CN110790757A - Thiophene indanone and carbazole based A-pi-D-pi-A type small molecule solar cell receptor material and preparation method thereof - Google Patents
Thiophene indanone and carbazole based A-pi-D-pi-A type small molecule solar cell receptor material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an A-pi-D-pi-A type micromolecule solar cell receptor material based on thiophene indanone and carbazole and a preparation method thereof. The receptor material has a structure shown in a general formula I; the method is characterized in that carbazole is used as a central core structure, groups such as thiophene, furan, benzene and the like are used as a pi bridge, and aldehyde groups at two ends are subjected to condensation reaction with active sites of thiophene indanone which is an electron-withdrawing group at normal temperature and normal pressure to obtain the symmetrical target molecule. The A-pi-D-pi-A type micromolecule solar cell receptor material based on the thiophene indanone and the carbazole has the advantages of simple synthesis method, easily controlled reaction conditions, higher yield, universal applicability and high-efficiency synthesis; can be widely applied to the fields of energy, life, analysis, material science and the like, and is particularly suitable for being used as organic micromolecule solar energy electricityPool acceptor materials, and the like.
Description
The technical field is as follows:
the invention relates to the field of solar cells, in particular to an A-pi-D-pi-A type micromolecule solar cell receptor material based on thiophene indanone and carbazole and a preparation method thereof.
Background art:
the thiophene indanone is a novel electron-withdrawing group which is developed in recent years and is widely concerned and paid attention to, and the thiophene indanone derivative is a good photosensitive material, has good stability, high molar extinction coefficient and narrower energy gap, and has the characteristics of good photophysical chemical properties, stability, high energy conversion efficiency and the like when being used as an end-blocking group of a symmetrical small-molecule receptor material. Therefore, the micromolecule solar cell receptor material taking the thiophene indanone as the end capping group has good application prospect in the field of organic micromolecule solar cells.
However, so far, there are few reports about the application of organic small molecule solar cells using thiophen indanone as a blocking group, and there are problems of lack of sufficient molecular design and necessary optimization of synthetic route, single structure and low photovoltaic efficiency. Therefore, the preparation of different types of thiophene indanone derivatives from simpler raw materials through a simple synthetic route is a difficult point which needs to be solved urgently.
The invention content is as follows:
one of the technical problems to be solved by the invention is to provide an A-pi-D-pi-A type micromolecule solar cell receptor material based on thiophene indanone and carbazole, which has the advantages of wider and stronger ultraviolet absorption, higher molar extinction coefficient and more stable photochemical property.
The invention also provides a preparation method of the A-pi-D-pi-A type micromolecule solar cell receptor material based on the thiophene indanone and the carbazole, which is simple in process and high in target molecule yield.
In order to better solve the first technical problem, the invention adopts the following technical scheme:
a thiophene indanone and carbazole based A-pi-D-pi-A type small molecule solar cell receptor material has a structure of a general formula I:
in the formula I, pi is specifically any one of the following structural units:
wherein n is a natural number of 1 to 20.
In order to better solve the second technical problem, the invention adopts the following technical scheme:
a preparation method of an A-pi-D-pi-A type small molecule solar cell receptor material based on thiophene indanone and carbazole comprises the following steps:
(1) under the alkaline environment, carrying out boron esterification reaction on 2, 7-dibromocarbazole and bis (pinacolato) boron ester to prepare an intermediate 1, wherein the structure is as follows:
(2) the intermediate 1 and 5-bromothiophene-2-formaldehyde are subjected to a suzuki reaction under the catalysis of a catalyst to obtain an intermediate 2, and the structure of the intermediate is as follows:
(3) the intermediate 1 and 5-bromofuran-2-formaldehyde are subjected to a suzuki reaction under the catalysis of a catalyst to obtain an intermediate 3, and the structure of the intermediate is as follows:
(4) the intermediate 1 and p-bromobenzaldehyde are subjected to a suzuki reaction under the catalysis of a catalyst to obtain an intermediate 4, and the structure of the intermediate is as follows:
(5) the intermediate 2 and the thiophene indanone undergo condensation reaction to obtain a target molecule CTC1, and the structure is as follows:
(6) the intermediate 3 and the thiophene indanone undergo condensation reaction to obtain a target molecule CTC2, and the structure is as follows:
(7) the intermediate 4 and the thiophene indanone undergo condensation reaction to obtain a target molecule CTC3, and the structure is as follows:
as a preferable technical solution, in the steps (2) to (4), the reaction solvent used in the suzuki reaction is a mixture of a toluene solvent and a 2M sodium carbonate solution; the volume ratio of the toluene solvent to the 2M sodium carbonate solution is 2: 1-4: 1.
In a preferable embodiment, in the steps (2) to (4), the molar ratio of the 5-bromothiophene-2-carbaldehyde to the intermediate 1, the molar ratio of the 5-bromofuran-2-carbaldehyde to the intermediate 1, and the molar ratio of the p-bromobenzaldehyde to the intermediate 1 are all 1:2 to 1: 6.
As a preferable technical scheme, in the steps (2) to (4), the reaction temperature of the suzuki coupling reaction is 90-110 ℃; the reaction time of the suzuki reaction is 24-36 hours.
As aIn a preferable technical scheme, in the steps (2) to (4), the catalyst is Pd (PPh)3)4。
In a preferable technical scheme, in the steps (5) to (7), the molar ratio of the intermediate 2 to the thiophenindione, the molar ratio of the intermediate 3 to the thiophenindione, and the molar ratio of the intermediate 4 to the thiophenindione are all 1:2 to 1: 8.
As a preferable technical scheme, in the steps (5) to (7), the reaction temperature of the condensation reaction is 0-70 ℃; the reaction time of the condensation reaction is 12-24 h.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
the invention provides a series of A-pi-D-pi-A type micromolecule solar cell receptor materials based on thiophene indanone and carbazole, which have novel structures, and the receptor materials have better planarity of target molecules, stronger electron-donating capability, benefit for charge transmission in molecules and excellent photoelectric performance by adding a pi bridge group between a donor unit and a receptor unit; in addition, the thiophene indanone is used as a blocking group, so that the molecules have relatively wide and strong ultraviolet absorption, relatively high molar extinction coefficient and relatively stable photochemical property, and a new idea is provided for constructing an organic solar cell material.
The invention also discloses a preparation method of the A-pi-D-pi-A type micromolecule solar cell receptor material based on thiophene indanone and carbazole, the preparation method synthesizes important intermediates 2-4 through a series of reactions, and finally, the intermediates and thiophene indanone groups are utilized to carry out condensation reaction to obtain a series of target molecules respectively taking thiophene, furan and benzene rings as pi bridges; the synthesis method of the receptor material is optimized, so that the synthesis yield of the compound is improved. The synthesis reaction conditions provided by the invention are easy to control, the product is simple to purify, the comprehensive yield is higher, and the method has universality.
By analyzing the spectral and electrochemical data of the target molecules, the target molecules have stable spectral absorption, obvious pi-pi accumulation phenomenon, narrow energy gap shown by electrochemistry, good stability in air and potential application value in the aspect of organic solar cell materials.
Description of the drawings:
FIG. 1 is a nuclear magnetic hydrogen spectrum of CTC 1;
FIG. 2 is a nuclear magnetic hydrogen spectrum of CTC 2;
FIG. 3 is a nuclear magnetic hydrogen spectrum of CTC 3;
figure 4 is a mass spectrum of CTC 1;
figure 5 is a mass spectrum of CTC 2;
figure 6 is a mass spectrum of CTC 3;
FIG. 7 is a thermogravimetric plot of CTC1, CTC2, CTC 3;
fig. 8 is a hole mobility plot for CTC1, CTC2, CTC3 blend films;
fig. 9 is an electron mobility plot for CTC1, CTC2, CTC3 blended films.
The specific implementation mode is as follows:
the present invention is further illustrated by the following examples, which are provided for the purpose of illustration only and are not intended to be limiting.
Example 1
(1) Synthesis of intermediate 1
Adding 2, 7-dibromo-9- (heptadecane-9-yl) -9-carbazole (2.86g, 5.1mmol), bis (pinacolato) boron ester (4g, 15.70mmol), potassium acetate (4g, 40mmol), 1,4 dioxane solvent (180mL) and magnetite into a dry and clean 250mL three-necked bottle, stirring to dissolve reactants, vacuumizing the system, replacing with argon, and adding a proper amount of catalyst Pd (dppf) Cl2Vacuumizing the system, replacing with argon, reacting at 80 deg.C overnight, monitoring by spot plate until the reaction is complete, stopping the reaction, cooling the system to room temperature, extracting with ethyl acetate for 3-5 times, washing with saturated NaCl solution for 3-5 times, retaining the organic phase, and adding anhydrous MgSO4The powder was dried, the solvent was removed under reduced pressure, and the product was isolated and purified by silica gel chromatography (ethyl acetate: petroleum ether ═ 12:1) to give intermediate 1(2.98g, 91% yield) as a white solid.1H NMR(400MHz,CDCl3)δ:7.82(d,J＝7.5Hz,1H),7.76–7.71(m,2H),2.04–1.95(m,2H),1.38(s,12H),1.17–0.98(m,10H),0.82(t,J＝7.1Hz,3H),0.53(s,2H).13C NMR(101MHz,CDCl3)δ:150.49,143.93,133.67,128.92,119.42,83.74,55.21,40.13,31.82,29.97,29.22,24.97,23.61,22.63,14.13.
(2) Synthesis of intermediate 2
Adding intermediate 1(2.49g,3.80mmol), 5-bromothiophene-2-formaldehyde (1.6g, 8.4mmol), tetrabutylammonium bromide (200mg, 0.62mmol), toluene (50mL) and magnetons into a dry and clean 250mL three-neck flask, stirring to dissolve reactants, adding potassium carbonate (30mL, 2M), continuing stirring for 10min, vacuumizing the system, replacing with argon, adding a proper amount of catalyst Pd (PPh)3)4Vacuumizing the system, replacing with argon, reacting at 90 deg.C for 36 hr, monitoring by a point plate until the reaction is completed, stopping the reaction, cooling the system to room temperature, extracting with appropriate amount of dichloromethane for 3-5 times, washing with appropriate amount of saturated NaCl solution for 3-5 times, retaining the organic phase, adding appropriate amount of anhydrous MgSO4The powder was dried, the solvent was removed under reduced pressure, and the product was purified by silica gel column chromatography (petroleum ether: dichloromethane: ethyl acetate: 10:2:1) to give intermediate 2(1.44g, 61%) as a yellow solid.1HNMR(400MHz,CDCl3)δ9.92(s,1H),8.10(d,J＝3.8Hz,1H),7.79(d,J＝3.9Hz,1H),7.70(s,1H),7.57(d,J＝6.4Hz,1H),7.51(s,1H),4.66–4.60(m,1H),2.32(dd,J＝9.0,4.4Hz,2H),2.19–1.81(m,2H),1.11(s,10H),0.77(d,J＝7.1Hz,3H).13C NMR(101MHz,CDCl3)δ:182.82,155.58,143.10,142.24,139.75,137.64,131.24,130.71,124.31,124.14–124.04,123.06,121.27,117.99,109.59,106.96,77.42,77.10,76.79,56.85,33.78,31.75,29.90,29.58–29.02,26.80,22.61,14.08.
(3) Synthesis of intermediate 3
The synthesis of intermediate 3 was similar to that of intermediate 2, using 5-bromofuran-2-carbaldehyde (1.49g, 8.4mmol) and intermediate 1(2.49g,3.80mmol) as reactants, and isolated and purified to give intermediate 3(1.42g, 63%) as a yellow solid.1H NMR(400MHz,CDCl3)δ:9.68(d,J＝4.4Hz,2H),8.14(d,J＝5.8Hz,2H),7.93(s,2H),7.67(d,J＝7.7Hz,2H),7.39(d,J＝3.7Hz,2H),6.97(s,2H),4.72–4.69(m,1H),2.34(dd,J＝9.9,4.0Hz,4H),2.02(dd,J＝15.0,9.5Hz,4H),1.10(s,21H),0.77(s,6H).13C NMR(101MHz,CDCl3)δ:177.07,160.56,160.05,152.07,143.06,141.93,139.64,128.27,126.94,126.54,125.13–121.89,121.08,120.62,119.50,116.98,108.25,107.94,105.82,77.31,77.05,76.73,57.05,55.78,40.27,33.86,31.72,29.87,29.54–29.01,26.79,23.74,22.54,14.01.
(4) Synthesis of intermediate 4
The synthesis of intermediate 4 was performed in a similar manner to intermediate 2, using p-bromobenzaldehyde (1.54g, 8.4mmol) and intermediate 1(2.49g,3.80mmol) as reactants, and isolated and purified to give intermediate 4(1.51g, 65%) as a yellow solid.1H NMR(400MHz,CDCl3)δ:10.10(s,1H),8.21(dd,J＝12.2,8.3Hz,1H),8.02(d,J＝8.0Hz,2H),7.88(s,2H),7.65(s,1H),7.53(d,J＝5.7Hz,1H),4.74–4.65(m,1H),2.37(dd,J＝9.6,4.5Hz,1H),2.01(dd,J＝14.3,9.5Hz,2H),1.12(s,10H),0.78(t,J＝6.9Hz,3H).13C NMR(101MHz,CDCl3)δ:191.96,148.33,135.07,130.35,128.16,127.73,121.16,120.89,118.82,110.48,107.85,77.37,77.06,76.74,56.66,33.84,31.74,29.73–29.07,26.85,22.58,14.04.
Example 1
Synthesis of target molecule CTC1
Adding the intermediate 2(156mg,0.25mmol), the thienylindanone (200mg, 1mmol), the chloroform (20mL) and the magnetons into a dry and clean 50mL three-necked bottle, stirring to dissolve reactants, vacuumizing the system, replacing with argon, adding pyridine (1mL) in an argon environment, reacting at normal temperature for 12h, monitoring by a point plate until the reaction is complete, adding 10mL of water to quench and stop the reaction, cooling the system to room temperature, extracting with a proper amount of dichloromethane for 3-5 times, washing with a proper amount of saturated NaCl solution for 3-5 times, retaining the organic phase, adding a proper amount of anhydrous MgSO (MgSO) into the organic phase4The powder was dried to remove excess solvent and purified by silica gel chromatography (petroleum ether: dichloromethane: ethyl acetate: 12:2:1) to give target small molecule CTC1(143mg, 58%) as a dark blue solid powder.1HNMR(400MHz,CDCl3)δ:8.89(s,1H),8.60(s,1H),8.58(s,1H),8.42(s,1H),8.22–8.17(m,1H),7.96(s,1H),7.85(s,1H),7.82(s,1H),7.20(d,J＝4.1Hz,1H),4.74(s,1H),2.41–2.33(m,2H),2.13(d,J＝6.2Hz,2H),1.12(d,J＝8.8Hz,10H),0.76(s,3H).MALDI-TOF-MS,m/z:calcd for C59H51N5O2S4[M]+:989.293；found 990.719.
Example 2
Synthesis of target molecule CTC2
The synthesis method of the target molecule CTC2 is similar to that of the target molecule CTC1, and the target molecule CTC2(143mg, 60%) is obtained by separating and purifying the intermediate 3(148mg, 0.25mmol) and the thienylidene (200mg, 1mmol) which are used as reactants.1H NMR(400MHz,CDCl3)δ:8.90(s,1H),8.59(s,1H),8.42(s,1H),8.20(s,1H),8.20(s,1H),7.96(s,1H),7.84(s,1H),7.21(s,1H),2.38(s,2H),2.14(s,2H),1.14(s,10H),0.78(s,3H).MALDI-TOF-MS,m/z:calcd for C59H51N5O4S2[M]+:957.338；found 958.496.
Example 3
Synthesis of target molecule CTC3
The synthesis method of the target molecule CTC3 is similar to that of the target molecule CTC1, and the target molecule CTC3(156mg, 64%) is obtained by separating and purifying the intermediate 4(153mg, 0.25mmol) and the thienylidene (200mg, 1mmol) which are used as reactants and is dark red solid powder.1H NMR(400MHz,CDCl3)δ:8.93(s,2H),8.70(s,2H),8.57(s,2H),8.21(dd,J＝11.5,8.4Hz,2H),8.02(d,J＝8.1Hz,4H),7.88(d,J＝11.8Hz,4H),7.65(d,J＝12.6Hz,2H),7.54(d,J＝7.0Hz,2H),5.11–4.32(m,1H),2.39(dd,J＝9.5,4.2Hz,2H),2.11–2.00(m,2H),1.13(s,21H),0.79(s,7H).MALDI-TOF-MS,m/z:calcd for C63H55N5O2S2[M]+:977.380；found978.028.
Respectively testing nuclear magnetic hydrogen spectrograms and mass spectrograms of target molecules, as shown in figures 1-6; and performing performance test on the target molecule.
1. Photophysical and electrochemical properties of the target molecules CTC1, CTC2, CTC3
(1) Physical Properties of light
Determining the CH positions of target molecules CTC1, CTC2 and CTC32Cl2UV-VIS absorption Spectrum on solution neutralized solid filmsThe results are shown in table 1;
(2) electrochemical performance
Three target molecules CTC1-3 were tested for electrochemical performance using cyclic voltammetry with a three-electrode system, as shown in table 2.
The specific test method comprises the following steps: the electrodes used in the test of the invention are respectively a working electrode Au, a reference electrode Ag/AgCl and a counter electrode Pt, the C-V cyclic voltammetry curve of ferrocene is taken as reference, and 0.1M tetrabutylammonium hexafluorophosphate acetonitrile solution is prepared as electrolyte. Assuming that the absolute energy level of ferrocene is 4.8eV under vacuum, a proper amount of ferrocene is added into the tetrabutylammonium hexafluorophosphate acetonitrile solution, the scanning speed is 0.1V/s, and the oxidation potential of the ferrocene is firstly tested to be 4.45 eV.
Table 1 basic spectral data of target molecules CTC1, CTC2, CTC3
TABLE 2 Cyclic voltammetry data for target molecules CTC1, CTC2, CTC3
From the results in table 1, the ultraviolet visible maximum absorption peaks of the target molecules CTC1, CTC2, CTC3 are 612nm, 578nm and 486nm respectively, and the molecules have wide and strong ultraviolet absorption and better planarity. The molar extinction coefficients of target molecules CTC1, CTC2 and CTC3 are 8.32 multiplied by 10 respectively4cm-1、9.29×104cm-1And 1.75X 104M-1cm-1. On the other hand, the target molecule has a shoulder at a position around 600nm, which is caused by ordered pi-pi stacking or aggregation-packing between molecules. In general, the ultraviolet absorption spectrum absorption range of the three small molecule films is widened, and the maximum absorption peak is also subjected to red shift, which shows that the ultraviolet absorption range and the intensity of the molecules are improved after the target molecules CTC1, CTC2 and CTC3 form a solid film.
As can be seen from the data tested in table 2: the initial oxidation potentials of target molecules CTC1, CTC2 and CTC3 are respectively 1.34V, 1.30V and 1.25V, and the initial reduction potentials are respectively-0.34V, -0.35V and-0.32V. The HOMO energy levels of target molecules CTC1, CTC2 and CTC3 are respectively-5.79 eV, -5.75eV and-5.70 eV; the LUMO levels of target molecules CTC1, -2, CTC3 were-4.11 eV, -4.10eV, and-4.13 eV, respectively. It can be seen that the LUMO level of the target molecule CTC2 with thiophene as pi-bridge is the highest, most likely to achieve high open-circuit voltage. The difference between the LUMO energy level of target molecules CTC1, CTC2 and CTC3 and the LUMO energy level of a donor is more than 0.3eV, so that the effective separation and transmission of charges are facilitated.
2. Structural planarity of target molecules CTC1, CTC2, CTC3
The planarity of the target molecules is characterized by density functional theory calculation of the target molecules CTC1, CTC2 and CTC3, and particularly, the included angles among unit groups in the target molecules CTC1, CTC2 and CTC3 are tested. The method comprises the following steps: let the dihedral angle between the electron-withdrawing unit (left) and the pi bridge (left) of target molecule CTC1 be a1The dihedral angle between the pi-bridge (left) and the fluorene-donor group is b1The dihedral angle between the fluorene donor group and the pi-bridge (right) is c1The dihedral angle between the pi-bridge (right) and the electron-withdrawing unit (right) is d1By analogy, the dihedral angles of the target molecules CTC2 and CTC3 in the molecule are a2、b2、c2、d2And a3、b3、c3、d3The data of the test are shown in Table 3.
TABLE 3 dihedral angles of the skeleton of the target molecule CTC1-3
From the data tested in table 3, it can be seen that the target molecules CTC1, CTC2, CTC3 are symmetric about the left and right, and the dihedral angles of the left and right sides are substantially the same, wherein the target molecule CTC2 with furan as pi bridge has better planarity, the dihedral angle is between 3 ° and 6 °, and the interaction force between molecules is stronger.
3. Thermal stability of target molecules CTC1, CTC2, CTC3
For systematic study of the thermal stability of the target molecules CTC1, CTC2, CTC3, the present invention uses thermogravimetric analysis (TGA) at N2At 20 ℃ for min-1The temperature is increased at a speed, the temperature of target molecules CTC1, CTC2 and CTC3 at the time of 5 percent weight loss is measured, and the thermal decomposition temperature (T) is obtaineddCalculated as 5% weight loss) and a thermogravimetric curve, the thermogravimetric curve is shown in fig. 7, and the thermal decomposition temperature data is shown in table 4;
TABLE 4 thermal decomposition temperature of CTC1-3
From the data in table 4 and figure 7, the thermal decomposition temperatures of target molecules CTC1, CTC2, CTC3 were 251 ℃, 222 ℃ and 173 ℃, respectively. It is not easy to see that the thermal decomposition temperature is continuously reduced, and different pi bridges are introduced into molecules, so that the thermal stability of the whole molecules is greatly influenced. Among them, CTC1, which is a pi-bridged thiophene molecule, has the best thermal stability. Overall, the target molecules CTC1, CTC2, CTC3 all have good thermal stability.
4. Mobility of target molecules CTC1, CTC2 and CTC3 blended film
To further understand the effect of molecular linking to different pi-bridging groups on the charge transport properties of the molecules. Target molecules CTC1, CTC2 and CTC3 and a donor material PTB7-Th are blended to prepare ITO/ZnO/PTB 7-target molecule/MoO with the film thickness of about 100nm3The hole mobility and the electron mobility of the small molecule acceptor material and the donor material PTB7-Th blend are tested by a space-limited current method under the condition that the chloronaphthalene additive is added, and the hole mobility curve and the electron mobility curve are shown in figures 8 and 9.
From fig. 8 and 9, it is calculated that: the hole mobility of target molecules CTC1, CTC2 and CTC3 is 4.42 × 10-4V-1s-1、3.19×10-4V-1s-1And 1.69X 10-4cm2V-1s-1Electron mobility of 6.24X 10, respectively-5V-1s-1、5.00×10-5V-1s-1And 2.28X 10-5cm2V-1s-1. The higher the mobility is, the more favorable the charge transmission is, the loss of exciton recombination is reduced, and therefore, the higher short-circuit current density and the higher filling factor are obtained.
The present invention is illustrated in detail by the above examples, but the present invention is not limited to the above methods, i.e., it is not meant to imply that the present invention must be carried out depending on the above reaction conditions. It will be apparent to those skilled in the art that any modifications to the present invention, equivalent substitutions of reaction solvents, catalysts, and changes in the specific reaction conditions, etc., are within the scope and disclosure of the present invention.
Claims (8)
1. A thiophene indanone and carbazole based A-pi-D-pi-A type small molecule solar cell receptor material is characterized by having a structure of a general formula I:
in the formula I, pi is specifically any one of the following structural units:
wherein n is a natural number of 1 to 20.
2. The preparation method of the A-pi-D-pi-A type small molecule solar cell receptor material based on the thiophene indanone and the carbazole, which is disclosed by claim 1, is characterized by comprising the following steps:
(1) under the alkaline environment, carrying out boron esterification reaction on 2, 7-dibromocarbazole and bis (pinacolato) boron ester to prepare an intermediate 1, wherein the structure is as follows:
(2) the intermediate 1 and 5-bromothiophene-2-formaldehyde are subjected to a suzuki reaction under the catalysis of a catalyst to obtain an intermediate 2, and the structure of the intermediate is as follows:
(3) the intermediate 1 and 5-bromofuran-2-formaldehyde are subjected to a suzuki reaction under the catalysis of a catalyst to obtain an intermediate 3, and the structure of the intermediate is as follows:
(4) the intermediate 1 and p-bromobenzaldehyde are subjected to a suzuki reaction under the catalysis of a catalyst to obtain an intermediate 4, and the structure of the intermediate is as follows:
(5) the intermediate 2 and the thiophene indanone undergo condensation reaction to obtain a target molecule CTC1, and the structure is as follows:
(6) the intermediate 3 and the thiophene indanone undergo condensation reaction to obtain a target molecule CTC2, and the structure is as follows:
(7) the intermediate 4 and the thiophene indanone undergo condensation reaction to obtain a target molecule CTC3, and the structure is as follows:
3. the method for preparing the thiophene indanone and carbazole based A-pi-D-pi-A type small molecule solar cell receptor material according to claim 2, wherein in the steps (2) to (4), the reaction solvent used in the suzuki reaction is a mixture of a toluene solvent and a 2M sodium carbonate solution; the volume ratio of the toluene solvent to the 2M sodium carbonate solution is 2: 1-4: 1.
4. The preparation method of the A-pi-D-pi-A type small molecule solar cell receptor material based on thiophene indanone and carbazole according to claim 2, wherein in the steps (2) to (4), the molar ratio of the 5-bromothiophene-2-formaldehyde to the intermediate 1, the molar ratio of the 5-bromofuran-2-formaldehyde to the intermediate 1, and the molar ratio of the p-bromobenzaldehyde to the intermediate 1 are all 1: 2-1: 6.
5. The preparation method of the thiophene indanone and carbazole based A-pi-D-pi-A type small molecule solar cell receptor material, according to claim 2, wherein in the steps (2) - (4), the reaction temperature of the suzuki coupling reaction is 90-110 ℃; the reaction time of the suzuki reaction is 24-36 hours.
6. The method for preparing the A-pi-D-pi-A type small molecule solar cell receptor material based on the thiophene indanone and the carbazole according to claim 2, wherein in the steps (2) to (4), the catalyst is Pd (PPh)3)4。
7. The preparation method of the A-pi-D-pi-A type small molecule solar cell receptor material based on thiophenindione and carbazole according to claim 2, wherein in the steps (5) to (7), the molar ratio of the intermediate 2 to thiophenindione, the molar ratio of the intermediate 3 to thiophenindione, and the molar ratio of the intermediate 4 to thiophenindione are all 1:2 to 1: 8.
8. The preparation method of the A-pi-D-pi-A type small molecule solar cell receptor material based on thiophene indanone and carbazole according to claim 2, wherein in the steps (5) - (7), the reaction temperature of the condensation reaction is 0-70 ℃; the reaction time of the condensation reaction is 12-24 h.
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