Synthesis method and application of asymmetric thiophene selenophenopyrrolo-pyrrolo-dione conjugated polymer
By replacing the sulfur element on the thiophene with selenium in the pyrrolopyrrolidone organic semiconductor material and performing side chain modification, the problem of insufficient flexibility in regulating intermolecular interactions and charge transport capabilities is solved, and its photoelectric properties are significantly improved.
Patent Information
- Application Number
- CN202510324898.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-19
- Publication Date
- 2025-06-06
AI Technical Summary
The existing pyrrolopyrrole dione organic semiconductor materials have insufficient flexibility in regulating intermolecular interactions, charge transport capabilities and solubility, which affects their photoelectric properties.
By replacing the sulfur element on the thiophene with selenium element, an asymmetric pyrrolopyrrole dione organic semiconductor polymer material is designed and synthesized, and the spatial arrangement and solubility of the material are regulated through side chain modification and copolymerization unit modification.
Optimization of the photoelectric properties of organic semiconductor materials has been achieved, and its performance in organic light emitting diodes, field effect transistors and electrochemical transistors has been improved.
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Figure CN120097988A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the field of organic semiconductor materials, and specifically relates to a preparation method and application of a novel diketopyrrolopyrrole organic semiconductor material. Background Art
[0002] Organic transistors are solid semiconductor devices made of organic small molecules or polymer materials, including organic field-effect transistors and organic electrochemical transistors. Organic field-effect transistors (OFETs) are thin-film transistors that use organic semiconductors to form channels. Due to their excellent properties, they can be used as the main component of flexible circuits and have great application prospects in the production of products such as displays, electronic paper, and radio frequency labels (C. Wang, et al., Chem. Rev. 2012, 112 , 2208). Organic electrochemical transistors (EOCT) are a new type of transistor technology based on semiconductor materials. They can conduct both ionic and electronic charges and are used as biosensors, electrophysiological sensors, neuromorphic devices, pressure sensors, or wearable and implantable devices. They are becoming a hot research area today (J. Song, et al., Adv. Mater. 2023,2300034.).
[0003] By adjusting the side groups, a series of pyrrolopyrrole diketo organic semiconductor materials have been designed and synthesized, showing excellent photoelectric properties and good stability (Q Liu, et al., Adv. Mater. 2020, 32 , 1903882). Pyrrolopyrrole diketo compounds with asymmetric side groups can more flexibly adjust the molecular properties such as intermolecular interactions, charge transfer ability, solubility, etc., greatly enriching the types of optoelectronic materials.
[0004] Based on the existing thiophene diketopyrrolopyrrole (TDPP) material, the present invention designs and synthesizes a new type of asymmetric diketopyrrolopyrrole organic semiconductor polymer material. By replacing the sulfur element on the side wing group thiophene with selenium, the spatial arrangement and solubility properties of the polymer are regulated, thereby affecting the photoelectric properties of the semiconductor material. By modifying the side chain of the thiophene selenophene diketopyrrolopyrrole skeleton, a variety of organic light-emitting diodes, field effect transistors and electrochemical transistor materials can be obtained. This DPP-type material designed and synthesized based on the asymmetric modification strategy of the side wing group has excellent photoelectric properties and can be used in organic photoelectric devices. Summary of the invention
[0005] One of the objectives of the present invention is to provide an asymmetric diketopyrrolopyrrole organic semiconductor material that can be applied to organic light emitting diodes (OLEDs), organic field effect transistors (OFETs), organic electrochemical transistors (OECTs) or other organic semiconductor devices.
[0006] The second object of the present invention is to provide a method for synthesizing an asymmetric diketopyrrolopyrrole organic semiconductor material.
[0007] The present invention uses diketopyrrolopyrrole (DPP) as the main body for modification, designs two side groups, thiophene and selenophene, for simultaneously modifying the diketopyrrolopyrrole (DPP) core group, and obtains an asymmetric diketopyrrolopyrrole skeleton. A class of DPP materials is designed through side chain modification and copolymerization unit modification, including small molecules and polymers containing thiophene selenophene diketopyrrolopyrrole structures as described in claims 1, 2, 3, 7, and 8, and the structure is as shown in the following figure:
[0008] The present invention also provides a method for synthesizing the above material, which comprises the following steps.
[0009] (1). Synthesis of a naked DPP core with a thiophene-selenophene side group. First, 2-thiophene ethyl ketone (compound 1) reacts with dimethyl carbonate in a toluene solution of sodium hydride to undergo a nucleophilic addition-elimination reaction to obtain 3-oxo-3-(2-thienyl) propionic acid methyl ester (compound 2). Compound 2 is dissolved in a mixed solvent of acetone / ethylene glycol dimethyl ether and reacts with methyl bromoacetate in the presence of sodium carbonate to obtain 2-(thiophene-2-carbonyl) succinic acid dimethyl ester (compound 3). Compound 3 is added to an acetic acid suspension of ammonium acetate and heated to obtain 5-oxo-2-(thiophene-2-yl)-4,5-dihydro-1H-pyrrole-3-carboxylic acid methyl ester (compound 4). Compound 4 and 2-cyanothiophene were added to a 2-methyl-2-butanol solution in which a sodium block was dissolved to obtain compound 5 (3-(selenophene-2-yl)-6-(thiophene-2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione)
[0010] (2) The synthesis method of SeTDPP monomers, including DPP compounds modified with alkyl side chains of different lengths, ethylene glycol side chains and half ethylene glycol and half alkyl side chains. N , N -methylformamide solution with a bromo side chain or an iodo side chain to undergo a nucleophilic substitution reaction to obtain a side chain modified SeTDPP of general formula 1. General formula 1 is dissolved in dichloromethane and N-Bromosuccinimide is brominated to obtain brominated SeTDPP monomer, general formula 2
[0011] (3). Synthesize polymers by stille polymerization. The specific synthesis method is as follows: add the brominated SeTDPP monomer of general formula 2, the aryltin reagent compound, tri(benzylideneacetone)dipalladium and tri(o-tolyl)phosphine to a mixed solvent of toluene and N,N-dimethylformamide and heat to 120°C for reaction. After the reaction, use a Soxhlet extractor to treat with methanol, acetone and chloroform in turn, and then use methanol to precipitate to obtain a polymer material of general formula 3
[0012] The present invention is based on the asymmetric modification strategy of side groups and develops a new type of organic optoelectronic material with DPP as the core. The proposed synthesis method has the advantages of easy availability of raw materials and simple operation. Moreover, the material structure can be modified according to needs, and can be widely used in the field of organic optoelectronics. BRIEF DESCRIPTION OF THE DRAWINGS
[0013] The present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments.
[0014] Figure 1 This is the hydrogen spectrum of compound 2 described in Example 1.
[0015] Figure 2 This is the hydrogen spectrum of compound 3 described in Example 1.
[0016] Figure 3 This is the hydrogen spectrum of compound 6 described in Example 1.
[0017] Figure 4 This is the hydrogen spectrum of compound 7 described in Example 1.
[0018] Figure 5 This is the hydrogen spectrum of PSeTDPP-TT described in Example 2.
[0019] Figure 6 Figure 1 for the abstract DETAILED DESCRIPTION
[0020] Unless otherwise defined, all technical and scientific terms herein have the same meaning as commonly understood by one of ordinary skill in the art to which this subject matter relates.
[0021] The present invention will be further described below in conjunction with embodiments, but the present invention is not limited to these embodiments.
[0022] Example 1: Taking the synthetic compound SeTDPP as an example, its structure is:
[0023] The reaction formula for synthesizing SeTDPP compound is:
[0024] Step 1: Add dimethyl carbonate (7.2 g, 40.0 mmol) to a mixture of NaH (4.4 g, 60% w / w, 112.0 mmol) and toluene (40 mL), heat to reflux, and dropwise add compound 1 (4.3 mL, 40.0 mmol). After hydrogen evolution stops, cool the reaction to room temperature. Dropwise add glacial acetic acid (12 mL) and then add ice water. Extract with ethyl acetate. Separate the organic layer, wash with water (40 mL) and brine (40 mL), and purify with Na 2 SO 4 After drying, the solvent was removed and column chromatography was performed using petroleum ether and ethyl acetate as eluents to obtain product 2 with a yield of 6.9 g (93%). 1 H NMR (600 MHz, CDCl 3 ) δ 7.74(dd, J = 3.8, 1.1 Hz, 1H), 7.71 (dd, J = 4.9, 1.1 Hz, 1H), 7.15 (dd, J = 5.0,3.8 Hz, 1H), 3.94 (s, 2H), 3.76 (s, 3H).
[0025] Step 2: Compound 2 (6.1 g, 33.0 mol), methyl 2-bromoacetate (5.0 g, 33.0 mol), sodium carbonate (6.9 g, 50.0 mol), acetone (40 mL) and 1,2-dimethoxyethane (10 mL) were added to the reaction. After refluxing for 16 h, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with brine and precipitated with Na 2 SO 4 After drying, the product 3 was separated and purified by column chromatography with a yield of 8.3 g (98%). 1 H NMR (600 MHz, CDCl 3 ) δ 7.90 (dd, J = 3.9,1.1 Hz, 1H), 7.72 (dd, J = 5.0, 1.0 Hz, 1H), 7.17 (dd, J = 4.9, 3.9 Hz, 1H), 4.71 (t, J = 7.2 Hz, 1H), 3.71 (s, 3H), 3.68 (s, 3H), 3.07 (d, J = 7.2 Hz, 2H).
[0026] Step 3: Acetic acid (50 mL) and ammonium acetate (28.0 g, 0.36 mol) were added to compound 3, and the mixture was stirred under reflux for 6 hours. After cooling to 0°C, the mixture was filtered, washed with water and methanol, and compound 4 was obtained in a yield of 46%. 1 H NMR (600 MHz, CDCl 3 ): δ 8.51, (br s, 1H), 7.79 (d, J = 3.6 Hz, 1H), 7.59 (d, J = 4.9Hz, 1H), 7.17 (dd, J = 4.2, 4.7 Hz, 1H), 3.78 (s, 3H), 3.54 (s, 2H).
[0027] Step 4: Sodium (0.68 g, 29.6 mmol) was added to a solution of ferric chloride (3 mg) in 2-methyl-2-butanol (30 mL) and heated to reflux until the sodium was completely consumed. The solution was cooled to 80 °C and 2-selenophenecarbonitrile (1.6 g, 10.1 mmol) was added dropwise. Compound 4 (1.88 g, 8.4 mmol) was added in batches. Stirred overnight at 90 °C and then cooled to room temperature. The reaction was quenched by adding glacial acetic acid (10 mL) in methanol (20 mL), and the mixture was stirred at 90 °C for 10 min. The precipitate was collected by filtration, washed with water and methanol, and dried under vacuum overnight. The crude product 5 was obtained with a yield of 1.49 g (51%). It can be used in the next step without further purification.
[0028] Step 5: To a solution of compound 5 (2.6 g, 6.1 mmol) in DMF (50 ml) was added K 2 CO 3 (8.8 g, 24.4 mmol) and heated to 120 ° C. After 1 hour, 2-octyldodecyl bromide (3.4 g, 24.4 mmol) was added dropwise. After stirring at 120 ° C for another 2 hours, the reaction mixture was poured into water and extracted with chloroform. The combined organic layers were washed with water and Na 2 SO 4 The product was dried and concentrated in vacuo. The product was purified by silica gel column chromatography using a mixture of petroleum ether and dichloromethane as the eluent. Finally, the product was recrystallized from ethanol to obtain product 6 with a yield of 2.6 g (46%). 1 H NMR (600 MHz, CDCl 3): 8.88 (dd,J = 0.9, 3.9 Hz, 1H), 8.80 (dd, J = 0.7, 3.9 Hz, 1H), 8.37 (dd with Sesatellites, J = 0.7, 5.5 Hz, 1H), 7.62 (dd, J = 0.9, 5.0 Hz, 1H), 7.62 (dd, J= 4.1, 5.5 Hz, 1H), 7.28 - 7.25 (m, 1H), 4.01 (d, J = 7.7 Hz, 2H), 3.97 (d, J= 7.7 Hz, 2H), 1.91, (br s, 2H), 1.28-1.21 (m, 64H), 0.89-0.81 (m, 12H).
[0029] Step 6: Compound 6 (0.909 g, 1.0 mmol) was dissolved in 15 mL of chloroform under argon protection. N-bromosuccinimide (0.392 g, 2.2 mmol) was then added in batches. After stirring overnight at room temperature, the mixture was poured into 100 mL of methanol and filtered. The product 7 was purified by recrystallization in ethanol. Yield 0.8 g (77% yield) 1 H NMR (600 MHz, CDCl 3 ): δ 8.63 (d, J = 4.2 Hz, 1H), 8.38 (d, J = 4.4 Hz, 1H), 7.39 (d, J =4.4 Hz, 1H), 7.21 (d, J = 4.2 Hz, 1H), 3.91 (d, J = 7.8 Hz, 2H), 3.87 (d, J =7.7 Hz, 2H), 1.87, (br s, 2H), 1.26-1.22 (m, 64H), 0.89-0.79 (m, 12H).
[0030] Example 2: Taking the synthesis of PSeTDPP-TT as an example, the general formula of the synthetic polymer material is shown, and the reaction formula is:
[0031] Compound 7 (106.6 mg, 0.10 mmol), 2,5-bis(trimethylstannyl)thieno[3,2-b]thiophene (46.6 mg, 0.10 mmol), Pd 2 (dba) 3 (2.7 mg, 0.003 mmol, 3 mol%) and (o-Tol) 3P (2.7 mg, 0.009 mmol) was added to a 25 ml reaction tube, and toluene (3 ml) and N,N-dimethylformamide (0.6 ml) were added under argon protection, and the reaction was carried out at 120°C for 12 hours. After the reaction, dibromothiophene was added for end-capping, and after cooling, the polymer material PSeTDPP-TT was obtained by using a Soxhlet extractor and then using methanol, acetone and chloroform for treatment, and then using methanol for precipitation.
Claims
1. A molecular structure of a small molecule of thiophene selenopyrrolopyrrole dione containing an alkyl side chain, characterized in that Has the following structure:
2. A molecular structure of a small molecule of thiophene selenopyrrolopyrrole dione containing an ethylene glycol side chain, characterized in that Has the following structure:
3. A molecular structure of a small molecule of thiophene selenophene pyrrolopyrrole dione with half ethylene glycol and half alkyl side chains, characterized in that Has the following structure:
4. The method for preparing a novel thiophene selenopyrrolopyrrole diketo compound structure with an alkyl side chain according to claim 1, characterized in that The following steps are involved: First, 2-thiophene ethyl ketone (compound 1) reacts with dimethyl carbonate in a toluene solution of sodium hydride to undergo a nucleophilic addition-elimination reaction to obtain 3-oxo-3-(2-thienyl) propionic acid methyl ester (compound 2). Compound 2 is dissolved in a mixed solvent of acetone / ethylene glycol dimethyl ether and reacts with methyl bromoacetate in the presence of sodium carbonate to obtain 2-(thiophene-2-carbonyl) succinic acid dimethyl ester (compound 3). Compound 3 is added to an acetic acid suspension of ammonium acetate and heated to obtain 5-oxo-2-(thiophene-2-yl)-4,5-dihydro-1H-pyrrole-3-carboxylic acid methyl ester (compound 4). Compound 4 and 2-cyanothiophene are added to a 2-methyl-2-butanol solution in which a sodium block is dissolved to obtain compound 5 (3-(selenophene-2-yl)-6-(thiophene-2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione). Compound 5 in potassium carbonate N , N -methylformamide solution to undergo nucleophilic substitution reaction with bromoalkyl side chain to obtain alkyl side chain modified SeTDPP, which was then dissolved in dichloromethane and N -Bromosuccinimide is brominated to obtain the brominated alkyl side chain SeTDPP, and the specific method is shown in the figure below:
5. The method for preparing a novel thiophene selenophene pyrrolopyrrole diketo compound structure with ethylene glycol side chain according to claim 2, characterized in that The following steps are involved: Compound 5 in potassium carbonate N , N -methylformamide solution with iodoethylene glycol side chain to undergo nucleophilic substitution reaction to obtain ethylene glycol side chain modified SeTDPP, which was then dissolved in dichloromethane and N -Bromosuccinimide is brominated to obtain bromoethylene glycol side chain SeTDPP, the specific method is shown in the figure below:
6. The method for preparing a novel half-ethylene glycol half-alkyl side chain thiophene selenophene pyrrolopyrrole diketo compound structure according to claim 3, characterized in that The following steps are involved: Compound 5 in potassium carbonate N , N -methylformamide solution with iodinated half-ethylene glycol half-alkyl side chain to undergo nucleophilic substitution reaction to obtain half-ethylene glycol half-alkyl side chain modified SeTDPP, which was then dissolved in dichloromethane and N -Bromosuccinimide is brominated to obtain brominated half-ethylene glycol half-alkyl side chain SeTDPP. The specific method is shown in the figure below:
7. A method for synthesizing a thiophene selenophene pyrrolopyrrole diketo copolymer, characterized in that: The method comprises the step of Stille polymerization of the structure shown in claim 1 and 2,5-bis(trimethyltin)-thieno[3,2-B]thiophene to obtain a polymer, and the step of Stille polymerization of the structures shown in claims 2 and 3 and (3,3'-methoxy-[2,2'-bithiophene]-5,5'-diyl)bis(trimethyltin) to obtain a polymer. The specific method is shown in the following figure:
8. A series of copolymers of thiophene selenophene pyrrolopyrrole dione and aromatic hydrocarbons, characterized in that Has the following structure:
9. Use of small molecules containing thiophene selenopyrrolopyrrole diketo structures as described in claims 1, 2, 3, 7, and 8 and their corresponding polymers in organic semiconductor optoelectronic devices such as organic field effect transistors (OFETs), organic electrochemical transistors (OECTs), organic light emitting diodes (OLEDs), and organic light emitting transistors (OLETs).
10. An organic electrochemical transistor and field effect transistor device, characterized in that: include: A bottom electrode, a top electrode, an electrolyte solution, and a polymer channel material, wherein the channel material is a polymer optoelectronic material prepared by the synthesis method of claim 8.