Preparation method of dimer, trimer and tetramer of diketopyrrolopyrrole and photophysical properties of dimer, trimer and tetramer of diketopyrrolopyrrole
By designing and synthesizing DPP-based polymers, the problem of short triplet life of existing SF materials is solved, efficient singlet splitting is achieved, and the performance of the material in organic photovoltaic cells is improved.
Patent Information
- Application Number
- CN202411712794.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-27
- Publication Date
- 2025-02-28
AI Technical Summary
The existing singlet splitting (SF) materials have a short triplet life, which limits their application in organic photovoltaic cells.
By designing and synthesizing dimers, trimers and tetramers with pyrrolopyrrolidone (DPP) as structural units, electron coupling between molecules is enhanced, and the delocalization of excitons is promoted, thereby improving the efficiency of singlet splitting.
It has achieved stable photooxygen thermal stability, high molar extinction coefficient, high singlet splitting rate and yield, which has enhanced the application potential of materials in organic photovoltaic cells.
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Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of chemistry and relates to a preparation method of a pyrrolopyrrole diketopyrrole dimer, trimer and tetramer and photophysical properties thereof. Background Art
[0002] As a common molecular building block, diketopyrrolopyrrole (DPP) has a high dielectric constant, high carrier mobility and good thermal / photostability. This makes DPP and its derivatives have a wide range of application potentials in organic optoelectronic materials, including organic field-effect transistors, organic photovoltaics, sensors, two-photon absorption materials and other fields. Among them, singlet fission (SF) is a strategy to improve photovoltaic efficiency. It can split a singlet exciton into two triplet excitons, so that the maximum triplet yield reaches 200%, significantly improving the utilization efficiency of solar energy. DPP has good light and thermal stability (in air), excellent solution processability and low price, and is considered to be one of the ideal materials for achieving high-efficiency SF.
[0003] At present, the triplet lifetime of SF materials is relatively short, which limits their application in organic photovoltaic cells. In order to overcome this limitation, it is particularly important to develop high-efficiency SF materials with long-life triplet states. By increasing the number of structural units of DPP and synthesizing monomers, dimers, trimers and tetramers with DPP as structural units, the electronic coupling between molecules can be enhanced, the delocalization of excitons can be promoted, and the efficiency of singlet fission can be improved. Therefore, the design and development of dimers, trimers and tetramers with DPP as structural units has important research and application value for improving the efficiency of singlet fission. Summary of the invention
[0004] In view of the problems existing in the above-mentioned prior art, the present invention provides monomers, dimers, trimers and tetramers with DPP as a structural unit and a preparation method thereof.
[0005] The monomer compound (i) and the molecular structure diagram are as follows:
[0006] The technical solution adopted by the present invention is carried out according to the following steps:
[0007] Preparation method of compound (v) Step 1: Place 3.0 g of 3,6-di(2-thienyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione and 5.52 g of anhydrous potassium carbonate in a 250 mL three-necked flask, and evacuate the flask three times with nitrogen gas. Step 2: Add 100 mL of anhydrous N,N-dimethylformamide at one time, and heat the mixture to 120°C and stir for 90 minutes under nitrogen protection; Step 3: Dissolve 4.13 g of isooctane bromide in a normal pressure dropping funnel filled with 50 mL of anhydrous N,N-dimethylformamide, and slowly add dropwise after all the solids in the three-necked flask are dissolved; Step 4: Heat the temperature to 130°C and maintain for 2 hours; Step 5: The solvent was removed by rotary evaporation, and the solid was extracted twice with 80 mL of dichloromethane and 100 mL of water. The organic phase was dried over anhydrous sodium sulfate and evaporated to dryness to remove dichloromethane to obtain a dark red crude product; Step 6: The dark red crude product in step 5 was passed through a column with dichloromethane / n-hexane (volume ratio of 1:1), and the first band was the product band, which was evaporated to dryness; Step 7: Recrystallize with dichloromethane / methanol (volume ratio of 1:6), then filter, collect the dark red precipitate on the filter paper, and dry it in vacuum at 40°C overnight to obtain compound (v) with a yield of 60%.
[0008] Preparation method of compound (vi) (vii) Step 1: Add 5.0 g of compound (v) into a 250 mL three-necked flask wrapped with aluminum foil; Step 2: Add 100 mL of chloroform at one time, and stir the mixture at 0°C for 30 minutes under nitrogen protection until it is completely dissolved; Step 3: Dissolve 1.69 g of N-bromosuccinimide in a normal pressure dropping funnel filled with 50 mL of chloroform. Wrap the normal pressure dropping funnel with aluminum foil. After all the solids in the three-necked flask are dissolved, slowly add dropwise; Step 4: The system reaction temperature continues to be maintained at 0°C and stirring is continued for 24 hours; Step 5: Methanol was added to the solution to quench the reaction, and the solvent was removed by rotary evaporation to obtain a dark red solid. Step 6: The dark red crude product in step 5 was passed through a column with dichloromethane / n-hexane (volume ratio of 1:1). The first band was the product band (ⅶ), and the second band was (ⅵ). The product was evaporated to dryness by rotary evaporation. Step 7: The first and second generations collected in step 6 were recrystallized using dichloromethane / methanol (volume ratio of 1:6), respectively, and then filtered to collect the precipitate on the filter paper, and dried under vacuum at 40°C overnight to obtain compound (ⅵ) with a yield of 40% and compound (ⅶ) with a yield of 30%.
[0009] Preparation method of compound (I) Step 1: Place 120.7 mg of compound (ⅶ), 51.02 mg of phenylboronic acid pinacol ester, 25 mg of tris(dibenzylideneacetone)dipalladium(0) and 32 mg of bis(2-diphenylphosphophenyl)ether in a 100 mL Shrek tube, and evacuate the tube three times and replace with nitrogen; Step 2: Take 27.64 g of anhydrous potassium carbonate in a 250 mL conical flask, add 100 mL of deionized water, sonicate until the solid is completely dissolved, prepare a 2 mol / L potassium carbonate aqueous solution, plug it with a rubber stopper, and pass nitrogen to deoxygenate for 30 min; Step 3: Put 100 mL of toluene in a 250 mL single-mouth bottle and 20 mL of anhydrous ethanol in a 100 mL single-mouth bottle, plug it with a rubber stopper, and pass nitrogen to deoxygenate for 30 min; Step 4: Add 24 mL of toluene, 2 mL of anhydrous ethanol, and 0.8 mL of anhydrous potassium carbonate into a Shrek tube, heat to 95°C and maintain for 8 hours; Step 5: The solvent was removed by rotary evaporation, and the solid was extracted twice with 80 mL of dichloromethane and 100 mL of water. The organic phase was dried over anhydrous sodium sulfate and evaporated to remove dichloromethane to obtain a solid; Step 6: The crude product in step 5 was passed through a column with dichloromethane / n-hexane (volume ratio of 1:1), and the main band, i.e., the product band, was collected and evaporated to dryness by rotary evaporation; Step 7: Recrystallize with dichloromethane / methanol (volume ratio of 1:6), then filter, collect the red precipitate on the filter paper, and dry it in vacuum at 40°C overnight to obtain compound (i) with a yield of 20%.
[0010] Preparation method of compound (ii) Step 1: Place 151.1 mg of compound (VI), 23.41 mg of 1,2-phenylenediboronic acid bis(pinacol) ester, 25 mg of tris(dibenzylideneacetone)dipalladium(0) and 32 mg of bis(2-diphenylphosphinophenyl)ether in a 100 mL Shrek tube, and evacuate the tube three times and replace with nitrogen; Step 2: Take 27.64 g of anhydrous potassium carbonate in a 250 mL conical flask, add 100 mL of deionized water, sonicate until the solid is completely dissolved, prepare a 2 mol / L potassium carbonate aqueous solution, plug it with a rubber stopper, and pass nitrogen to deoxygenate for 30 min; Step 3: Put 100 mL of toluene in a 250 mL single-mouth bottle and 20 mL of anhydrous ethanol in a 100 mL single-mouth bottle, plug it with a rubber stopper, and pass nitrogen to deoxygenate for 30 min; Step 4: Add 24 mL of toluene, 2 mL of anhydrous ethanol, and 0.8 mL of anhydrous potassium carbonate into a Shrek tube, heat to 95°C and maintain for 8 hours; Step 5: The solvent was removed by rotary evaporation, and the solid was extracted twice with 80 mL of dichloromethane and 100 mL of water. The organic phase was dried over anhydrous sodium sulfate and evaporated to remove dichloromethane to obtain a solid; Step 6: The crude product in step 5 was passed through a column with dichloromethane / n-hexane (volume ratio of 2:1), and the main band, i.e., the product band, was collected and evaporated to dryness by rotary evaporation; Step 7: Recrystallize with dichloromethane / methanol (volume ratio of 1:6), then filter, collect the red precipitate on the filter paper, and dry it in vacuum at 40°C overnight to obtain compound (i) with a yield of 30%.
[0011] Preparation method of compound (VIII) Step 1: Take 151.1 mg of compound (ⅶ), 58.52 mg of 1,2-phenylenediboronic acid bis(pinacol) ester, 10 mg of tris(dibenzylideneacetone)dipalladium(0) and 22 mg of bis(2-diphenylphosphophenyl) ether in a 100 mL Shrek tube, evacuate and replace with nitrogen three times; Step 2: Take 27.64 g of anhydrous potassium carbonate in a 250 mL conical flask, add 100 mL of deionized water, sonicate until the solid is completely dissolved, prepare a 2 mol / L potassium carbonate aqueous solution, plug it with a rubber stopper, and pass nitrogen to deoxygenate for 30 min; Step 3: Put 100 mL of toluene in a 250 mL single-mouth bottle and 20 mL of anhydrous ethanol in a 100 mL single-mouth bottle, plug it with a rubber stopper, and pass nitrogen to deoxygenate for 30 min; Step 4: Add 24 mL of toluene, 2 mL of anhydrous ethanol, and 0.8 mL of anhydrous potassium carbonate into a Shrek tube, heat to 95°C and maintain for 8 hours; Step 5: The solvent was removed by rotary evaporation, and the solid was extracted twice with 80 mL of dichloromethane and 100 mL of water. The organic phase was dried over anhydrous sodium sulfate and evaporated to remove dichloromethane to obtain a solid; Step 6: The crude product in step 5 was passed through a column with dichloromethane / n-hexane (volume ratio of 2:1), and the main band, i.e., the product band, was collected and evaporated to dryness by rotary evaporation; Step 7: Recrystallize with dichloromethane / methanol (volume ratio of 1:6), then filter, collect the red precipitate on the filter paper, and dry it in vacuum at 40°C overnight to obtain compound (ⅷ) with a yield of 15%.
[0012] Preparation method of compound (III) Step 1: Place 136.5 mg of compound (ⅶ), 364.5 mg of compound (ⅷ), 25 mg of tris(dibenzylideneacetone)dipalladium(0) and 22 mg of bis(2-diphenylphosphinophenyl)ether in a 100 mL Shrek tube, and evacuate the tube three times and replace with nitrogen; Step 2: Take 27.64 g of anhydrous potassium carbonate in a 250 mL conical flask, add 100 mL of deionized water, sonicate until the solid is completely dissolved, prepare a 2 mol / L potassium carbonate aqueous solution, plug it with a rubber stopper, and pass nitrogen to deoxygenate for 30 min; Step 3: Put 100 mL of toluene in a 250 mL single-mouth bottle and 20 mL of anhydrous ethanol in a 100 mL single-mouth bottle, plug it with a rubber stopper, and pass nitrogen to deoxygenate for 30 min; Step 4: Add 24 mL of toluene, 2 mL of anhydrous ethanol, and 0.8 mL of anhydrous potassium carbonate into a Shrek tube, heat to 95°C and maintain for 8 hours; Step 5: The solvent was removed by rotary evaporation, and the solid was extracted twice with 80 mL of dichloromethane and 100 mL of water. The organic phase was dried over anhydrous sodium sulfate and evaporated to remove dichloromethane to obtain a solid; Step 6: The crude product in step 5 was passed through a column with dichloromethane / n-hexane (volume ratio of 5:2), and the main band, i.e., the product band, was collected and evaporated to dryness by rotary evaporation; Step 7: Recrystallize with dichloromethane / methanol (volume ratio of 1:6), then filter, collect the red precipitate on the filter paper, and dry it in vacuum at 40°C overnight to obtain compound (III) with a yield of 8%.
[0013] Preparation method of compound (ⅸ) Step 1: Place 136.5 mg of compound (ⅶ), 145.8 mg of compound (ⅲ), 25 mg of tris(dibenzylideneacetone)dipalladium(0) and 32 mg of bis(2-diphenylphosphinophenyl)ether in a 100 mL Shrek tube, and evacuate the tube three times and replace with nitrogen; Step 2: Take 27.64 g of anhydrous potassium carbonate in a 250 mL conical flask, add 100 mL of deionized water, sonicate until the solid is completely dissolved, prepare a 2 mol / L potassium carbonate aqueous solution, plug it with a rubber stopper, and pass nitrogen to deoxygenate for 30 min; Step 3: Put 100 mL of toluene in a 250 mL single-mouth bottle and 20 mL of anhydrous ethanol in a 100 mL single-mouth bottle, plug it with a rubber stopper, and pass nitrogen to deoxygenate for 30 min; Step 4: Add 24 mL of toluene, 2 mL of anhydrous ethanol, and 0.8 mL of anhydrous potassium carbonate into a Shrek tube, heat to 95°C and maintain for 8 hours; Step 5: The solvent was removed by rotary evaporation, and the solid was extracted twice with 80 mL of dichloromethane and 100 mL of water. The organic phase was dried over anhydrous sodium sulfate and evaporated to remove dichloromethane to obtain a solid; Step 6: The crude product in step 5 was passed through a column with dichloromethane / n-hexane (volume ratio of 5:2), and the main band, i.e., the product band, was collected and evaporated to dryness by rotary evaporation; Step 7: Recrystallize with dichloromethane / methanol (volume ratio of 1:6), then filter, collect the red precipitate on the filter paper, and dry it in vacuum at 40°C overnight to obtain compound (ⅸ) with a yield of 20%.
[0014] Preparation method of compound (iv) Step 1: Place 240.6 mg of compound (ⅶ), 18.72 mg of 1,2-phenylenediboronic acid bis(pinacol) ester, 25 mg of tris(dibenzylideneacetone)dipalladium(0) and 32 mg of bis(2-diphenylphosphinophenyl) ether in a 100 mL Shrek tube, and evacuate the tube three times and replace with nitrogen; Step 2: Take 27.64 g of anhydrous potassium carbonate in a 250 mL conical flask, add 100 mL of deionized water, sonicate until the solid is completely dissolved, prepare a 2 mol / L potassium carbonate aqueous solution, plug it with a rubber stopper, and pass nitrogen to deoxygenate for 30 min; Step 3: Put 100 mL of toluene in a 250 mL single-mouth bottle and 20 mL of anhydrous ethanol in a 100 mL single-mouth bottle, plug it with a rubber stopper, and pass nitrogen to deoxygenate for 30 min; Step 4: Add 24 mL of toluene, 2 mL of anhydrous ethanol, and 0.8 mL of anhydrous potassium carbonate into a Shrek tube, heat to 95°C and maintain for 8 hours; Step 5: The solvent was removed by rotary evaporation, and the solid was extracted twice with 80 mL of dichloromethane and 100 mL of water. The organic phase was dried over anhydrous sodium sulfate and evaporated to remove dichloromethane to obtain a solid; Step 6: The crude product in step 5 was passed through a column with dichloromethane / n-hexane (volume ratio of 4:1), and the main band, i.e., the product band, was collected and evaporated to dryness by rotary evaporation; Step 7: Recrystallize with dichloromethane / methanol (volume ratio of 1:6), then filter, collect the red precipitate on the filter paper, and dry it in vacuum at 40°C overnight to obtain compound (iv) with a yield of 4%.
[0015] Under degassing conditions, the singlet yields and rates of the dimer compound (ii), trimer compound (iii) and tetramer compound (iv) were (45% and 3.71ns, 66% and 1.62ns and for trimer, 85% and 1.08ns), respectively.
[0016] The beneficial effects of the present invention are as follows: the present invention proposes a design and synthesis scheme for a class of pyrrolopyrrole diketo derivatives. On the one hand, by increasing the number of pyrrolopyrrole diketo units, dimers, trimers, and tetramers based on pyrrolopyrrole diketo are synthesized, the conjugated structure of the compound is expanded, and a new type of small molecule singlet fission material with stable photo-oxidation thermal stability, high molar extinction coefficient, high singlet fission rate and yield is obtained. On the other hand, by increasing the number of units, the dispersion performance of the red pigment can be improved, the thermal stability performance of the series of pigments can be improved, and the cost can be saved. BRIEF DESCRIPTION OF THE DRAWINGS
[0017] The present invention is further described below in conjunction with the accompanying drawings and embodiments.
[0018] Figure 1 It is a schematic diagram of the preparation process of the present invention;
[0019] Figure 2 is the NMR image of compound (v);
[0020] Figure 3 is the mass spectrum of compound (v);
[0021] Figure 4 is the NMR image of compound (ⅵ);
[0022] Figure 5 is the mass spectrum of compound (ⅵ);
[0023] Figure 6 is the NMR image of compound (ⅶ);
[0024] Figure 7 is the mass spectrum of compound (ⅶ);
[0025] Figure 8 is the NMR image of compound (ⅰ);
[0026] Fig. 9 is the mass spectrum of compound (i);
[0027] Fig.10 is the NMR image of compound (ii);
[0028] Fig.11 is the mass spectrum of compound (ii);
[0029] Fig.12 is the NMR image of compound (ⅷ);
[0030] Fig.13 is the mass spectrum of compound (ⅷ);
[0031] Fig.14 is the NMR image of compound (ⅸ);
[0032] Fig.15 is the mass spectrum of compound (ⅸ);
[0033] Fig.16 is the NMR image of compound (ⅲ);
[0034] Fig.17 is the mass spectrum of compound (iii);
[0035] Fig.18 is the NMR image of compound (ⅳ);
[0036] Fig.19 is the mass spectrum of compound (iv);
[0037] Fig. 20 It is the UV-visible absorption spectrum of diketopyrrolopyrrole dimer, trimer and tetramer in benzonitrile solution;
[0038] Fig.21 It is the fluorescence spectrum of diketopyrrolopyrrole dimer, trimer and tetramer in benzonitrile solution;
[0039] Fig. 22 It is the femtosecond transient absorption spectrum of diketopyrrolopyrrole dimer, trimer and tetramer in benzonitrile solution;
[0040] Fig.23 It is the nanosecond transient absorption spectrum of diketopyrrolopyrrole dimer, trimer and tetramer in benzonitrile solution;
[0041] Fig.24 It is the sensitized nanosecond transient absorption spectrum of diketopyrrolopyrrole dimer, trimer and tetramer in benzonitrile solution;
[0042] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Any ordinary technician familiar with the profession can smoothly implement the present invention according to the drawings and the above description. However, any technician familiar with the profession can make some changes, modifications and equivalent changes made by using the technical content disclosed above without departing from the scope of the technical solution of the present invention, which are all equivalent embodiments of the present invention. At the same time, any equivalent changes, modifications and evolutions made to the above embodiments based on the implementation technology of the present invention are within the protection scope of the technical solution of the present invention.
Claims
1. Synthesizing diketopyrrolopyrrole dimers, trimers, and tetramers by reaction, wherein each polymer unit is connected by diketopyrrolopyrrole molecular units through covalent bonds; in, The solvent used in the reaction is anhydrous N,N-dimethylformamide, chloroform or dichloromethane, and the reaction is carried out under nitrogen protection.
2. The preparation method according to claim 1, wherein The structure of the diketopyrrolopyrrole monomer is shown in formula (i), the structure of the dimer is shown in formula (ii), the structure of the trimer is shown in formula (iii), and the structure of the tetramer is shown in formula (iv).
3. The preparation method according to claim 1, wherein The dimer compound (ii), trimer compound (iii) and tetramer compound (iv) have the following photophysical properties: In benzonitrile solution, the UV-visible absorption spectra, fluorescence spectra and transient absorption spectra of the dimer, trimer and tetramer show significant photophysical properties, such as the triplet quantum yield and singlet fission rate are 45% and 3.71ns (dimer), 66% and 1.62ns (trimer), and 85% and 1.08ns (tetramer), respectively.