention have excellent photoresponse and corresponding device performance at wavelengths of 1300 nm and above.

Claims (11)

Organic semiconducting polymer represented by the following formula:

where X is the first repeating unit of formula I;

Y is a second repeating unit represented by formula II;

A ¹ group and A ² group are electron-withdrawing groups, the A ¹ group is different from the A ² group, and the A ² group is

Does not include;
D ¹ and D ² groups are electron donating groups;
sp ¹ -sp ⁴ are independently selected from the group consisting of unsubstituted arylene groups, substituted arylene groups, unsubstituted heteroarylene groups, and substituted heteroarylene groups;
a and b are real numbers, 0<a<1, 0<b<1, a+b=1;
c, d, e, and f are each an integer selected from 0 to 5 and are independent of each other; and the absorption wavelength of the first repeating unit X is longer than 1000 nm, and the absorption wavelength of the second repeating unit The absorption wavelength of unit Y is less than 1000 nm. The organic semiconducting polymer of claim 1, wherein the D ¹ and D ² groups are independently selected from the group consisting of:

In the formula, R ¹ to R ⁴ are a hydrogen atom, a halogen, a cyano group, a C1 to C30 straight chain alkyl group, a C3 to C30 branched alkyl group, a C1 to C30 silyl group, a C2 to C30 ester group, a C1 to C30 alkoxy group , C1-C30 thioalkyl group, C1-C30 haloalkyl group, C2-C30 alkene group, C2-C30 alkyne group, C2-C30 cyano group-containing hydrocarbon group, C1-C30 nitro group-containing hydrocarbon group, C1-C30 hydroxy group consisting of a containing hydrocarbon group, a C3-C30 keto group-containing hydrocarbon group, a C5-C20 cyclic hydrocarbon group, a C5-C20 heterocyclic hydrocarbon group, a C5-C20 aryl group, and a C5-C20 heteroaryl group. independently selected from the group, said cyclic hydrocarbon group, said heterocyclic hydrocarbon group, said aryl group, and said heteroaryl group are unsubstituted or at least one of R ⁵ -R ⁹ and is monocyclic, polycyclic, or fused ring; and R ⁵ to R ⁹ are a hydrogen atom, a halogen, a cyano group, a C1 to C30 straight chain alkyl group, a C3 to C30 branched Alkyl group, C1-C30 silyl group, C2-C30 ester group, C1-C30 alkoxy group, C1-C30 thioalkyl group, C1-C30 haloalkyl group, C2-C30 alkene group, C2-C30 alkyne group, C2-C30 cyano group independently selected from the group consisting of C1-C30 nitro-containing hydrocarbon groups, C1-C30 hydroxy-containing hydrocarbon groups, and C3-C30 keto-containing hydrocarbon groups. The organic semiconducting polymer according to claim 1, wherein the A ¹ group is selected from the group consisting of:

where X is selected from oxygen (O), sulfur (S), or selenium (Se);
R ¹⁰ and R ¹¹ are hydrogen atom, C1 to C30 straight chain alkyl group, C3 to C30 branched alkyl group, C1 to C30 silyl group, C2 to C30 ester group, C1 to C30 alkoxy group, C1 to C30 thioalkyl group, C1 ~C30 haloalkyl group, C2-C30 alkene group, C2-C30 alkyne group, C2-C30 cyano group-containing hydrocarbon group, C1-C30 nitro group-containing hydrocarbon group, C1-C30 hydroxy group-containing hydrocarbon group, C3-C30 independently selected from the group consisting of a keto group-containing hydrocarbon group, and a C5-C20 cyclic hydrocarbon group, a C5-C20 heterocyclic hydrocarbon group, a C5-C20 aryl group, and a C5-C20 heteroaryl group; The cyclic hydrocarbon group, the heterocyclic hydrocarbon group, the aryl group, and the heteroaryl group are unsubstituted or substituted with at least one of R ¹³ to R ¹⁷ , and is monocyclic, polycyclic, or fused ring; and R ¹³ to R ¹⁷ are a hydrogen atom, halogen, cyano group, C1 to C30 straight chain alkyl group, C3 to C30 branched alkyl group, C1 to C30 silyl group , C2-C30 ester group, C1-C30 alkoxy group, C1-C30 thioalkyl group, C1-C30 haloalkyl group, C2-C30 alkene group, C2-C30 alkyne group, C2-C30 cyano group-containing hydrocarbon group, C1-C30 independently selected from the group consisting of nitro group-containing hydrocarbon groups, C1-C30 hydroxy group-containing hydrocarbon groups, and C3-C30 keto group-containing hydrocarbon groups. The organic semiconducting polymer according to claim 1, wherein the A ² group is selected from the group consisting of;

where X is selected from oxygen (O), sulfur (S), or selenium (Se);
R ¹⁸ to R ¹⁹ are hydrogen atom, halogen, cyano group, C1 to C30 straight chain alkyl group, C3 to C30 branched alkyl group, C1 to C30 silyl group, C2 to C30 ester group, C1 to C30 alkoxy group, C1 to C30 thioalkyl group, C1-C30 haloalkyl group, C2-C30 alkene group, C2-C30 alkyne group, C2-C30 cyano group-containing hydrocarbon group, C1-C30 nitro group-containing hydrocarbon group, C1-C30 hydroxy group-containing hydrocarbon group independently selected from the group consisting of C3-C30 keto group-containing hydrocarbon groups;
R ²⁰ to R ²¹ are hydrogen atom, C1 to C30 straight chain alkyl group, C3 to C30 branched alkyl group, C1 to C30 silyl group, C2 to C30 ester group, C1 to C30 alkoxy group, C1 to C30 thioalkyl group, C1 ~C30 haloalkyl group, C2-C30 alkene group, C2-C30 alkyne group, C2-C30 cyano group-containing hydrocarbon group, C1-C30 nitro group-containing hydrocarbon group, C1-C30 hydroxy group-containing hydrocarbon group, C3-C30 independently selected from the group consisting of a keto group-containing hydrocarbon group, and a C5-C20 cyclic hydrocarbon group, a C5-C20 heterocyclic hydrocarbon group, a C5-C20 aryl group, and a C5-C20 heteroaryl group; The cyclic hydrocarbon group, the heterocyclic hydrocarbon group, the aryl group, and the heteroaryl group are unsubstituted or substituted with at least one of R ²² to R ²⁶ , and is monocyclic, polycyclic, or fused ring; and R ²² to R ²⁶ are a hydrogen atom, halogen, cyano group, C1 to C30 straight chain alkyl group, C3 to C30 branched alkyl group, C1 to C30 silyl group , C2-C30 ester group, C1-C30 alkoxy group, C1-C30 thioalkyl group, C1-C30 haloalkyl group, C2-C30 alkene group, C2-C30 alkyne group, C2-C30 cyano group-containing hydrocarbon group, C1-C30 independently selected from the group consisting of nitro group-containing hydrocarbon groups, C1-C30 hydroxy group-containing hydrocarbon groups, and C3-C30 keto group-containing hydrocarbon groups. The organic semiconducting polymer of claim 1, wherein sp ¹ -sp ⁴ are independently selected from the group consisting of:

where X is selected from oxygen (O), sulfur (S), or selenium (Se);
R ²⁷ to ²⁸ are a hydrogen atom, halogen, cyano group, C1 to C30 straight chain alkyl group, C3 to C30 branched alkyl group, C1 to C30 silyl group, C2 to C30 ester group, C1 to C30 alkoxy group, C1 to C30 Thioalkyl group, C1-C30 haloalkyl group, C2-C30 alkene group, C2-C30 alkyne group, C2-C30 cyano group-containing hydrocarbon group, C1-C30 nitro group-containing hydrocarbon group, C1-C30 hydroxy group-containing hydrocarbon group , and C3-C30 keto group-containing hydrocarbon groups. 2. The organic semiconducting polymer of claim 1, wherein the optical bandgap Eg ^opt of the organic semiconducting polymer in the form of a thin film is less than 0.9 eV. A substrate and
an electrode module disposed on the substrate and comprising a first electrode and a second electrode;
an active layer disposed between the first electrode and the second electrode and comprising at least one of the organic semiconductor polymers according to claim 1;
Equipped with
at least one of the electrodes, including the first electrode and the second electrode, is made from a transparent or translucent material;
Organic optoelectronic devices. 8. The organic optoelectronic device according to claim 7, wherein the first electrode, the active layer and the second electrode are arranged sequentially from bottom to top on the substrate. 8. The organic optoelectronic device according to claim 7, wherein the second electrode, the active layer and the first electrode are arranged sequentially from bottom to top on the substrate. 7. The active layer comprises at least one p-type organic semiconductor polymer and at least one n-type organic semiconductor compound, and the p-type organic semiconductor polymer comprises the polymer according to claim 1. The organic optoelectronic device described in . 8. The organic optoelectronic device according to claim 7, wherein the optical bandgap E _g ^opt of at least one of the n-type semiconductor compounds is 2.0 eV or less.

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