阅读说明：本技术 含醌式-给体-受体单元的聚合物半导体及其制备和应用 (Polymer semiconductors containing quinoid donor-acceptor units, their preparation and use ) 是由 刘迅成 刘成 梁欢欢 于 2021-09-15 设计创作，主要内容包括：本发明公开了一种含醌式-给体-受体单元的聚合物半导体及其制备和应用。其合成方法是将(3Z,6Z)-3,6-双((5-溴噻吩-2-基)亚甲基)哌嗪-2,5-二酮、碳酸钾和烷基溴或烷基碘混合在N,N-二甲基甲酰胺中,在惰性气体下反应,冷却,抽滤,将滤液蒸发浓缩,过硅胶柱层析,用无水乙醇重结晶得到产物,将产物溶于干燥的四氢呋喃溶液中,冷却,滴加正丁基锂,搅拌反应,加入三甲基氯化锡,然后缓慢将温度升至室温,并搅拌,再用水淬灭反应,并用二氯甲烷萃取,干燥,过滤旋干,重结晶后获得油状的M品；再以M品为原料进行Stille偶联聚合反应来制备所述聚合物。本发明聚合物具有载流子迁移率高、合成简单、产率较高的特点,在有机光电领域具有很大的发展前景和潜力。(The invention discloses a polymer semiconductor containing a quinone type donor-acceptor unit, and preparation and application thereof. Mixing (3Z, 6Z) -3, 6-bis ((5-bromothiophene-2-yl) methylene) piperazine-2, 5-diketone, potassium carbonate and alkyl bromide or alkyl iodide in N, N-dimethylformamide, reacting under the action of inert gas, cooling, performing suction filtration, evaporating and concentrating filtrate, performing silica gel column chromatography, recrystallizing by using absolute ethyl alcohol to obtain a product, dissolving the product in a dry tetrahydrofuran solution, cooling, dropwise adding N-butyl lithium, stirring for reaction, adding trimethyltin chloride, slowly raising the temperature to room temperature, stirring, quenching the reaction by using water, extracting by using dichloromethane, drying, filtering, spin-drying, and recrystallizing to obtain an oily M product; and performing Stille coupling polymerization reaction on the M product serving as a raw material to prepare the polymer. The polymer has the characteristics of high carrier mobility, simple synthesis and high yield, and has great development prospect and potential in the field of organic photoelectricity.)

1. A polymeric semiconductor comprising a quinone-donor-acceptor unit, characterized by the general chemical structure:

wherein A is any one of the following structural formulas:

r is C1-C60 alkyl.

2. A process for the preparation of a polymeric semiconductor containing a quinoid-donor-acceptor unit according to claim 1, comprising the steps of:

1) adding (3Z, 6Z) -3, 6-bis ((5-bromothiophene-2-yl) methylene) piperazine-2, 5-diketone, potassium carbonate, alkyl bromide or alkyl iodide and dried N, N-dimethylformamide into a reaction bottle under the condition of inert gas, heating for reaction, cooling to room temperature, carrying out suction filtration to obtain a filtrate, evaporating and concentrating the filtrate, carrying out silica gel column chromatography, carrying out spin drying, recrystallizing with absolute ethyl alcohol to obtain a product, dissolving the product in a dried tetrahydrofuran solution, cooling and freezing under the condition of inert gas, slowly dropwise adding N-butyl lithium, stirring for 1-2 hours, adding trimethyltin chloride, slowly heating to room temperature, stirring for 10-15 hours, quenching the reaction with water, extracting with dichloromethane, drying without water, after the solvent is dried by spinning, the solvent is recrystallized by absolute ethyl alcohol to obtain an oily M product;

2) performing Stille coupling polymerization reaction on the M product serving as a raw material and the compound A to prepare a polymer semiconductor with a main chain containing a quinoid-donor-acceptor unit; wherein compound a is any one of the following structural formulas:

3. a process for the preparation of a polymeric semiconductor containing a quinoid-donor-acceptor unit according to claim 2, characterized in that: the n-butyllithium in the step 1) was a hexane solution having a concentration of 1.6 mol/L.

4. A process for the preparation of a polymeric semiconductor containing a quinoid-donor-acceptor unit according to claim 2, characterized in that: step 1) the (3Z, 6Z) -3, 6-bis ((5-bromothien-2-yl) methylene) piperazine-2, 5-dione, potassium carbonate, alkyl bromide or iodide, and dried N, N-dimethylformamide were added to a reaction flask, followed by stirring at 90 to 110 ℃ for 2 hours.

5. A process for the preparation of a polymeric semiconductor containing a quinoid-donor-acceptor unit according to claim 2, characterized in that: the evaporation concentration in the step 1) is reduced pressure rotary evaporation concentration.

6. A process for the preparation of a polymeric semiconductor containing a quinoid-donor-acceptor unit according to claim 2, characterized in that: performing silica gel column chromatography in the step 1), wherein the eluent is hexane/dichloromethane with the ratio of 9:1 to 3: 1.

7. A process for the preparation of a polymeric semiconductor containing a quinoid-donor-acceptor unit according to claim 2, characterized in that: step 1), the temperature reduction and freezing are carried out until the temperature is reduced to-78 ℃; the stirring time after the n-butyllithium is added is 1.5 hours; after warming to room temperature, the mixture was stirred for 12 hours.

8. A process for the preparation of a polymeric semiconductor containing a quinoid-donor-acceptor unit according to claim 2, characterized in that: the Stille coupling polymerization reaction process is as follows: under the condition of inert gas, adding M, compound A and tris (dibenzylideneacetone) dipalladium [ Pd ]₂(dba)₃]Dissolving tri (o-methylphenyl) phosphorus in anhydrous toluene, ventilating for 30 min, heating the solution to reflux, reacting for 72 h, adding 2-trimethyltin thiophene for end capping when the reaction is finished, removing all bromine groups, adding 2-bromothiophene for end capping after 3 h, and removing bromine groupsCooling all trimethyl tin groups to room temperature, precipitating the mixture with methanol, filtering, sequentially performing Soxhlet extraction on the obtained precipitate with methanol, acetone, ethyl acetate, chloroform and chlorobenzene, evaporating the solvent of the polymer solution obtained by the Soxhlet extraction in a rotary evaporator, concentrating, slowly adding the polymer solution into anhydrous methanol for separation, filtering, and drying in a vacuum drying oven at 40 ℃ for two days.

9. Use of a polymeric semiconductor containing a quinoid-donor-acceptor unit according to claim 1 as a semiconducting polymer.

Technical Field

The invention relates to a semiconductor polymer, in particular to a polymer semiconductor with a main chain containing quinoid-donor-acceptor units, a preparation method and application thereof.

Background

Semiconducting polymers are of interest because of their wide application in Organic Field Effect Transistors (OFETs), Organic Photovoltaics (OPVs) and other electronic devices. How to change the molecular structure to adjust the front rail energy level and achieve high carrier mobility is one of the most fundamental problems of semiconductor polymers. Currently, strategies have been proposed to improve carrier mobility by effectively controlling carrier hopping between chains and intra-chain transport efficiency, such as rational design of novel structural units, side-chain engineering, and optimization of active layer processing and device structure. In these attempts, the leading-edge orbital hybridization design strategy of the polymeric donor-acceptor (D-A) unit has been widely applied to modulate the optoelectronic properties.

In addition to D-A type polymers, quinoid units have optoelectronic properties such as electronic, optical, and magnetic properties, and therefore conjugated polymers containing quinoid (Q) units are receiving increasing attention. In the quinoid polymer, resonance between the quinoid structure and the aromatic structure results in minimization of Bond Length Alternation (BLA), which is achieved by reduction of the energy difference between the aromatic structure of the polymer and the quinoid structure. In addition, due to the high coplanarity of the polymer main chain, pi-orbital overlap can be enhanced, the effective conjugation length is increased, and pi-pi interaction between polymer chains is promoted, so that carrier transport is improved.

Despite the increasing interest in quinoid polymers, a few quinoid structural units are available for conjugated polymers, such as benzobispyrrolidinone and benzo [1,2-b:4,5-b ] bithiophene-2, 6-dione. These extended p-quinodimethane units are sufficiently stable and can be used as efficient structural units for constructing narrow band gap polymers. However, since they all contain an electron-withdrawing group having a carbonyl group at the terminal, the lowest occupied orbital (LUMO level) is significantly lowered, and as a result, the boundary between a pure p-quinodimethane (p-QM) structural unit and a conventional electron acceptor is blurred, and even if the strain is extended, a larger ring is formed, and steric hindrance may occur, which may affect the device properties of the polymer.

Disclosure of Invention

The invention aims to provide a polymer semiconductor containing a quinone type donor-acceptor unit, and preparation and application thereof. The polymer has the characteristics of high carrier mobility, simple synthesis and high yield, and has great development prospect and potential in the field of organic photoelectricity.

The technical scheme of the invention is as follows: a polymeric semiconductor having a main chain comprising quinoid-donor-acceptor units, having the general chemical structure:

wherein A is any one of the following structural formulas:

r is C1-C60 alkyl.

A method for preparing the aforementioned polymer semiconductor having a main chain containing a quinoid-donor-acceptor unit, comprising the steps of:

1) adding (3Z, 6Z) -3, 6-bis ((5-bromothiophene-2-yl) methylene) piperazine-2, 5-diketone, potassium carbonate, alkyl bromide or alkyl iodide and dried N, N-dimethylformamide into a reaction bottle under the condition of inert gas, heating for reaction, cooling to room temperature, carrying out suction filtration to obtain a filtrate, evaporating and concentrating the filtrate, carrying out silica gel column chromatography, carrying out spin drying, recrystallizing with absolute ethyl alcohol to obtain a product, dissolving the product in a dried tetrahydrofuran solution, cooling and freezing under the condition of inert gas, slowly dropwise adding N-butyl lithium, stirring for 1-2 hours, adding trimethyltin chloride, slowly heating to room temperature, stirring for 10-15 hours, quenching the reaction with water, extracting with dichloromethane, drying without water, after the solvent is dried by spinning, the solvent is recrystallized by absolute ethyl alcohol to obtain an oily M product;

2) performing Stille coupling polymerization reaction on the M product serving as a raw material and the compound A to prepare a polymer semiconductor with a main chain containing a quinoid-donor-acceptor unit; wherein compound a is any one of the following structural formulas:

in the aforementioned process for producing a polymer semiconductor having a main chain containing a quinoid-donor-acceptor unit, step 1) said n-butyllithium is a hexane solution having a concentration of 1.6 mol/L.

In the aforementioned method for preparing a polymer semiconductor having a main chain containing a quinoid-donor-acceptor unit, step 1) is performed by adding the (3Z, 6Z) -3, 6-bis ((5-bromothien-2-yl) methylene) piperazine-2, 5-dione, potassium carbonate, alkyl bromide or alkyl iodide, and dried N, N-dimethylformamide to a reaction flask, and then reacting the mixture with stirring at 90 to 110 ℃ for 2 hours.

In the preparation method of the polymer semiconductor with the main chain containing the quinoid-donor-acceptor unit, the evaporation concentration in the step 1) is reduced pressure rotary evaporation concentration.

The preparation method of the polymer semiconductor with the main chain containing the quinoid-donor-acceptor unit comprises the step 1) of silica gel column chromatography, wherein the eluent is hexane/dichloromethane in a ratio of 9:1 to 3: 1.

In the preparation method of the polymer semiconductor with the main chain containing the quinoid-donor-acceptor unit, the temperature reduction freezing in the step 1) is to reduce the temperature to-78 ℃; the stirring time after the n-butyllithium is added is 1.5 hours; after warming to room temperature, the mixture was stirred for 12 hours.

In the preparation method of the polymer semiconductor with the main chain containing the quinoid-donor-acceptor unit, the Stille coupling polymerization reaction process is as follows: under the condition of inert gas, adding M, compound A and tris (dibenzylideneacetone) dipalladium [ Pd ]₂(dba)₃]Dissolving tris (o-methylphenyl) phosphorus in anhydrous toluene, ventilating for 30 minutes, heating the solution to reflux, reacting for 72 hours, adding 2-trimethyltin thiophene end capping to remove all bromine groups when the reaction is finished, adding 2-bromothiophene end capping after 3 hours, removing all trimethyltin groups, cooling to room temperature, precipitating the mixture with methanol, filtering, sequentially performing Soxhlet extraction on the obtained precipitate with methanol, acetone, ethyl acetate, chloroform and chlorobenzene, evaporating the solvent of the polymer solution obtained by the Soxhlet extraction in a rotary evaporator, concentrating, slowly adding the polymer solution into anhydrous methanol for precipitation, filtering, and finally adding the polymer solution into a reactor for reactionDrying in a vacuum drying oven at 40 deg.C for two days.

The use of a polymer semiconductor having a main chain comprising quinoid-donor-acceptor units as described above as a semiconducting polymer.

The invention has the advantages of

1. The invention designs a polymer semiconductor with a main chain containing a quinoid-donor-acceptor unit by a quinoid-donor-acceptor (Q-D-A) design strategy, and the polymer has the advantage of high carrier mobility.

2. The invention has simple synthesis path and higher yield, and the yield of the product obtained by the Stille coupling polymerization reaction can reach 84 percent.

In conclusion, the polymer has the advantages of high carrier mobility, simplicity in synthesis and high yield, and has great development prospect and potential in the field of organic photoelectricity.

Drawings

FIG. 1 is a chemical structural formula of a quinoid-donor-acceptor polymer prepared in example 1 of the present invention;

FIG. 2 is a chemical structural formula of a prior donor-acceptor (D-A) polymer PT3B 1;

FIG. 3 is a chemical structural formula of a prior quinoid-donor (Q-D) polymer PAQM-3T;

Detailed Description

The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.

Examples of the invention

Example 1

The synthetic route is as above

1) Adding (3Z, 6Z) -3, 6-bis ((5-bromothiophene-2-yl) methylene) piperazine-2, 5-dione (1.6mmol, 1eq), potassium carbonate (8.0mmol, 5eq), alkyl bromide (6.4mmol, 4eq) and N, N-dimethylformamide (15mL) into a reaction bottle under the condition of inert gas, heating to 90-110 ℃, reacting for 2 hours, cooling to room temperature, carrying out suction filtration on a reaction mixture, concentrating a filtrate through silica gel column by reduced pressure rotary evaporation, carrying out chromatographic separation (the ratio of hexane to dichloromethane is 9:1 to 3: 1), carrying out recrystallization by using absolute ethyl alcohol after spin drying to obtain a required compound 1 which is an orange solid;

2) dissolving the compound 1(600mg, 0.53mmol, 1eq) in a dry tetrahydrofuran (40mL) solution under an inert gas condition, cooling to-78 ℃, slowly dropwise adding n-butyllithium (0.83mL, 1.6M, 2.5eq), stirring for reacting for 1-2 hours, adding trimethyltin chloride (1.43mL, 1M, 2.7eq), slowly raising the temperature of the mixture to room temperature, stirring for 10-15 hours, then quenching the reaction with water, extracting with dichloromethane, drying with anhydrous magnesium sulfate, filtering, spin-drying a solvent, and recrystallizing with anhydrous ethanol to obtain the oily target compound 2 with a yield of 96%;

3) under inert gas conditions, compound 2(0.306mmol, 1eq), compound 3(0.306mmol, 1eq) and tris (dibenzylideneacetone) dipalladium [ Pd ]₂(dba)₃]Dissolving (7mg) and tri (o-methylphenyl) phosphorus (9mg) in anhydrous toluene, ventilating for 30 minutes, heating the solution to reflux, reacting for 72 hours, adding 2-trimethyltin thiophene (0.1mL) for end capping at the end of polymerization reaction, removing all bromine groups, adding 2-bromothiophene (0.2mL) for end capping after 3 hours, removing all trimethyltin groups, cooling to room temperature after the reaction is finished, slowly adding the mixture into anhydrous methanol for precipitation, filtering, extracting and purifying the solid in a Soxhlet extractor by using methanol, acetone, ethyl acetate, chloroform and chlorobenzene in turn, evaporating the solvent in the solution obtained by Soxhlet extraction in a rotary evaporator, concentrating to 2mL, then slowly adding the mixture into 500mL of anhydrous methanol for precipitation, filtering, and drying in a vacuum drying oven at 40 ℃ for two days to obtain the novel quinoid-donor (Q-D-A) polymer (yield-84-A) %).

The polymer obtained in this example was named PAQM-BT, and the structural formula is shown in FIG. 1, and the other two semiconducting polymers are donor-acceptor (D-A) polymer PT3B1 (shown in FIG. 2) and quinoid-donor (Q-D) polymer PAQM-3T (shown in FIG. 3). Compared with PAQM-3T, PAQM-BT shows lower Highest Occupied Molecular Orbital (HOMO) energy level,Stronger backbone planarity, stronger interchain interactions and higher crystallinity, resulting in more efficient interchain charge hopping. In addition, PAQM-BT has smaller effective hole mass (m) through theoretical calculation_h ^*) Indicating efficient hole transport within the PAQM-BT backbone. All these factors together lead to a large increase in hole mobility, up to 5.10cm² V^–1s^–1One and four orders of magnitude higher than PAQM-3T and PT3B1, respectively.

Example 2

The synthetic route of this example is the same as that of example 1, except that the raw material for preparing compound 1 is different, and the structural formula of the synthesized compound 1 is shown in the specificationThe structural formula of the compound 3 is

Example 3

The synthetic route of this example is the same as that of example 1, except that the raw material for preparing compound 1 is different, and the structural formula of the synthesized compound 1 is shown in the specificationThe structural formula of the compound 3 is

The above description is only for the purpose of illustrating the present invention and the appended claims, and the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution and the inventive concept of the present invention within the technical scope of the present invention.