阅读说明：本技术 一种双氮杂晕苯二酰亚胺n-型聚合物及其制备方法和用途 (Dinitroaza-coronene diimide n-type polymer and preparation method and application thereof ) 是由 王士凡 孙华 董黎明 堵锡华 么冰 臧运晓 于 2021-08-27 设计创作，主要内容包括：本发明公开了一种双氮杂晕苯二酰亚胺n-型聚合物及其制备方法和用途,其结构通式如式I-a或I-b所示：其中：n为小于等于100万的正整数；X选自氧、硫、硒；R1、R2彼此独立地选自氢、氟、氯、C1-C12的取代或未取代的烷基；R3选自C1-C30的取代或未取代的烷基、C2-C30的取代或未取代的烯基、C2-C30的取代或未取代的炔基、C3-C30取代或未取代的环烷基、C6-C60取代或未取代的芳基、C3-C30取代或未取代的杂环芳基、C1-C30取代或未取代的烷氧基、C1-C30取代或未取代的硅烷基；L选自氢或乙烯基。本发明的基于双氮杂晕苯二酰亚胺的聚合物具有更大的平面核心和更多扩展的共轭结构。(The invention discloses a dinitroaza halo diimide n-type polymer, a preparation method and application thereof, wherein the general structural formula is shown as formula I-a or I-b: wherein: n is a positive integer less than or equal to 100 ten thousand; x is selected from oxygen, sulfur and selenium; r1, R2 are independently from each other selected from hydrogen, fluorine, chlorine, C1-C12 substituted or unsubstituted alkyl; r3 is selected from C1-C30 substituted or unsubstituted alkyl, C2-C30 substituted or unsubstituted alkenyl, C2-C30 substituted or unsubstituted alkynyl, C3-C30 substituted or unsubstituted cycloalkyl, C6-C60 substituted or unsubstituted aryl, C3-C30 substituted or unsubstituted heterocyclic aryl, C1-C30 substituted or unsubstituted alkoxy, C1-C60 substituted or unsubstituted alkoxy30 substituted or unsubstituted silane groups; l is selected from hydrogen or vinyl. The dinitroaza-coronene diimide-based polymers of the present invention have a larger planar core and more extended conjugated structures.)

1. A dinitroaza coronenimide n-type polymer characterized by: the structural general formula is shown as formula I-a or I-b:

wherein:

n is a positive integer less than or equal to 100 ten thousand;

x is selected from oxygen, sulfur and selenium;

r1, R2 are independently from each other selected from hydrogen, fluorine, chlorine, C1-C12 substituted or unsubstituted alkyl;

r3 is selected from C1-C30 substituted or unsubstituted alkyl, C2-C30 substituted or unsubstituted alkenyl, C2-C30 substituted or unsubstituted alkynyl, C3-C30 substituted or unsubstituted cycloalkyl, C6-C60 substituted or unsubstituted aryl, C3-C30 substituted or unsubstituted heterocyclic aryl, C1-C30 substituted or unsubstituted alkoxy, C1-C30 substituted or unsubstituted silyl;

l is vinyl.

2. The diaza-halodiimide n-type polymer of claim 1, wherein: the polymer is one of structures shown in formulas I-1 to I-8:

3. a method of preparing a diaza-halodiimide n-type polymer of claim 1, wherein: the method comprises the following steps:

(1) preparing a compound III from a compound IV of a compound V formula by a Pictet-Spengler reaction;

(2) carrying out coupling reaction on compound III and compound II raw materials under the action of a catalyst to obtain a compound I; the reaction formula is as follows:

4. the method of preparing a diaza-coronene diimide n-type polymer according to claim 3, wherein: the catalyst is Pd (PPh)₃)₄。

5. Use of the diaza-halobenzimide n-type polymer of claim 1 in an organic semiconductor.

6. Use according to claim 5, characterized in that: the polymer is used as an active layer material of an organic solar cell and an organic field effect transistor.

Technical Field

The invention belongs to the technical field of high-molecular photoelectric materials, and particularly relates to an n-type polymer based on a main chain structure of dinitrodiazo coronene diimide, and a preparation method and application thereof.

Background

The organic semiconductor is a core component of organic electroluminescent devices, Organic Field Effect Transistors (OFETs), organic solar cells, organic photodetectors, memories and logic circuits, has wide application prospects, and is a hotspot in the research field of organic photoelectric functional materials and devices. Organic semiconductor materials are largely classified into hole transport type (p-type) materials and electron transport type (n-type) materials according to the kind of carriers. The organic semiconductor material reported in the literature is mainly a p-type material, and the material is relatively stable in air and has relatively high hole mobility. The n-type organic semiconductor is relatively few, the performance is not high, most of n-type materials are sensitive to air, when a positive electric field is applied, negative ions, particularly carbanions, induced on the interface of the semiconductor and the insulating layer easily react with oxygen and water in the air, and the prepared device is poor in stability, so that the practical application of the device is limited. The high-performance n-type material can be used for preparing p-n junctions, bipolar transistors, complementary logic circuits, organic photovoltaic devices and the like. Therefore, designing and synthesizing n-type organic semiconductor materials with high mobility, high stability and good processability is a great challenge in the preparation and application research of organic electronic devices.

Perylene diimides (PBI) are important n-type semiconductor materials and have many applications in organic electronics. As a derivative of PBI, coronene diimide (CBI) has also attracted considerable research interest. On the one hand, like PBI, CBI derivatives and analogs exhibit lower LUMO orbital energies, facilitating electron acceptance and transport. CBI, on the other hand, has a larger planar core and more extended conjugated structures than PBI, which can have a significant impact on electron distribution properties and the ability to self-assemble into ordered supramolecular structures, which contributes to improved device performance. In fact, CBI-based polymers exhibit better mobility in organic field effect transistors and higher power conversion efficiency in organic solar cells. The general idea of developing novel PBI analogs by using perylene tetracene as a starting material and perylene dianhydride as a key intermediate has been proved to be reasonable and effective, so that the general idea should be popularized and developed into efficient n-type semiconductor materials.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide a dinitroaza coronendiimide n-type polymer and a preparation method and application thereof.

In order to achieve the purpose, the invention adopts the following technical scheme:

a dinitroaza halo diimide n-type polymer, its structural formula is shown as formula I-a or I-b:

wherein:

n is a positive integer less than or equal to 100 ten thousand;

x is selected from oxygen, sulfur and selenium;

r1, R2 are independently from each other selected from hydrogen, fluorine, chlorine, C1-C12 substituted or unsubstituted alkyl;

r3 is selected from C1-C30 substituted or unsubstituted alkyl, C2-C30 substituted or unsubstituted alkenyl, C2-C30 substituted or unsubstituted alkynyl, C3-C30 substituted or unsubstituted cycloalkyl, C6-C60 substituted or unsubstituted aryl, C3-C30 substituted or unsubstituted heterocyclic aryl, C1-C30 substituted or unsubstituted alkoxy, C1-C30 substituted or unsubstituted silyl;

l is vinyl.

Preferably, the polymer is one of the structures shown in formulas I-1 to I-8:

a method for preparing a dinitroaza coronene diimide n-type polymer comprises the following steps:

(1) preparing a compound III from a compound IV of a compound V formula by a Pictet-Spengler reaction;

(2) carrying out coupling reaction on compound III and compound II raw materials under the action of a catalyst to obtain a compound I; the reaction formula is as follows:

the use of the bis-aza-halosdiimide n-type polymer of the present invention in organic semiconductors. Specifically, the polymer is used as an active layer material of an organic solar cell and an organic field effect transistor.

The organic field effect transistor device is of a top gate/bottom contact device structure, the top gate/bottom contact device structure has a good packaging effect, and the n-type characteristic of the device can be enhanced; chromium or gold is used as a source electrode and a drain electrode respectively; silicon dioxide/silicon base modified by Octadecyl Trichlorosilane (OTS) is selected as a substrate. The n-type semiconductor layer is prepared by a spin coating method, and the molecular stacking arrangement and the device performance are further improved by solvent selection, solvent blending and other methods.

Has the advantages that: compared with the prior art, the invention has the advantages that:

(1) compared with the halo diimide, the dinitroaza halo diimide provided by the invention has higher LUMO energy level, lower HOMO energy level and expanded pi electron cloud distribution, and the positive change can ensure that a novel polymer based on the dinitroza halo diimide has good light absorption characteristic and more flexible energy level adjustability, and meanwhile, the electron-withdrawing property of a pyridine ring can ensure the n-type characteristic of the compound.

(2) The dinitroaza-halo-phenyl diimide provided by the invention has a larger planar core and more expanded conjugated structures, can have great influence on the electron distribution characteristics and the capability of self-assembling into an ordered supermolecular structure, and is beneficial to improving the device performance.

(3) The polymer based on the dinitroaza-coronene diimide has good mobility in an organic field effect transistor and good photoelectric conversion efficiency in an organic solar cell.

Drawings

FIG. 1 is a schematic diagram of an organic field effect transistor device structure;

fig. 2 is a schematic structural diagram of an organic solar cell device.

Detailed Description

The present invention will be further explained with reference to examples.

The present invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the specific material ratios, process conditions and results thereof described in the examples are illustrative only and should not be taken as limiting the invention as detailed in the claims.

Example 1

This example provides an n-type polymer of diaza-halobenzimide having the structure shown in formula I-1 below:

the synthetic route for n-type polymer I-1 of diaza-halodiimide is shown below:

the preparation method of the n-type polymer I-1 of the dinitroaza coronene diimide specifically comprises the following steps:

0.12mmol of compound III-1,0.12mmol of hexa-n-butylditin, 6.0mg of Pd (PPh)₃)₄Adding into a 10mL Schlenk tube, adding 1.9mL of dry toluene and 0.5mL of dry N, N-Dimethylformamide (DMF) under the protection of nitrogen, stirring at 120 ℃ for reacting overnight, cooling to room temperature, pouring the solution into 100mL of methanol for precipitation, performing suction filtration, and performing Soxhlet extraction on the product by sequentially using methanol and acetone. And finally collecting the chloroform for concentration, re-precipitating in methanol, and filtering. The purified product was dried under vacuum to give a dark solid with about 86% yield. Elemental analysis: (C)₈₂H₁₀₆Br₂N₄O₄S₂) Theoretical value C, 77.07; h, 8.52; n, 4.38; found C, 77.10; h, 8.51; n,4.46, GPC (CHCl)₃):M_n/M_w＝14.2/37.2kg/mol.。

Synthesis procedure of Compound III-1: adding 0.5mmol of 5-bromothiophene-2-formaldehyde, 0.2mmol of compound V-1 and a proper amount of iodine into a 50mL Schlenk tube, adding 30mL of dried tetrahydrofuran under the protection of nitrogen, irradiating by an ultraviolet lamp, stirring at 50 ℃ for reacting overnight, cooling to room temperature, extracting, and purifying by column chromatography to obtain a compound III-1 with the yield of about 85%. Elemental analysis (C)₈₂H₁₀₆Br₂N₄O₄S₂) Theoretical value C, 68.60; h, 7.44; n, 3.90; found C, 68.72; h, 7.34; n,3.87, HRMS (ESI) M/z (M +): theoretical value 1432.60; found 1432.81.

Example 2

This example provides an n-type polymer of diaza-halobenzimide having the structure shown in formula I-2 below:

the synthetic route for n-type polymer I-2 of diaza-halodiimide is shown below:

the preparation method of the n-type polymer I-2 of the dinitroaza coronene diimide specifically comprises the following steps:

0.12mmol of Compound III-2, 0.12mmol of hexa-n-butylditin, 6.0mg of Pd (PPh)₃)₄Adding into a 10mL Schlenk tube, adding 1.9mL of dry toluene and 0.5mL of dry DMF under the protection of nitrogen, stirring at 120 ℃ for reacting overnight, cooling to room temperature, pouring the solution into 100mL of methanol for precipitation, performing suction filtration, and performing Soxhlet extraction on the product by sequentially using methanol and acetone. And finally collecting the chloroform for concentration, re-precipitating in methanol, and filtering. The purified product was dried under vacuum to give a dark solid with about 80% yield. Elemental analysis (C)₈₂H₁₀₈N₄O₆) Theoretical value C, 79.06; h, 8.74; n, 4.50; found 78.87 for C; h, 8.34; n,4.45, GPC (CHCl)₃):M_n/M_w＝12.2/36.2kg/mol。

Synthesis procedure of Compound III-2: adding 0.5mmol of 5-bromofuran-2-formaldehyde, 0.2mmol of compound V-1 and a proper amount of iodine into a 50mL Schlenk tube, adding 30mL of dried tetrahydrofuran under the protection of nitrogen, irradiating by an ultraviolet lamp, stirring at 50 ℃ for reacting overnight, cooling to room temperature, extracting, and purifying by column chromatography to obtain a compound III-2 with the yield of about 88%. Elemental analysis (C)₈₂H₁₀₆Br₂N₄O₄S₂) Theoretical value C, 70.17; h, 7.61; n, 3.99; found C, 70.22; h, 7.56; n,3.78, HRMS (ESI) M/z (M +): theoretical value 1400.65; found 1400.21.

Example 3

This example provides an n-type polymer of diaza-halobenzimide having the structure shown in formula I-3 below:

the synthetic route for n-type polymer I-3 of diaza-halodiimide is shown below:

the preparation method of the n-type polymer I-3 of the dinitroaza coronene diimide specifically comprises the following steps: 0.12mmol of the compound III-3, 0.12mmol of hexa-n-butylditin, 6.0mg of Pd (PPh)₃)₄Adding into a 10mL Schlenk tube, adding 1.9mL of dry toluene and 0.5mL of dry DMF under the protection of nitrogen, stirring at 120 ℃ for reacting overnight, cooling to room temperature, pouring the solution into 100mL of methanol for precipitation, performing suction filtration, and performing Soxhlet extraction on the product by sequentially using methanol and acetone. And finally collecting the chloroform for concentration, re-precipitating in methanol, and filtering. The purified product was dried under vacuum to give a dark solid with about 78% yield. Elemental analysis (C)₈₂H₁₀₈N₄O₄Se₂) Theoretical value C, 71.80; h, 7.94; n, 4.08; found C, 71.54; h, 7.34; n,4.01, GPC (CHCl)₃):M_n/M_w＝10.2/30.1kg/mol。

Synthesis procedure for Compound III-3: adding 0.5mmol of 5-bromoselenol-2-formaldehyde, 0.2mmol of compound V-1 and a proper amount of iodine into a 50mL Schlenk tube, adding 30mL of dried tetrahydrofuran under the protection of nitrogen, irradiating by an ultraviolet lamp, stirring at 50 ℃ for reacting overnight, cooling to room temperature, extracting, and purifying by column chromatography to obtain a compound III-3 with the yield of about 82%. Elemental analysis (C)₈₂H₁₀₆Br₂N₄O₄Se₂) Theoretical value C, 64.39; h, 6.99; n, 3.66; found C, 64.22; h, 6.32; n,3.24, HRMS (ESI) M/z (M +): theoretical value 1528.49; found 1529.79.

Example 4

This example provides an n-type polymer of diaza-halobenzimide having the structure shown in formula I-4 below:

the synthetic route for n-type polymer I-4 of diaza-halodiimide is shown below:

the preparation method of the n-type polymer I-4 of the dinitroaza coronene diimide specifically comprises the following steps: 0.12mmol of Compound III-1, 0.12mmol of trans-1, 2-bis (tributyltin) ethylene, 6.0mg of Pd (PPh)₃)₄Adding into a 10mL Schlenk tube, adding 1.9mL of dry toluene and 0.5mL of dry DMF under the protection of nitrogen, stirring at 120 ℃ for reacting overnight, cooling to room temperature, pouring the solution into 100mL of methanol for precipitation, performing suction filtration, and performing Soxhlet extraction on the product by sequentially using methanol and acetone. And finally collecting the chloroform for concentration, re-precipitating in methanol, and filtering. The purified product was dried under vacuum to give a dark solid with about 87% yield. Elemental analysis (C)₈₅H₁₁₂N₄O₄S₂) Theoretical value C, 77.46; h, 8.57; n, 4.25; found C, 77.01; h, 8.02; n,4.65, GPC (CHCl)₃):M_n/M_w＝21.2/57.2kg/mol。

Example 5

This example provides an n-type polymer of diaza-halobenzimide having the structure shown in formula I-5 below:

the synthetic route for n-type polymer I-5 of diaza-coronene diimide is shown below:

the preparation method of the n-type polymer I-5 of the dinitroaza coronene diimide specifically comprises the following steps: 0.12mmol of the compound III-5, 0.12mmol of hexa-n-butylditin, 6.0mg of Pd (PPh)₃)₄Adding into a 10mL Schlenk tube, adding 1.9mL of dry toluene and 0.5mL of dry DMF under the protection of nitrogen, stirring at 120 ℃ for reacting overnight, cooling to room temperature, pouring the solution into 100mL of methanol for precipitation, filtering, and sequentially using the productSoxhlet extraction of methanol and acetone was performed. And finally collecting the chloroform for concentration, re-precipitating in methanol, and filtering. The purified product was dried under vacuum to give a dark solid with about 82% yield. Elemental analysis (C)₈₂H₁₀₆F₂N₄O₄S₂) Theoretical value C, 74.96; h, 8.13; n, 4.26; found C, 74.43; h, 8.32; n,4.65, GPC (CHCl)₃):M_n/M_w＝18.1/33.2kg/mol。

Synthesis procedure for Compound III-5: adding 0.5mmol of 4-fluoro-5-bromothiophene-2-formaldehyde, 0.2mmol of compound V-1 and a proper amount of iodine into a 50mL Schlenk tube, adding 30mL of dried tetrahydrofuran under the protection of nitrogen, irradiating by an ultraviolet lamp, stirring at 50 ℃ for reacting overnight, cooling to room temperature, extracting, and purifying by column chromatography to obtain the compound shown as the formula III-5, wherein the yield is about 84%. Elemental analysis (C)₈₂H₁₀₄Br₂F₂N₄O₄S₂) Theoretical value C, 66.92; h, 7.12; n, 3.81; found C, 66.32; h, 7.32; n,3.19, HRMS (ESI) M/z (M +): theoretical value 1468.58; found 1469.08.

Example 6

This example provides an n-type polymer of diaza-halobenzimide having the structure shown in formula I-6 below:

the synthetic route for n-type polymer I-6 of diaza-halodiimide is shown below:

the preparation method of the n-type polymer I-6 of the dinitroaza coronene diimide specifically comprises the following steps: 0.12mmol of Compound III-6, 0.12mmol of hexa-n-butylditin, 6.0mg of Pd (PPh)₃)₄Adding into a 10mL Schlenk tube, adding 1.9mL dry toluene and 0.5mL dry DMF under nitrogen protection, and stirringReacting at 120 ℃ overnight, cooling to room temperature, pouring the solution into 100mL of methanol for precipitation, performing suction filtration, and performing Soxhlet extraction on the product by sequentially using methanol and acetone. And finally collecting the chloroform for concentration, re-precipitating in methanol, and filtering. The purified product was dried under vacuum to give a dark solid with about 82% yield. Elemental analysis (C)₈₂H₁₀₆Cl₂N₄O₄S₂) Theoretical value C, 73.13; h, 7.93; n, 4.16; found C, 73.10; h, 7.74; n,4.23, GPC (CHCl)₃):M_n/M_w＝17.3/31.4kg/mol。

Synthesis procedure for Compound III-6: adding 0.5mmol of 4-chloro-5-bromothiophene-2-formaldehyde, 0.2mmol of compound V-1 and a proper amount of iodine into a 50mL Schlenk tube, adding 30mL of dried tetrahydrofuran under the protection of nitrogen, irradiating by an ultraviolet lamp, stirring at 50 ℃ for reacting overnight, cooling to room temperature, extracting, and purifying by column chromatography to obtain the compound shown as the formula III-6, wherein the yield is about 84%. Elemental analysis (C)₈₂H₁₀₄Br₂Cl₂N₄O₄S₂) Theoretical value C, 65.46; h, 6.97; n, 3.72; found C, 65.12; h, 6.76; n,3.42, HRMS (ESI) M/z (M +): theoretical value 1500.52; found 1500.23.

Example 7

This example provides an n-type polymer of diaza-halobenzimide having the structure shown in formula I-7 below:

the synthetic route for n-type polymer I-7 of diaza-halodiimide is shown below:

the preparation method of the n-type polymer I-7 of the dinitroaza coronene diimide specifically comprises the following steps: 0.12mmol of the compound III-7, 0.12mmol of hexa-n-butylditin, 6.0mg of Pd (PPh)₃)₄Adding into a 10mL Schlenk tube, adding 1.9mL of dry toluene and 0.5mL of dry DMF under the protection of nitrogen, stirring at 120 ℃ for reacting overnight, cooling to room temperature, pouring the solution into 100mL of methanol for precipitation, performing suction filtration, and performing Soxhlet extraction on the product by sequentially using methanol and acetone. And finally collecting the chloroform for concentration, re-precipitating in methanol, and filtering. The purified product was dried under vacuum to give a dark solid with about 90% yield. Elemental analysis (C)₉₄H₁₃₂N₄O₄S₂) Theoretical value C, 78.07; h, 9.20; n, 3.87; found C, 78.12; h, 9.32; n,3.67, GPC (CHCl)₃):M_n/M_w＝27.4/39.4kg/mol。

Synthesis procedure for Compound III-7: adding 0.5mmol of 4-hexyl-5-bromothiophene-2-formaldehyde, 0.2mmol of compound V-1 and a proper amount of iodine into a 50mL Schlenk tube, adding 30mL of dried tetrahydrofuran under the protection of nitrogen, irradiating by an ultraviolet lamp, stirring at 50 ℃ for reacting overnight, cooling to room temperature, extracting, and purifying by column chromatography to obtain a compound III-7 with the yield of about 82%. Elemental analysis (C)₉₄H₁₃₀Br₂N₄O₄S₂) Theoretical value C, 70.39; h, 8.17; n, 3.49; found C, 70.12; h, 8.37; n,3.67, HRMS (ESI) M/z (M +): theoretical value 1600.79; found 1601.03.

Example 8

This example provides an n-type polymer of diaza-halobenzimide having the structure shown in formula I-8 below:

the synthetic route for n-type polymer I-8 of diaza-halodiimide is shown below:

the preparation method of the n-type polymer I-8 of the dinitroaza coronene diimide specifically comprises the following steps: 0.12mmol of compound III-8,0.12mmol of hexa-n-butylditin, 6.0mg of Pd (PPh)₃)₄Adding into a 10mL Schlenk tube, adding 1.9mL of dry toluene and 0.5mL of dry DMF under the protection of nitrogen, stirring at 120 ℃ for reacting overnight, cooling to room temperature, pouring the solution into 100mL of methanol for precipitation, performing suction filtration, and performing Soxhlet extraction on the product by sequentially using methanol and acetone. And finally collecting the chloroform for concentration, re-precipitating in methanol, and filtering. The purified product was dried under vacuum to give a dark solid with about 80% yield. Elemental analysis (C)₈₂H₁₀₄F₄N₄O₄S₂) Theoretical value C, 72.96; h, 7.77; n, 4.15; found C, 72.43; h, 7.65; n,4.23, GPC (CHCl)₃):M_n/M_w＝12.1/31.2kg/mol。

The synthesis steps of the compound shown as the compound III-8 are as follows: adding 0.5mmol of 3, 4-2-fluoro-5-bromothiophene-2-formaldehyde, 0.2mmol of a compound shown as a compound V-1 and a proper amount of iodine into a 50mL Schlenk tube, adding 30mL of dried tetrahydrofuran under the protection of nitrogen, irradiating by an ultraviolet lamp, stirring at 50 ℃ for reacting overnight, cooling to room temperature, extracting, and purifying by column chromatography to obtain a compound III-8 with the yield of about 82%. Elemental analysis (C)₈₂H₁₀₂Br₂F₄N₄O₄S₂) Theoretical value C, 65.33; h, 6.82; n, 3.72; found C, 65.51; h, 6.52; n,3.34, HRMS (ESI) M/z (M +): theoretical value 1504.56; found 1504.03.

Example 9

This example provides an n-type polymer of diaza-halobenzimide having the structure shown in formula I-9 below:

the synthetic route for n-type polymer I-9 of diaza-coronene diimide is shown below:

the preparation method of the n-type polymer I-9 of the dinitroaza coronene diimide specifically comprises the following steps: 0.12mmol of the compound III-8, 0.12mmol of trans-1, 2-bis (tributyltin) ethylene, 6.0mg of Pd (PPh)₃)₄Adding into a 10mL Schlenk tube, adding 1.9mL of dry toluene and 0.5mL of dry DMF under the protection of nitrogen, stirring at 120 ℃ for reacting overnight, cooling to room temperature, pouring the solution into 100mL of methanol for precipitation, performing suction filtration, and performing Soxhlet extraction on the product by sequentially using methanol and acetone. And finally collecting the chloroform for concentration, re-precipitating in methanol, and filtering. The purified product was dried under vacuum to give a dark solid with about 82% yield. Elemental analysis (C)₈₆H₁₁₀F₄N₄O₄S₂) Theoretical value C, 73.57; h, 7.90; n, 3.99; found C, 73.07; h, 7.42; n,3.12, GPC (CHCl)₃):M_n/M_w＝10.1/28.1kg/mol。

Example 10

This example provides an n-type polymer of diaza-halobenzimide having the structure shown in formula I-10 below:

the synthetic route for n-type polymer I-10 of diaza-halodiimide is shown below:

the preparation method of the n-type polymer I-10 of the dinitroaza coronene diimide specifically comprises the following steps: 0.12mmol of the compound III-9, 0.12mmol of trans-1, 2-bis (tributyltin) ethylene, 6.0mg of Pd (PPh)₃)₄Adding into a 10mL Schlenk tube, adding 1.9mL of dry toluene and 0.5mL of dry DMF under the protection of nitrogen, stirring at 120 ℃ for reacting overnight, cooling to room temperature, pouring the solution into 100mL of methanol for precipitation, performing suction filtration, and performing Soxhlet extraction on the product by sequentially using methanol and acetone. Finally collecting trichloromethane for concentrationReprecipitating in methanol, filtering. The purified product was dried under vacuum to give a dark solid with about 85% yield. Elemental analysis (C)₈₆H₁₁₀C_l4N₄O₄S₂) Theoretical value C, 70.28; h, 7.54; n, 3.81; found C, 70.10; h, 7.24; n,3.91, GPC (CHCl)₃):M_n/M_w＝11.3/29.1kg/mol。

Synthesis procedure for Compound III-9: adding 0.5mmol of 3, 4-dichloro-5-bromothiophene-2-formaldehyde, 0.2mmol of compound V-1 and a proper amount of iodine into a 50mL Schlenk tube, adding 30mL of dried tetrahydrofuran under the protection of nitrogen, irradiating by an ultraviolet lamp, stirring at 50 ℃ for reacting overnight, cooling to room temperature, extracting, and purifying by column chromatography to obtain the compound shown as the formula III-6, wherein the yield is about 89%. Elemental analysis (C)₈₂H₁₀₂Br₂C_l4N₄O₄S₂) Theoretical value C, 62.59; h, 6.53; n, 3.56; found C, 62.12; h, 6.32; n,3.76, HRMS (ESI) M/z (M +): theoretical value 1568.45; found 1568.23.

Example 11

This example provides an organic field effect transistor device, as shown in FIG. 2, on SiO₂And constructing a device with a top gate and bottom contact structure on the carrier. Octadecyltrichlorosilane (OTS) modified silicon dioxide as a substrate, and a chromium/gold (3 nm/10nm, respectively) source electrode and drain electrode were prepared by photolithography, with a channel length L of 20 μm and a width W of 1 mm. A thin film of the organic semiconductor layer was drawn from CHCl at 3000rpm₃The solution (about 6mg/mL) was cast and annealed in a glove box at 180 ℃ for 10 minutes. The Cytop acts as a dielectric layer. The characteristics of the OFET devices were measured using an Agilent 4155B semiconductor parameter analyzer. The mobility was determined in the saturated state using the following formula: i is_DS＝(μWC_i/2L)(V_G-V_T)²Wherein I_DSIs the drain-source current, μ is the field effect mobility, W is the channel width, L is the channel length, C_iIs the capacitance per unit area, V, of the gate dielectric layer_TIs the threshold voltage.

The organic semiconductor layer was formed using the bis-aza-halo-phthalimide n-type polymer synthesized in the above example, respectively, and the organic field effect transistor device performance parameters are shown in table 1:

TABLE 1

Example 12

This example provides a polymer solar cell device structure (ITO/PEDOT: PSS/active layer/LiF/Al). about 35nm of PEDOT: PSS (Baytron P4083) was first spin coated onto an ITO substrate, then a 10mg/mL solution of polymer (PM6: bis aza coronene diimide n-type polymer) in chlorobenzene was spin coated onto PEDOT: PSS as the active layer, about 85nm, the sample was transferred to a vacuum evaporation system, 1nm of LiF and 100nm of Al were thermally deposited as the cathode, and the effective area of each device was about 0.12cm². The J-V curve of this example was measured using Keithley 236 and controlled by computer using Lab View software. A xenon lamp is matched with an AM1.5G filter to be used as a white light source for simulating sunlight, and the light source is corrected to be 100mW/cm by a standard silicon cell (Hamamatsu S1133)². The testing of the J-V curves of the devices was performed in a glove box. External quantum efficiency was measured automatically under computer control using a lock-in amplifier equipped with a chopper (SR830, Stanford Research System), 75W xenon lamp. The characteristic parameters can be read from the J-V curve: open circuit voltage (V)_oc) Short-circuit current (J)_sc) Meanwhile, the Filling Factor (FF) and the Photoelectric Conversion Efficiency (PCE) of the device can be calculated.

The organic semiconductor layer was prepared from the dinitroaza-triphenyldiimide n-type polymer synthesized in the above example, and the performance parameters of the organic solar cell device are shown in table 2:

TABLE 2

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.