CN110746440A - Organic solar cell receptor material with diindeno bithiophene as core and preparation method and application thereof - Google Patents

Organic solar cell receptor material with diindeno bithiophene as core and preparation method and application thereof Download PDF

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CN110746440A
CN110746440A CN201911074347.XA CN201911074347A CN110746440A CN 110746440 A CN110746440 A CN 110746440A CN 201911074347 A CN201911074347 A CN 201911074347A CN 110746440 A CN110746440 A CN 110746440A
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solar cell
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谢素原
郑珊瑜
安明伟
裴亚茜
邓林龙
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Xiamen University
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Abstract

The invention discloses an organic solar cell receptor material taking diindeno bithiophene as a core, and the structure is based on diindeno-thiophene [2,3-b ]]The thiophene six-ring is taken as A central electron-donating unit, A pi electron connecting unit and A terminal electron-pulling unit are introduced to form the organic acceptor material with an A-Q-D-Q-A type structure, and the structure diagram is shown as follows:
Figure DDA0002261926220000011
the preparation method takes bithiophene with strong electron-donating group as a core, introduces a benzene ring and an aromatic hydrocarbon side chain through coupling reaction, closes the ring under an acid environment, and introduces a bridge unit with an aromatic structure, and mostPost-addition of terminal electron withdrawing groups; the molecules can be used as an acceptor material of an active layer of an organic solar cell, are more matched with an energy band gap of a polymer donor, have stronger light absorption in a visible-near infrared region and are complementary with the light absorption of the donor material, so that the requirement of improving the efficiency of an organic solar cell device is met; meanwhile, the molecules can be used for constructing a ternary organic solar cell.

Description

Organic solar cell receptor material with diindeno bithiophene as core and preparation method and application thereof
Technical Field
The invention relates to the technical field of solar cell materials, in particular to an organic solar cell receptor material taking diindeno bithiophene as a core, and a preparation method and application thereof.
Background
With the continuous consumption of fossil energy, mankind faces increasingly serious energy crisis and environmental problems. Solar energy is taken as green renewable energy, and a solar cell for converting the solar energy into electric energy becomes a global research hotspot. The traditional silicon-based battery has complex production process, difficult degradation of inorganic materials and poor environment friendliness. The organic solar cell material has various and controllable structures, is simple to prepare, has light weight and flexibility, can be prepared in a large area and at low cost, and can be applied to portable wearable electronic devices, building glass, automobile intelligent window systems and the like.
Organic solar cells were first reported in 1958 using single-crystal anthracene as the light absorbing layer. Then, the fullerene and the derivative thereof are widely applied to organic solar cells due to excellent charge transport properties. Researchers can lead the photoelectric conversion efficiency of the organic solar cell based on the fullerene acceptor to reach 10.8% through reasonable design of active layer molecules and optimization of cell devices.
In recent five years, the development of organic photovoltaic materials based on conjugated small molecule receptors is rapid, the light absorption range of the small molecule receptors of the organic solar cells can be red shifted to a visible-near infrared region, the energy level can be adjusted in a large range, and the organic photovoltaic materials can be matched with various donor materials. At present, the development of the receptor materials is mainly dominated by small molecule conjugated long chains. The IEIC molecule and the ITIC molecule are synthesized by using indacenodithiophene as an intermediate nucleus, isooctane thiophene as a bridge and end group dicyan indandione at the university of Beijing in 2015 which is the subject group of Shawei. Subsequently, the IEICO-4F star molecule is designed by replacing isooctyl on bridged thiophene with isooctyloxy under the condition that the central core structure is kept unchanged by the glow-building subject group of the institute of chemistry of the Chinese academy of sciences, and the efficiency of a single junction device reaches 10.0%. The band gap of the octacyclo-oxa small-molecule condensed ring receptor reported by the task group of Dinghuing in 2017 is only 1.26eV, and a single junction device can reach 12.16%. The field is rapidly developed later, and many subject groups report that the efficiency of organic solar cells based on the dominance of conjugated small molecules is greatly improved. Among them, the maximum efficiency of single junction devices has exceeded 15%, while the maximum efficiency of stacked devices has exceeded 17%.
The fused ring small molecule receptor reported at present has a complex structure, expensive synthetic raw materials, difficult preparation process, single chemical structure and limited regulation of material band gap and spectral absorption. Meanwhile, the existing micromolecule acceptor material has a rigid structure, and most of electron donor cores in condensed rings form sp2The hybrid orbitals are not favorable for stacking arrangement of donor and acceptor, and influence phase separation of the active layer.
Disclosure of Invention
The invention aims to provide an organic solar cell receptor material taking diindeno bithiophene as A core, and simultaneously improve the preparation method of the existing solar cell receptor material, and the diindeno-thieno [2,3-b ] thiophene six-membered ring is taken as the core, and A pi electron connecting unit and A terminal receptor unit are introduced to form the organic receptor material with an A-Q-D-Q-A type structure, so that the effective conjugation length of the material and the accumulation mode of A donor receptor in an active layer can be adjusted, the energy level and the spectrum absorption range of the material can be adjusted, and the efficiency of A cell device can be improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the organic solar cell receptor material taking diindeno bithiophene as a core has the following structural general formula:
wherein R is1Is hydrogen atom, C3-15 linear or branched alkyl, C3-15 linear or branched alkoxy, CA solubilizing group such as a phenylalkyl group having 3 to 15 carbon atoms, a phenylalkoxy group having 3 to 15 carbon atoms, a thienylalkyl group having 3 to 15 carbon atoms, or a thienylalkoxy group having 3 to 15 carbon atoms.
Wherein Q is a pi electron connection unit, and the chemical structural formula of the pi electron connection unit is one of the following types:
wherein, X is one of oxygen atom, sulfur atom or selenium atom; r2-R5Are independently selected from hydrogen atom, aryl, hydroxyl, carbonyl, halogen atom, C3-15 straight-chain or branched-chain alkyl, and C3-15 straight-chain or branched-chain alkoxy.
Wherein, A is an end group electron pulling unit, and the chemical structural formula of the end group electron pulling unit is one of the following:
wherein R is6、R7Are independently selected from hydrogen atoms and straight chain or branched chain alkyl with 1-15 carbon atoms; r8、R9Are independently selected from hydrogen atoms, halogen atoms, methyl or methoxy.
Preferred embodiments of the present invention are selected from the following compounds:
Figure BDA0002261926200000032
Figure BDA0002261926200000051
Figure BDA0002261926200000061
a method for preparing an organic solar cell receptor material with diindeno bithiophene as a core comprises the following steps:
Figure BDA0002261926200000062
(1) synthesis of Compound 1: adding N-chlorosuccinimide into N, N-dimethylformamide solution of bithiophene in a single-neck round-bottom flask, stirring at room temperature for several hours, adding water for quenching after TLC monitoring reaction is finished, transferring the reaction solution into a separating funnel, extracting with diethyl ether, drying an organic phase with anhydrous sodium sulfate, and performing column chromatography with a petroleum ether eluent to obtain a white solid, namely a bilateral chloro-bithiophene product 1; the ratio of the N-chlorosuccinimide to the bithiophene to the N, N-dimethylformamide is 10-20 mmol, 20-50 mmol and 40-100 mL; the structural characterization data are:1H NMR(400MHz,CDCl3),δ(ppm):6.19(s,2H)；13C NMR(100MHz,CDCl3),δ(ppm):134.7,130.8,118.9；MALDI-TOF MS(m/z):207.9(M-)。
(2) synthesis of Compound 3: taking a double-mouth round-bottom flask, carrying out anhydrous and anaerobic treatment, dropwise adding a tetramethyl piperidine MgCl. LiCl catalyst into a tetrahydrofuran solution of dichlorothiophene under the protection of nitrogen, stirring at room temperature for 1-5 hours, reducing the reaction temperature to-80-0 ℃, adding ethyl cyanoformate to carry out unilateral hydroformylation, and monitoring by TLC (thin layer chromatography) to obtain a unilateral hydroformylation product 2; repeating the hydroformylation again, after the reaction is finished, adding an ammonium chloride aqueous solution into the reaction solution for quenching, transferring the reaction solution into a separating funnel, extracting with diethyl ether, drying an organic phase with anhydrous sodium sulfate, and performing column chromatography with a petroleum ether/dichloromethane eluent to obtain a white solid, namely a bilateral hydroformylation product 3; the compound 1, tetramethyl piperidine MgCl. LiCl, ethyl cyanoformate and tetrahydrofuran are mixed according to the proportion of 10-18 mmol, 10-30 mmol, 5-25 mmol and 30-70 mL; the structural characterization data are:1H NMR(400MHz,CDCl3),δ(ppm):7.14(m,2H),7.19(m,2H),4.04(q,J＝7.1Hz,2H),1.01(t,J＝7.1Hz,3H)；13C NMR(100MHz,CDCl3),δ(ppm):160.2,137.5,134.8,133.7,132.3,130.6,129.8,129.4,128.1,127.9,123.1,61.5,14.1；MALDI-TOF MS(m/z):389.9(M-)。
(3) synthesis of Compound 4: taking a double-opening round-bottom flask, carrying out anhydrous anaerobic treatment, sequentially adding a product 3, phenylboron, a palladium catalyst and cesium carbonate, displacing gas for 3 times, adding a toluene solvent under the protection of nitrogen to carry out Suzuki coupling reaction at a reaction temperature of 60-120 ℃, reacting overnight, monitoring by TLC (thin layer chromatography), cooling to room temperature, adding water to quench, transferring a reaction solution into a separating funnel, extracting with dichloro, drying an organic phase with anhydrous sodium sulfate, and carrying out column chromatography with petroleum ether/dichloromethane eluent to obtain a light yellow solid after spin-drying; the ratio of the compound 3, phenylboronic ester, a palladium catalyst, cesium carbonate and toluene is 5-20 mmol, 12-32 mmol, 1-5 mmol, 30-90 mmol and 15-40 mL; the structural characterization data are:1H NMR(500MHz,CDCl3),δ(ppm):7.56-7.61(m,4H),7.44-7.46(m,6H),4.30(q,J＝7.1Hz,4H),1.27(t,J＝7.1Hz,6H)；13C NMR(125MHz,CDCl3),δ(ppm):162.0,154.0,137.4,133.4,130.0,129.0,128.0,120.3,61.0,14.0；MALDI-TOF MS(m/z):436.1(M-)。
(4) synthesis of Compound 5: taking a double-mouth round-bottom flask, carrying out anhydrous and anaerobic treatment, adding a compound 4, displacing gas for 3 times, adding a tetrahydrofuran solvent under the protection of nitrogen, heating until the reaction liquid flows back, adding one of different Grignard reagents such as a C3-15 straight-chain or branched-chain alkyl group, a C3-15 straight-chain or branched-chain alkoxy group, a C3-15 phenylalkyl group, a C3-15 phenylalkoxy group, a C3-15 thiophenylalkyl group, a C3-15 thiophenylalkoxy group and the like under the protection of nitrogen, reacting overnight, carrying out TLC monitoring reaction, cooling to room temperature, adding water for quenching, transferring the reaction liquid into a separating funnel, extracting with diethyl ether, and drying an organic phase with anhydrous sodium sulfate; directly dissolving the product in n-octane by using a double-opening round-bottom flask, adding glacial acetic acid and sulfuric acid, dehydrating and closing a ring under an acidic condition, adding water for quenching after the reaction is finished, transferring the reaction liquid into a separating funnel, extracting with ethyl acetate, drying an organic phase with anhydrous sodium sulfate, and performing column chromatography with a petroleum ether eluent to obtain a yellow oily substance to obtain a diindenothiopheno [2,3-b ] thiophene six-membered ring; the ratio of the compound 4 to the Grignard reagent to the tetrahydrofuran is 4-14 mmol, 10-40 mmol, and 20-60 mL; the ratio of the ring-closing precursor, the glacial acetic acid, the sulfuric acid and the n-octane is 3-9 mmol, 0.1-1.5 mmol and 10-35 mL.
(5) Synthesis of Compound 6: taking a double-mouth round-bottom flask, carrying out anhydrous and anaerobic treatment, adding a compound 5 and copper bromide/aluminum oxide powder prepared in advance, dissolving the compound 5 and the copper bromide/aluminum oxide powder in a carbon tetrachloride solution, heating the solution under stirring at 40-80 ℃ for overnight reaction, cooling the solution to room temperature after TLC monitoring reaction is finished, filtering the solution by using filter paper, and carrying out evaporation concentration to directly obtain bi-edge brominated diindenothiopheno [2,3-b ] thiophene and a yellow solid product 6; the ratio of the compound 5, copper bromide/aluminum oxide and carbon tetrachloride is 3-12 mmol, 8-25 mmol and 10-30 mL.
(6) Synthesis of compound 7: taking a double-opening round-bottom flask, carrying out anhydrous and anaerobic treatment, adding a compound 6 to displace gas for 3 times, adding a tetrahydrofuran solvent under the protection of nitrogen, carrying out bromine-lithium displacement reaction by using n-butyllithium at a low temperature, reacting at-78 ℃ for 1-5 hours, then adding isopropanol pinacol borate, slowly heating to room temperature for overnight reaction, adding water for quenching after the reaction is finished, transferring the reaction solution to a separating funnel, extracting by using ethyl acetate, drying an organic phase by using anhydrous sodium sulfate, and directly using a crude product after spin-drying without further purification for next-step synthesis; the mixture ratio of the compound 6, n-butyllithium, isopropanol pinacol borate and carbon tetrachloride is 2-15 mmol, 5-30 mmol, 7-20 mmol and 8-40 mL.
(7) Synthesis of compound 8: taking a double-opening round bottom flask, carrying out anhydrous anaerobic treatment, sequentially adding a product 7, a pi electronic connection unit, a palladium tetratriphenylphosphine catalyst and cesium carbonate, displacing gas for 3 times, adding toluene under the protection of nitrogen to carry out Suzuki coupling reaction, heating the reaction to 70-120 ℃, reacting overnight, monitoring the reaction by TLC, cooling to room temperature, adding water to quench, transferring the reaction solution to a separating funnel, extracting with dichloro, drying an organic phase with anhydrous sodium sulfate, and carrying out column chromatography with petroleum ether/dichloromethane eluent to obtain a yellowish red solid after spin-drying; the compound 7, the pi electron connection unit, the palladium tetratriphenylphosphine catalyst, the cesium carbonate and the toluene are mixed according to a ratio of 0.2-2 mmol, 0.4-4.4 mmol, 0.1-0.8 mmol, 3-15 mmol and 10-50 mL.
(8) Synthesis of compound 9: dissolving a compound 8 in chloroform in a double-mouth round-bottom flask, carrying out Knoevenagel condensation reaction with an electron pulling unit under the alkalescent condition, and after TLC monitoring reaction is finished, directly enabling a reaction solvent to pass through a column by using a petroleum ether/dichloromethane eluent to obtain the final organic solar cell receptor material taking diindenobithiophene as a core; the ratio of the compound 8, the electron pulling unit, the pyridine and the chloroform is 0.2-2.2 mmol, 0.3-3.0 mmol, 0.01-0.5 mmol and 10-50 mL.
The diindenothiopheno [2,3-b ] thiophene six-membered ring electron donor central unit is synthesized firstly, and then the fused ring conjugated organic solar cell receptor material with the push-pull electron structure is synthesized through Suzuki coupling reaction and Knoevenagel condensation reaction, so that the preparation process is simple and controllable.
The invention provides an organic solar cell receptor material taking diindeno bithiophene as a core, and realizes the application of the organic solar cell material. Specifically, the acceptor material of the organic solar cell is the conjugated condensed ring organic small molecule acceptor, and the structural formula of the donor material PTB7-Th is as follows:
Figure BDA0002261926200000091
the invention provides an organic solar cell layered bulk heterojunction structure which sequentially comprises a glass substrate, an anode, a hole transport layer, an active layer, an electron transport layer and a cathode from bottom to top; the organic solar cell receptor material taking diindenobithiophene as a core is applied to an active layer.
After the technical scheme is adopted, compared with the background technology, the invention has the following beneficial effects:
1. the invention provides an organic solar cell receptor material taking diindeno bithiophene as A core, wherein A central electron-donating unit is diindeno-thieno [2,3-b ] thiophene, A pi electron connecting unit and A terminal receptor unit are introduced to form the receptor material with an A-Q-D-Q-A type structure, the molecular structure is simple and stable, the synthetic raw materials are cheap and easy to obtain, the preparation process is simple and controllable, and the industrial application is facilitated.
2. The different pi electron connection units can effectively adjust the conjugation length of molecules and the accumulation mode of a donor and an acceptor in an active layer, and simultaneously form sp3The hybrid orbit has a ladder-shaped whole molecule, and is beneficial to forming a good interpenetrating network structure for the receptor in the active layer.
3. According to the invention, different end-pulling electronic units can effectively regulate and control the energy level and spectral absorption of materials, meet the requirements of organic batteries on different energy levels, absorb sunlight in a visible region and a near infrared region, have a wider light absorption range, and improve the utilization rate of the organic solar batteries on the sunlight.
4. The organic solar cell receptor material taking diindeno bithiophene as a core has good solubility and film forming property, so that the preparation process of the active layer based on the material is simpler and more controllable.
5. The invention provides an organic solar cell receptor material taking diindeno bithiophene as a core and a simple and flexible preparation method, which overcome the defects of receptor molecular materials reported at present: the existing materials have complicated structures, expensive synthetic raw materials and difficult preparation process, and have single chemical structures, the regulation of material band gaps and the regulation of spectral absorption are limited, meanwhile, the existing small molecule acceptor materials have rigid structures, most electron donor cores in condensed rings form sp2Hybrid orbitals, which are detrimental to the stacking alignment of donor receptors, affect phase separation of the active layer, etc. The organic solar cell with the metal oxide layer is applied to an organic solar cell, and the requirement for improving the efficiency of a cell device is met.
Drawings
FIG. 1 is a scheme showing the synthesis scheme of SMOPV-1, an acceptor material prepared in example 1 of the present invention;
FIG. 2 is a scheme showing the synthesis scheme of SMOPV-3, an acceptor material prepared in example 3 of the present invention;
FIG. 3 is a synthetic scheme of the acceptor material SMOPV-5 prepared in example 5 of the present invention;
FIG. 4 is a nuclear magnetic hydrogen spectrum of an acceptor material SMOPV-1 prepared in example 1 of the present invention;
FIG. 5 is a nuclear magnetic carbon spectrum of an acceptor material SMOPV-1 prepared in example 1 of the present invention;
FIG. 6 is a nuclear magnetic hydrogen spectrum of an acceptor material SMOPV-3 prepared in example 3 of the present invention;
FIG. 7 is a nuclear magnetic carbon spectrum of an acceptor material SMOPV-3 prepared in example 3 of the present invention;
FIG. 8 is a nuclear magnetic hydrogen spectrum of an acceptor material SMOPV-5 prepared in example 5 of the present invention;
FIG. 9 is a nuclear magnetic carbon spectrum of SMOPV-5, an acceptor material prepared in example 5 of the present invention;
FIG. 10 shows the UV-VIS-NIR absorption spectrum of SMOPV-1/3/5 as an acceptor material in chlorobenzene solution;
FIG. 11 is a J-V curve of the acceptor material SMOPV-3 in a solar cell device with a device structure of ITO/PEDOT: PSS/PTB7-Th: SMOPV-3/Ca/Al.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The test methods described in the following examples are conventional methods unless otherwise specified; the materials, reagents and the like used are commercially available unless otherwise specified.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Example 1
The structural formula of the acceptor material (SMOPV-1) of the organic solar cell with the conjugated condensed ring small molecule as the core is as follows:
Figure BDA0002261926200000111
the preparation method of SMOPV-1 comprises the following steps (1) to (8):
(1) synthesis of Compound 1:
Figure BDA0002261926200000112
adding N-chlorosuccinimide into an N, N-dimethylformamide solution of bithiophene in a single-neck round-bottom flask, stirring for several hours at room temperature, monitoring by TLC, adding water for quenching after the reaction is finished, transferring the reaction solution into a separating funnel, extracting with diethyl ether, drying an organic phase with anhydrous sodium sulfate, and performing column chromatography with a petroleum ether eluent after the organic phase is dried to obtain a white solid, namely a bilateral-chloro bithiophene product 1; wherein the proportion of N-chlorosuccinimide, bithiophene and N, N-dimethylformamide is 10-20 mmol, 20-50 mmol and 40-100 mL; the yield is 90.4%; the structural characterization data are:1H NMR(400MHz,CDCl3),δ(ppm):6.19(s,2H)；13C NMR(100MHz,CDCl3),δ(ppm):134.7,130.8,118.9；MALDI-TOF MS(m/z):207.9(M-)。
(2) synthesis of Compound 3:
Figure BDA0002261926200000121
taking a double-mouth round-bottom flask, carrying out anhydrous and anaerobic treatment, dropwise adding a tetramethyl piperidine MgCl. LiCl catalyst into a tetrahydrofuran solution of dichlorothiophene under the protection of nitrogen, stirring at room temperature for 1-5 hours, reducing the reaction temperature to-80-0 ℃, and adding ethyl cyanoformate.
Carrying out unilateral hydroformylation and monitoring by TLC to obtain a unilateral hydroformylation product 2; repeating the hydroformylation again, after the reaction is finished, adding an ammonium chloride aqueous solution into the reaction solution for quenching, transferring the reaction solution into a separating funnel, extracting with diethyl ether, drying an organic phase with anhydrous sodium sulfate, and performing column chromatography with a petroleum ether/dichloromethane eluent to obtain a white solid, namely a bilateral hydroformylation product 3; wherein the ratio of the compound 1, tetramethyl piperidine MgCl, LiCl, ethyl cyanoformate and tetrahydrofuran is 10-18 mmol10 to 30mmol, 5 to 25mmol, 30 to 70 mL; the yield was 74.5%; the structural characterization data are:1H NMR(400MHz,CDCl3),δ(ppm):7.14(m,2H),7.19(m,2H),4.04(q,J＝7.1Hz,2H),1.01(t,J＝7.1Hz,3H)；13C NMR(100MHz,CDCl3),δ(ppm):160.2,137.5,134.8,133.7,132.3,130.6,129.8,129.4,128.1,127.9,123.1,61.5,14.1；MALDI-TOF MS(m/z):389.9(M-)。
(3) synthesis of Compound 4:
Figure BDA0002261926200000122
taking a double-opening round-bottom flask, carrying out anhydrous anaerobic treatment, sequentially adding a product 3, phenylboron, a palladium catalyst and cesium carbonate, displacing gas for 3 times, adding a toluene solvent under the protection of nitrogen to carry out Suzuki coupling reaction at the reaction temperature of 60-120 ℃, reacting overnight, after TLC monitoring reaction is finished, cooling to room temperature, adding water to quench, transferring a reaction solution into a separating funnel, extracting with dichloro, drying an organic phase with anhydrous sodium sulfate, and carrying out column chromatography with a petroleum ether/dichloromethane eluent to obtain a light yellow solid after spin-drying; wherein the proportion of the compound 3, phenylboronic ester, a palladium catalyst, cesium carbonate and toluene is 5-20 mmol, 12-32 mmol, 1-5 mmol, 30-90 mmol and 15-40 mL; the yield was 83.3%; the structural characterization data are:1H NMR(500MHz,CDCl3),δ(ppm):7.56-7.61(m,4H),7.44-7.46(m,6H),4.30(q,J＝7.1Hz,4H),1.27(t,J＝7.1Hz,6H)；13CNMR(125MHz,CDCl3),δ(ppm):162.0,154.0,137.4,133.4,130.0,129.0,128.0,120.3,61.0,14.0；MALDI-TOF MS(m/z):436.1(M-)。
(4) synthesis of Compound 5:
Figure BDA0002261926200000131
taking a double-mouth round-bottom flask, carrying out anhydrous and anaerobic treatment, adding a compound 4, replacing gas for 3 times, adding a tetrahydrofuran solvent under the protection of nitrogen, reacting at the temperature of 60-120 ℃, adding a phenylhexyl Grignard reagent under the protection of nitrogen, reacting overnight, and monitoring the reaction junction by TLC (thin layer chromatography)Cooling to room temperature, adding water for quenching, transferring the reaction liquid into a separating funnel, extracting with diethyl ether, and drying the organic phase with anhydrous sodium sulfate; directly dissolving the product in n-octane by using a double-opening round-bottom flask, adding glacial acetic acid and sulfuric acid, dehydrating and closing a ring under an acidic condition, adding water for quenching after the reaction is finished, transferring the reaction liquid into a separating funnel, extracting with ethyl acetate, drying an organic phase with anhydrous sodium sulfate, and performing column chromatography with a petroleum ether eluent to obtain a yellow oily substance after the organic phase is dried in a spinning mode to obtain the diindenothiopheno [2,3-b ] thiophene [2]A thiophene six-membered ring; wherein the proportion of the compound 4, the phenylhexyl Grignard reagent and the tetrahydrofuran is 4-14 mmol, 10-40 mmol and 20-60 mL; the ring-closing precursor, the glacial acetic acid, the sulfuric acid and the n-octane are mixed according to the proportion of 3-9 mmol, 0.1-1.5 mmol and 10-35 mL; the yield was 51.8%; the structural characterization data are:1H NMR(400MHz,CD2Cl2),δ(ppm):7.39(t,J＝7.6Hz,4H),7.26-7.30(m,4H),7.14(d,J＝8.4Hz,8H),7.07(d,J＝8.4Hz,8H),2.55(t,J＝7.6Hz,8H),1.55-1.60(m,8H),1.30-1.35(m,24H),0.85-0.89(m,12H)；13C NMR(150MHz,CD2Cl2),δ(ppm):153.2,146.9,142.6,140.2,137.7,136.1,128.5,128.0,125.9,119.0,63.2,35.7,31.9,29.4,22.0,14.1；MALDI-TOF MS(m/z):956.6(M-)。
(5) synthesis of Compound 6:
Figure BDA0002261926200000141
taking a double-mouth round-bottom flask, carrying out anhydrous and anaerobic treatment, adding a compound 5 and copper bromide/aluminum oxide powder prepared in advance, dissolving the compound 5 and the copper bromide/aluminum oxide powder in a carbon tetrachloride solution, heating to 50-80 ℃ under stirring, carrying out overnight reaction, cooling to room temperature after TLC monitoring reaction, filtering by using filter paper, and directly obtaining bilaterally brominated diindenothiopheno [2,3-b ] after evaporation and concentration]Thiophene, yellow solid product 6; wherein the proportion of the compound 5, copper bromide/aluminum oxide and carbon tetrachloride is 3-12 mmol, 8-25 mmol and 10-30 mL; the yield was 91.3%; the structural characterization data are:1H NMR(600MHz,CD2Cl2),δ(ppm):7.51(s,2H),7.42(d,J＝7.8Hz,2H),7.23(d,J＝7.8Hz,2H),7.09(q,J＝8.6Hz,16H),2.54(t,J＝7.8Hz,8H),1.52-1.67(m,8H),1.26-1.32(m,24H),0.84-0.86(m,12H)；13C NMR(150MHz,CD2Cl2),δ(ppm):155.3,147.2,142.3,141.9,139.3,136.7,136.4,130.8,128.5,129.2,128.7,127.8,120.2,119.8,63.4,35.8,32.0,31.7,29.5,29.34,23.0,14.3；MALDI-TOF MS(m/z):1112.3(M-)。
(6) synthesis of compound 7:
Figure BDA0002261926200000142
taking a double-opening round-bottom flask, carrying out anhydrous and anaerobic treatment, adding a compound 6 to displace gas for 3 times, adding a tetrahydrofuran solvent under the protection of nitrogen, carrying out bromine-lithium displacement reaction by using n-butyl lithium under the condition of low temperature, reacting at-78 ℃ for 1-5 hours, then adding isopropanol pinacol borate, slowly heating overnight for 12 hours to room temperature for reaction, adding water for quenching after the reaction is finished, transferring the reaction liquid to a separating funnel, extracting by using ethyl acetate, drying an organic phase by using anhydrous sodium sulfate, and directly using a crude product after spin-drying without further purification for next-step synthesis; wherein the proportion of the compound 6, n-butyl lithium, isopropanol pinacol borate and carbon tetrachloride is 2-15 mmol, 5-30 mmol, 7-20 mmol and 8-40 mL.
(7) Synthesis of Compound 8-1:
Figure BDA0002261926200000151
taking a double-opening round-bottom flask, carrying out anhydrous and anaerobic treatment, sequentially adding a product 7, a pi electronic connection unit 5-bromothiophene-2-acetaldehyde, a tetratriphenylphosphine palladium catalyst and cesium carbonate, replacing gas for 3 times, adding toluene under the protection of nitrogen to carry out Suzuki coupling reaction at the reaction temperature of 60-120 ℃, reacting overnight, after TLC monitoring reaction is finished, cooling to room temperature, adding water to quench, transferring the reaction liquid to a separating funnel, extracting with dichloro, drying an organic phase with anhydrous sodium sulfate, and carrying out column chromatography with petroleum ether/dichloromethane to obtain a yellowish red solid eluent; wherein, the compound is 7, 5-bromothiophene-2-acetaldehyde, and palladium tetratriphenylphosphineThe ratio of the catalyst, cesium carbonate and toluene is 0.2-2 mmol, 0.4-4.4 mmol, 0.1-0.8 mmol, 3-15 mmol and 10-50 mL; the yield was 61.2%; the structural characterization data are:1H NMR(600MHz,CDCl3),δ(ppm):9.85(s,2H),7.69(d,J＝7.2Hz,4H),7.61(d,J＝8.4Hz,2H),7.40(d,J＝7.8Hz,2H),7.35(d,J＝3.6Hz,2H),7.17(d,J＝8.4Hz,8H),7.10(d,J＝8.4Hz,8H),2.56(t,J＝7.8Hz,8H),1.55-1.65(m,8H),1.27-1.31(m,24H),0.84-0.86(m,12H)；13C NMR(150MHz,CDCl3),δ(ppm):182.7,154.7,154.4,148.1,142.5,142.1,141.9,139.7,139.2,137.4,136.9,130.6,128.6,127.9,126.2,123.2,119.5,63.4,35.6,31.7,31.3,29.2,22.6,14.1；MALDI-TOF MS(m/z):1176.5(M-)。
(8) synthesis of Compound 9-1:
Figure BDA0002261926200000152
dissolving a compound 8-1 in chloroform in a double-mouth round-bottom flask, carrying out Knoevenagel condensation reaction with a malononitrile indanone electron pulling unit under the alkalescent condition, and after TLC monitoring reaction is finished, directly passing reaction liquid through a column by using a petroleum ether/dichloromethane eluent to obtain the final organic solar cell taking diindenobithiophene as a core; wherein the ratio of the compound 8-1 to the electron pulling unit to the pyridine to the chloroform is 0.2-2.2 mmol: 0.3-3.0 mmol: 0.01-0.5 mmol: 10-50 mL; the yield was 84.7%; the structural characterization data are:1H NMR(500MHz,CDCl3),δ(ppm):8.85(s,2H),8.70(d,J＝7.0Hz,2H),7.93-7.95(m,2H),7.83(d,J＝4.5Hz,2H),7.73-7.79(m,8H),7.21(d,J＝8.5Hz,8H),7.12(d,J＝8.0Hz,8H),2.57(t,J＝7.5Hz,8H),1.60-1.63(m,8H),1.25-1.35(m,24H),0.82-0.87(m,12H)；13C NMR(150MHz,CDCl3),δ(ppm):188.4,160.5,154.6,148.7,146.3,140.0,139.5,138.0,136.9,136.2,135.2,134.6,128.7,128.0,125.4,124.8,123.8,122.4,123.8,122.4,119.7,114.6,114.5,77.2,77.0,76.8,69.6,63.5,35.6,31.7,31.2,29.7,29.2,22.6,14.0；MALDI-TOF MS(m/z):1528.6(M-)。
example 2
The structural formula of the acceptor material (SMOPV-2) of the organic solar cell with the conjugated condensed ring small molecule as the core is as follows:
Figure BDA0002261926200000161
the preparation method of SMOPV-2 comprises the following steps (1) to (8):
wherein, the steps (1) to (7) in the SMOPV-2 preparation method are the same as the preparation steps (1) to (7) in the example 1;
(8) synthesis of Compound 9-2:
Figure BDA0002261926200000162
dissolving a compound 8-1 in chloroform in a double-mouth round-bottom flask, carrying out Knoevenagel condensation reaction on the compound and a difluoromalononitrile indanone electron unit under a weak alkaline condition, and after TLC monitoring reaction is finished, directly passing reaction liquid through a column by using a petroleum ether/dichloromethane eluent to obtain the final organic solar cell taking diindenobithiophene as a core; wherein the ratio of the compound 8-1 to the electron pulling unit to the pyridine to the chloroform is 0.2-2.2 mmol: 0.3-3.0 mmol: 0.01-0.5 mmol: 10-50 mL; the yield was 78.5%;1H NMR、13the compound obtained by C NMR and MALDI-TOF MS surface was the target product 9-2.
Example 3
The structural formula of the acceptor material (SMOPV-3) of the organic solar cell with the conjugated condensed ring small molecule as the core is as follows:
Figure BDA0002261926200000171
the preparation method of SMOPV-3 comprises the following steps (1) to (8):
wherein, the steps (1) to (6) in the SMOPV-3 preparation method are the same as the preparation steps (1) to (6) in the example 1;
(7) synthesis of Compound 8-2:
Figure BDA0002261926200000172
taking a double-opening round-bottom flask, carrying out anhydrous and anaerobic treatment, sequentially adding a product 7, 5-bromo-4- ((2-ethylhexyl) oxy) thiophene-2-formaldehyde as a pi electronic connection unit, a tetratriphenylphosphine palladium catalyst and cesium carbonate, replacing gas for 3 times, adding toluene under the protection of nitrogen to carry out Suzuki coupling reaction, heating until reaction liquid is refluxed and reacted overnight, cooling to room temperature after TLC monitoring reaction is finished, adding water to quench, transferring the reaction liquid to a separating funnel, extracting with dichloro, drying an organic phase with anhydrous sodium sulfate, and carrying out column chromatography by using petroleum ether/dichloromethane as an eluent to obtain a yellowish red solid after spin-drying; wherein the ratio of the compound 7, 5-bromo-4- ((2-ethylhexyl) oxy) thiophene-2-formaldehyde, palladium tetratriphenylphosphine catalyst, cesium carbonate and toluene is 0.2-2 mmol, 0.4-4.4 mmol, 0.1-0.8 mmol, 3-15 mmol, and 10-50 mL; the yield is 58.6%; the structural characterization data are:1H NMR(600MHz,CDCl3),δ(ppm):9.96(s,2H),7.64(s,2H),7.59(d,J＝7.8Hz,2H),7.39(d,J＝7.8Hz,2H),7.17(d,J＝8.4Hz,8H),7.10(d,J＝8.4Hz,8H),6.98(s,2H),4.08(d,J＝6.0Hz,2H),2.56(t,J＝7.8Hz,8H),1.75-1.79(m,2H),1.60-1.61(m,12H),1.26-1.35(m,36H),0.85-0.97(m,24H)；13C NMR(150MHz,CDCl3),δ(ppm):180.8,165.2,154.5,153.5,148.3,142.7,142.3,139.7,139.5,137.1,30.9,128.1,125.9,123.4,120.3,119.6,111.7,74.6,63.5,39.7,35.7,31.8,31.4,30.6,29.3,29.1,24.0,23.1,22.7,14.3,14.2,11.3；MALDI-TOF MS(m/z):1432.6(M-)。
(8) synthesis of Compounds 9-3:
Figure BDA0002261926200000181
dissolving a compound 8-2 in chloroform in a double-mouth round-bottom flask, carrying out Knoevenagel condensation reaction on the compound and a difluoromalononitrile indanone electron unit under a weak alkaline condition, and after TLC monitoring reaction is finished, directly passing reaction liquid through a column by using a petroleum ether/dichloromethane eluent to obtain the final organic solar cell taking diindenobithiophene as a core; wherein the proportion of the compound 8-2, the electron withdrawing unit, the pyridine and the chloroform is 0.2-2.2 m0.3-3.0 mmol, 0.01-0.5 mmol, 10-50 mL; the yield was 77.5%; the structural characterization data are:1H NMR(500MHz,CDCl3),δ(ppm):9.17(s,2H),8.49-8.52(m,2H),7.77-7.81(m,4H),7.63(t,J＝7.2Hz,2H),7.45(d,J＝7.8Hz,2H),7.20(d,J＝8.4Hz,8H),7.13(d,J＝8.4Hz,8H),7.05(s,2H),4.13-4.18(m,4H),2.58(t,J＝7.8Hz,8H),1.87-1.90(m,2H),1.60-1.62(m,12H),1.25-1.35(m,36H),0.84-0.97(m,24H)；13C NMR(150MHz,CDCl3),δ(ppm):186.5,170.2,160.8,158.9,154.7,149.1,142.9,142.4,139.3,137.6,134.3,133.5,128.8,128.6,128.0,126.9,119.8,117.8,117.6,115.1,14.7,114.5,109.9,107.7,63.5,35.6,31.7,31.3,30.1,29.7,29.2,29.0,23.5,23.0,22.6,14.1,14.0,11.0；MALDI-TOF MS(m/z):1528.6(M-)。
example 4
The structural formula of the acceptor material (SMOPV-4) of the organic solar cell with the conjugated condensed ring small molecule as the core is as follows:
Figure BDA0002261926200000191
the preparation method of SMOPV-4 comprises the following steps (1) to (8):
wherein, the preparation method of SMOPV-4 comprises the same steps (1) to (7) as the preparation steps (1) to (7) in the example 3;
(8) synthesis of Compounds 9-4:
Figure BDA0002261926200000192
dissolving a compound 8-2 in chloroform in a double-mouth round-bottom flask, carrying out Knoevenagel condensation reaction on the compound and a dichloromalononitrile indanone electron unit under the alkalescent condition, and after TLC monitoring reaction is finished, directly passing reaction liquid through a column by using a petroleum ether/dichloromethane eluent to obtain the final organic solar cell taking diindenobithiophene as a core; wherein the ratio of the compound 8-2 to the electron pulling unit to the pyridine to the chloroform is 0.2-2.2 mmol to 0.3-3.0 mmol to 0.01-0.5 mmol to 10-50 mL; the yield was 75.8%,1H NMR、13c NMR and MALDI-TOF MS surfacesThe obtained compound is the target product 9-4.
Example 5
The structural formula of the acceptor material (SMOPV-5) of the organic solar cell with the conjugated condensed ring small molecule as the core is as follows:
the preparation method of SMOPV-5 comprises the following steps (1) to (8):
wherein, the steps (1) to (6) in the SMOPV-5 preparation method are the same as the preparation steps (1) to (6) in the example 1;
(7) synthesis of Compounds 8-3:
Figure BDA0002261926200000202
taking a double-mouth round-bottom flask, carrying out anhydrous and anaerobic treatment, and sequentially adding a product 7 and 6-bromo-2-octyl thiophene [3,4-b ] as a pi electron connection unit]Thiophene-4-formaldehyde, a palladium tetratriphenylphosphine catalyst and cesium carbonate, replacing gas for 3 times, adding toluene under the protection of nitrogen for Suzuki coupling reaction, heating until reaction liquid is refluxed and reacted overnight, cooling to room temperature after TLC monitoring reaction is finished, adding water for quenching, transferring the reaction liquid into a separating funnel, extracting with dichloro, drying an organic phase with anhydrous sodium sulfate, and performing column chromatography with petroleum ether/dichloromethane eluent after spin drying to obtain a yellowish red solid; wherein, the compound is 7, 6-bromo-2-octyl thiophene [3,4-b]The ratio of the thiophene-4-formaldehyde to the palladium tetratriphenylphosphine catalyst to the cesium carbonate to the toluene is 0.2-2 mmol, 0.4-4.4 mmol, 0.1-0.8 mmol, 3-15 mmol and 10-50 ml; the structural characterization data are:1H NMR(600MHz,CDCl3),δ(ppm):9.84(s,2H),7.77(s,2H),7.64(d,J＝7.8Hz,2H),7.46(d,J＝7.8Hz,2H),7.21(d,J＝8.4Hz,8H),7.12(d,J＝8.4Hz,8H),6.80(s,2H),2.82(t,J＝7.8Hz,4H),2.57(t,J＝7.8Hz,8H),1.70-1.75(m,4H),1.56-1.61(m,8H),1.26-1.40(m,44H),0.85-0.89(m,18H)；13C NMR(150MHz,CDCl3),δ(ppm):179.4,154.4,148.0,143.9,142.7,142.2,141.3,139.8,138.7,137.0,131.0,128.6,127.9,127.5,125.2,124.4,119.7,113.0,63.4,35.6,31.9,31.7,31.3,30.4,29.7,29.4,29.3,29.2,29.1,22.7,22.6,14.1,14.0；MALDI-TOF MS(m/z):1512.7(M-)。
(8) synthesis of Compounds 9-5:
Figure BDA0002261926200000211
dissolving a compound 8-3 in chloroform in a double-mouth round-bottom flask, carrying out Knoevenagel condensation reaction on the compound and a difluoromalononitrile indanone electron unit under a weak alkaline condition, and after TLC monitoring reaction is finished, directly passing reaction liquid through a column by using a petroleum ether/dichloromethane eluent to obtain the final organic solar cell taking diindenobithiophene as a core; wherein the ratio of the compound 8-3 to the electron pulling unit to the pyridine to the chloroform is 0.2-2.2 mmol to 0.3-3.0 mmol to 0.01-0.5 mmol to 10-50 ml; the yield was 76.4%; the structural characterization data are:1H NMR(500MHz,CDCl3),δ(ppm):8.93(s,2H),8.51-8.53(m,2H),7.88(s,2H),7.81(d,J＝8.4Hz,2H),7.65(t,J＝7.2Hz,2H),7.51(d,J＝7.8Hz,2H),7.23(d,J＝8.4Hz,8H),7.15(d,J＝8.4Hz,8H),6.83(s,2H),2.82(t,J＝7.2Hz,4H),2.58(t,J＝7.8Hz,8H),1.72-1.74(m,4H),1.57-1.62(m,8H),1.25-1.34(m,44H),0.84-0.89(m,18H)；13C NMR(150MHz,CDCl3),δ(ppm):186.5,158.8,154.7,154.5,150.9,148.9,143.2,143.1,142.4,140.1,139.5,137.7,136.7,134.4,133.4,130.7,128.7,127.9,125.4,123.2,120.0,118.8,114.9,114.9,114.8,114.7,68.1,63.5,35.6,31.8,31.7,31.4,29.7,29.3,29.2,29.1,22.7,22.6,14.1,14.0；MALDI-TOF MS(m/z):1936.8(M-)。
example 6
The structural formula of the acceptor material (SMOPV-6) of the organic solar cell with the conjugated condensed ring small molecule as the core is as follows:
Figure BDA0002261926200000221
the preparation method of SMOPV-6 comprises the following steps (1) to (8):
wherein, the preparation method of SMOPV-6 comprises the same steps (1) to (7) as those of the preparation steps (1) to (7) of example 5;
(8) synthesis of Compounds 9-6:
Figure BDA0002261926200000222
dissolving a compound 8-3 in chloroform in a double-mouth round-bottom flask, carrying out Knoevenagel condensation reaction on the compound and a dichloromalononitrile indanone electron unit under the alkalescent condition, and after TLC monitoring reaction is finished, directly passing reaction liquid through a column by using a petroleum ether/dichloromethane eluent to obtain the final organic solar cell taking diindenobithiophene as a core; wherein the ratio of the compound 8-3 to the electron pulling unit to the pyridine to the chloroform is 0.2-2.2 mmol to 0.3-3.0 mmol to 0.01-0.5 mmol to 10-50 ml; the yield was 66.5%,1H NMR、13the compound obtained by C NMR and MALDI-TOF MS surface was the target product 9-6.
Example 7
The structural formula of the acceptor material (SMOPV-7) of the organic solar cell with the conjugated condensed ring small molecule as the core in the embodiment is as follows:
Figure BDA0002261926200000223
the preparation method of SMOPV-7 comprises the following steps (1) to (8):
wherein, the preparation method of SMOPV-7 has the same steps (1) to (7) as the preparation steps (1) to (7) in the example 5;
(8) synthesis of Compounds 9-7:
Figure BDA0002261926200000231
dissolving a compound 8-3 in chloroform in a double-mouth round-bottom flask, carrying out Knoevenagel condensation reaction on the compound and a dimethyl malononitrile indanone electron unit under the alkalescent condition, and after TLC monitoring reaction is finished, directly passing reaction liquid through a column by using a petroleum ether/dichloromethane eluent to obtain the final organic solar cell taking diindenobithiophene as a core; wherein, the compound 8-3, the electrodeThe ratio of the subunit, pyridine and chloroform is 0.2-2.2 mmol, 0.3-3.0 mmol, 0.01-0.5 mmol and 10-50 ml; the yield was 57.4%;1H NMR、13the compound obtained by C NMR and MALDI-TOF MS surface was the target product 9-7.
Example 8
The structural formula of the acceptor material (SMOPV-8) of the organic solar cell with the conjugated condensed ring small molecule as the core is as follows:
Figure BDA0002261926200000232
the preparation method of SMOPV-8 comprises the following steps (1) to (8):
wherein, the preparation method of SMOPV-8 has the same steps (1) to (7) as the preparation steps (1) to (7) in the example 5;
(8) synthesis of Compounds 9-8:
Figure BDA0002261926200000241
dissolving a compound 8-3 in chloroform in a double-mouth round-bottom flask, carrying out Knoevenagel condensation reaction with a malononitrile thiophene ketone electron unit under the alkalescent condition, and after TLC monitoring reaction is finished, directly passing reaction liquid through a column by using petroleum ether/dichloromethane eluent to obtain the final organic solar cell taking diindeno-bithiophene as a core; wherein the ratio of the compound 8-3 to the electron pulling unit to the pyridine to the chloroform is 0.2-2.2 mmol, 0.3-3.0 mmol, 0.01-0.5 mmol, 10-50 mL, and the yield is 44.2%;1H NMR、13the compound obtained by C NMR and MALDI-TOF MS surface was the target product 9-8.
Example 9
The structural formula of the acceptor material (SMOPV-9) of the organic solar cell with the conjugated condensed ring small molecule as the core is as follows:
Figure BDA0002261926200000242
the preparation method of SMOPV-9 comprises the following steps (1) to (8):
wherein, the preparation method of SMOPV-9 comprises the same steps (1) to (7) as those of the preparation steps (1) to (7) of example 5;
(8) synthesis of Compounds 9-9:
Figure BDA0002261926200000243
dissolving a compound 8-3 in chloroform in a double-mouth round-bottom flask, carrying out Knoevenagel condensation reaction with a malononitrile tetralone electron pulling unit under a weak alkaline condition, and after TLC monitoring reaction is finished, directly passing reaction liquid through a column by using petroleum ether/dichloromethane eluent to obtain the final organic solar cell taking diindenobithiophene as a core; wherein the ratio of the compound 8-3 to the electron pulling unit to the pyridine to the chloroform is 0.2-2.2 mmol: 0.3-3.0 mmol: 0.01-0.5 mmol: 10-50 mL; the yield was 35.7%;1H NMR、13the compound obtained by C NMR and MALDI-TOF MS surface was the target product 9-9.
Example 10
The diindeno-bithiophene core organic solar cell receptor material prepared in example 3 is applied to an organic solar cell device and photovoltaic performance characterization thereof.
The transparent conductive glass with the strip-shaped ITO electrode etched on the surface is sequentially cleaned by ultrasonic oscillation of a cleaning agent, deionized water, acetone and isopropanol, dried and treated with ultraviolet ozone for 10 minutes; and then, spin-coating a layer of PEDOT (PSS) on the surface of the conductive glass at the rotating speed of 3000rmp for 30 seconds, and then annealing at 150 ℃ for 15 min. The sheet was then transferred to a glove box. Then, 1:1 by weight of 1, 8-Diiodooctane (DIO) and 20.0mg/mL total concentration of PTB7-Th, which are receptor mixed solutions prepared by the present invention, were stirred overnight and spin-coated at 1700rmp for 45 seconds to prepare an active layer; and finally, respectively evaporating a layer of Ca with the thickness of 20nm and an Al electrode with the thickness of 80nm by using an evaporation instrument to obtain a complete device.
The diindeno-bithiophene core organic solar cell receptor material prepared in example 3 is applied to a cell device, and the measurement of the device is carried out at 100mW/cm2Solar moduleThe current-voltage curve under the illumination of the simulator AM 1.5G is shown in FIG. 11, and the J of each device can be read from FIG. 11sc、VocAnd calculates FF and PCE.
Mixing fullerene derivative (PC)61BM、PC71BM, etc.) into the bulk heterojunction described above, forming a ternary blended organic solar cell. The ternary organic solar cell maintains a single cell structure, and a complementary absorption third component (fullerene derivative) is introduced into the binary active layer, so that the advantages of high electron mobility of fullerene receptors and high visible-near infrared absorption of non-fullerene receptors are combined. The three components form an ideal gradient electronic structure, the spectrum absorption is widened, the electronic transmission is improved, and the short-circuit current density of the battery is obviously improved.
The results show that the organic solar cell receptor material taking diindeno bithiophene as the core has photoelectric conversion efficiency as an active layer of an organic solar cell, and is a very potential active receptor material.
The hydrogen spectrum and the carbon spectrum of the diindeno-bithiophene core organic solar cell receptor material prepared in the examples 1, 3 and 5 and the small molecular structure of the intermediate step are tested by a nuclear magnetic instrument spectrum BrukeraV 600; the test results are shown in fig. 4 to 9.
The diindeno-bithiophene core organic solar cell receptor materials prepared in examples 1, 3 and 5 were subjected to ultraviolet-visible absorption spectrum test on a Carry-5000 ultraviolet-visible light-near infrared spectrophotometer. First, the acceptor material was separately dissolved in chlorobenzene at a concentration of 10%-5mol/L, absorption profile of the test solution, and the test results are shown in FIG. 10.
The diindeno-bithiophene core organic solar cell receptor materials prepared in examples 1, 3 and 5 were subjected to charged chemical testing, and the redox potential of the molecules was tested by cyclic voltammetry. In the invention, an electrochemical workstation is used for testing electrochemical properties, an electrolytic cell is a three-electrode system (a glassy carbon electrode is a working electrode, a platinum wire electrode is an auxiliary electrode, a silver/silver chloride electrode is a reference electrode), ferrocene is taken as an internal standard, dried acetonitrile is taken as a solvent, 0.1mol/L tetrabutylammonium hexafluorophosphate is taken as a supporting electrolyte, and the scanning speed is 100 mV/s. And scanning under the protection of nitrogen to obtain a cyclic voltammetry curve. The LUMO energy level of the SMOPV-1 is-3.88 eV, the HOMO is-5.59 eV and the corresponding band gap is 1.71eV obtained by a cyclic voltammetry test; the LUMO energy level of the SMOPV-3 is-3.1 eV, the HOMO is-5.61 eV and the corresponding band gap is 1.70 eV; the LUMO energy level of SMOPV-5 is-4.00 eV, the HOMO is-5.55 eV, and the corresponding band gap is 1.55 eV.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (10)

1. An organic solar cell receptor material taking diindeno bithiophene as a core is characterized by having the following chemical structural formula:
Figure FDA0002261926190000011
wherein R is1Is one of hydrogen atom, straight chain or branched chain alkyl with 3-15 carbon atoms, straight chain or branched chain alkoxy with 3-15 carbon atoms, phenylalkyl with 3-15 carbon atoms, phenylalkoxy with 3-15 carbon atoms, thiophenyl with 3-15 carbon atoms and thiophenyl alkoxy with 3-15 carbon atoms; q is a pi electron linking unit selected from aromatic ring derivatives; a is an end group pull electronic unit.
2. The diindenobithiophene-based organic solar cell acceptor material of claim 1, wherein Q is a pi electron linking unit having a chemical structural formula of one of:
Figure FDA0002261926190000012
wherein, X is one of oxygen atom, sulfur atom or selenium atom; r2-R5Are independently selected from hydrogen atom, aryl, hydroxyl, carbonyl, halogen atom, C3-15 straight-chain or branched-chain alkyl, and C3-15 straight-chain or branched-chain alkoxy.
3. The diindenobithiophene-based organic solar cell receptor material of claim 1, wherein A is an end-group electron withdrawing unit, and the chemical structural formula of the end-group electron withdrawing unit is one of the following formulas:
Figure FDA0002261926190000013
wherein R is6、R7Are independently selected from hydrogen atoms and straight chain or branched chain alkyl with 1-15 carbon atoms; r8、R9Are independently selected from hydrogen atoms, halogen atoms, methyl or methoxy.
4. The diindenobithiophene-based organic solar cell receptor material of any one of claims 1-3, wherein when R is1When the compound is a phenylhexyl, Q is monothiophene, and A is 2- (3-oxo-2, 3-dihydro-1H-indene-1-ylidene) malononitrile, the organic solar cell receptor material taking diindenobithiophene as a core is SMOPV-1, and the structural formula of the SMOPV-1 is as follows:
Figure FDA0002261926190000021
5. the diindenobithiophene-based organic solar cell receptor material of any one of claims 1-3, wherein when R is1When the compound is a phenylhexyl, Q is monothiophene, and A is 2- (5, 6-difluoro-3-oxo-2, 3-dihydro-1H-indene-1-ylidene) malononitrile, the organic solar cell receptor material taking diindenobithiophene as a core is SMOPV-2, and the structural formula of the SMOPV-2 is as follows:
Figure FDA0002261926190000022
6. the diindenobithiophene-based organic solar cell receptor material of any one of claims 1-3, wherein when R is1When the conjugated small molecule organic solar cell acceptor material is a phenylhexyl group, Q is 3- ((2-ethylhexyl) oxy) thiophene, A is 2- (5, 6-difluoro-3-oxo-2, 3-dihydro-1H-indene-1-ylidene) malononitrile, the conjugated small molecule organic solar cell acceptor material is SMOPV-3, and the SMOPV-3 has a structural formula:
Figure FDA0002261926190000023
7. the diindenobithiophene-based organic solar cell receptor material of any one of claims 1-3, wherein when R is1When the compound is a phenylhexyl, Q is 2-hexylthienothiophene, and A is 2- (3-oxo-2, 3-dihydro-1H-indene-1-ylidene) malononitrile, the organic solar cell receptor material taking diindenobithiophene as a core is SMOPV-4, and the structural formula of the SMOPV-4 is as follows:
8. the diindenobithiophene-based organic solar cell receptor material of any one of claims 1-3, wherein when R is1When the compound is a phenylhexyl, Q is 2-hexylthienothiophene, A is 2- (5, 6-difluoro-3-oxo-2, 3-dihydro-1H-indene-1-ylidene) malononitrile, the organic solar cell receptor material taking diindenobithiophene as a core is SMOPV-5, and the SMOPV-5 has a structural formula:
Figure FDA0002261926190000032
9. the preparation method of the diindeno-bithiophene core-based organic solar cell receptor material as claimed in any one of claims 1 to 8, comprising the following steps:
1) adding N-chlorosuccinimide into N, N-dimethylformamide solution of bithiophene, and stirring at room temperature to obtain bilateral chlorinated bithiophene;
2) at room temperature, dripping a tetramethyl piperidine MgCl & LiCl catalyst into a tetrahydrofuran solution of dichloro bithiophene, then reducing the reaction temperature, and adding ethyl cyanoformate to carry out unilateral hydroformylation; repeating the above-mentioned hydroformylation reaction again to obtain dichloro-bithiophene with bilateral hydroformylation;
3) carrying out Suzuki coupling reaction on the double-sided aldehyde dichlorodithiophene product and phenylboron ester to obtain a ring-closing precursor;
4) reacting the ring-closing precursor obtained in the step 3) with a Grignard reagent; dehydrating and ring-closing under acidic condition to obtain a diindenothiopheno [2,3-b ] thiophene six-membered ring;
5) heating a diindenothiopheno [2,3-b ] thiophene six-membered ring and copper bromide/aluminum oxide in a carbon tetrachloride solution under stirring for overnight reaction to obtain a bilaterally brominated diindenothiopheno [2,3-b ] thiophene six-membered ring;
6) carrying out bromine-lithium exchange reaction on the bilaterally brominated diindenothiopheno [2,3-b ] thiophene six-membered ring product in the step 5) by using n-butyl lithium at the temperature of-80 to-40 ℃, then adding isopropanol pinacol borate at the temperature of-80 to-40 ℃, standing overnight for 12h, slowly heating to room temperature, and reacting to obtain a bilaterally boron lipidated diindenothiopheno [2,3-b ] thiophene six-membered ring;
7) carrying out Suzuki coupling reaction on the bilateral boron lipidated diindenothiopheno [2,3-b ] thiophene six-membered ring obtained in the step 6) and the pi electron connecting unit described in the claim 2 to obtain a diindenothiophene product containing a bridge unit;
8) carrying out Knoevenagel condensation reaction on the diindenodithiophene product containing the bridge unit obtained in the step 7) and the electron pulling unit in the claim 3 under the pyridine alkalescence condition to finally obtain the diindenodithiophene-based organic solar cell receptor material.
10. The use of the diindenobithiophene-based organic solar cell receptor material according to any one of claims 1 to 9, wherein: the organic solar cell is of a layered bulk heterojunction structure and sequentially comprises a glass substrate, an anode, a hole transport layer, an active layer, an electron transport layer and a cathode from bottom to top; the organic solar cell receptor material taking diindenobithiophene as a core is applied to an active layer.
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