CN112920204A - Electron acceptor organic solar cell material based on thiadiazole quinoxaline structure and preparation method and application thereof - Google Patents
Electron acceptor organic solar cell material based on thiadiazole quinoxaline structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an electron acceptor organic solar cell material based on a thiadiazole quinoxaline structure, and a preparation method and application thereof. The structural formula of the material is shown as formula I: in the formula I, pi is selected from any one of a non-structure, a structure shown in a formula II and a structure shown in a formula III; in the formula I, A is selected from any one of a structure shown in a formula IV, a structure shown in a formula V and a structure shown in a formula VI; in the formula IV, X is at least one of hydrogen, fluorine, chlorine and methyl; in the formula I, R and R1Both are C1-C8 alkyl or alkoxy, and R1The alkyl or alkoxy of C1-C8 is straight chain or branched chain, which are the same or different. The invention relates to application of a compound shown as a formula IIn the preparation of solar cells.
Description
Technical Field
The invention relates to an electron acceptor organic solar cell material based on a thiadiazole quinoxaline structure, and a preparation method and application thereof, and belongs to the field of organic solar cells.
Background
Compared with the traditional silicon-based solar cell, the organic solar cell is favored by global research and industry due to the advantages of simple manufacturing process, low cost, flexibility and the like. The history of organic solar cell research dates back to the sixties of the twentieth century, and the research group at the university of california in the united states discovered the photovoltaic phenomenon for the first time in single-section organic solar cell devices, namely magnesium phthalocyanine. In the next decades, the active layer in organic solar cell devices has undergone three structural changes, monolayer, bilayer and bulk heterojunction. The Dengqingyun doctor of Kodak company in the last eighties developed a double-layer heterojunction organic solar cell device taking phthalocyanine copper and tetracarboxyl perylene derivatives as donor and acceptor, and the photoelectric conversion efficiency of the double-layer heterojunction organic solar cell device was close to 1%. By the nineties of the twentieth century, a Heggel research group at the university of California, Santa Barbara, discovers that light-induced ultra-fast charge transfer exists between a conjugated polymer and fullerene (PC61BM), and a bulk heterojunction organic solar cell device is prepared for the first time, so that the separation and diffusion efficiency of excitons is greatly improved, and the photoelectric conversion efficiency of the organic solar cell is further improved. Since then, the research direction of bulk heterojunction organic solar cells using fullerene derivative PCBM as acceptor material has been receiving wide attention from the scientific research community. In the past decades, numerous research efforts have been carried out on the use of fullerene derivatives as receptors in organic solar cells.
However, the fullerene material has some insurmountable defects, such as difficulty in energy level modulation, narrow absorption range, difficulty in purification, high cost and the like, and the improvement of the current and the efficiency of the organic solar cell is severely restricted. In 2006, the concept of two-dimensional linear conjugation was first proposed by the chemical research institute of academy of sciences of china, li-gewagfang, and polythiophene derivatives containing conjugated branched chains were designed. By using the concept of two-dimensional linear structure, researchers have successively designed and synthesized many donor and acceptor materials with excellent device performance.
A typical organic solar cell is composed of five parts, namely conductive glass, a hole transport layer, an active layer, an electron transport layer, a counter electrode and the like. The material of the donor and the acceptor of the active layer is used as a core part to absorb sunlight to generate excitons, and the excitons are separated into free charges and then are transmitted to corresponding electrodes, so that the structure is a key structure which directly determines the performance of the solar cell. Therefore, a considerable part of research work has been focused mainly on the design and synthesis of donor and acceptor materials for organic solar cells.
Among them, the organic solar cell small molecule acceptor material is most popular composed of two parts: an A-D-A type material composed of an electron Donor (Donor) and an electron Acceptor (Acceptor), namely an Acceptor-Donor-Acceptor type material, such as ITIC, Y6 is a high-efficiency small molecule Acceptor material of the type, and a conjugated BrIdge group (BrIdge) is added on the basis to form the A-pi-D-pi-A type material, such as IEICO-4F. The electron donor is a condensed ring aromatic hydrocarbon unit with an electron-rich structure, and generates photoelectrons after being excited by sunlight; the structure of the conjugated bridge group is various, and generally has structural characteristics such as large ring or polycyclic conjugated double bond, and the like, and commonly has thiophene, bithiophene, porphyrin and the like, and the conjugated bridge group mainly plays two roles: firstly, the absorption spectrum of the organic solar cell material is widened, and the utilization rate of incident sunlight is improved; and the second is to conduct the photoelectrons generated by the excitation of the electron donor to the electron acceptor unit. Electron acceptors are commonly used as electron-deficient building blocks such as indolone and rhodanine. Although the performance of the solar cell device prepared based on the acceptor micromolecule material with the fused ring as the core is good, the synthesis steps are long, and the synthesis cost is high. Therefore, the research and development of the novel efficient small molecule receptor material with the non-condensed ring as the core structure has important theoretical and practical significance.
Disclosure of Invention
The invention aims to provide a micromolecular electron acceptor organic solar cell material based on a thiadiazole quinoxaline structure, and a preparation method and application thereof.
The invention provides a compound, which has a structural formula shown in a formula I:
in the formula I, pi is selected from any one of a non-structure, a structure shown in a formula II and a structure shown in a formula III;
in the formula I, A is selected from any one of a structure shown in a formula IV, a structure shown in a formula V and a structure shown in a formula VI;
in the formula IV, X is at least one of hydrogen, fluorine, chlorine and methyl;
in the formula I, R and R1Both are C1-C8 alkyl or alkoxy, and R1The alkyl or alkoxy of C1-C8 is straight chain or branched chain, which are the same or different.
In the above compounds, the compound represented by formula I is selected from any one of the following (a1) and (a2):
(A1) pi is the structure shown in the formula II; a is the structure shown in the formula IV, X is fluorine atom, R is octyl, R1Is hexyl;
(A2) pi is the structure shown in the formula III; a is the structure shown in the formula VI, and R is hexyl, R1Is octyl.
The invention provides a method for preparing the compound shown in the formula I, when in the compound shown in the formula I, pi is the structure shown in the formula II, and A is the structure shown in the formula IV, the method comprises the following steps:
1) carrying out coupling reaction on a reactant 1 and a reactant 2 in an organic solvent a under the action of a Pd catalyst to obtain an intermediate P1, wherein the reactant 1 is selected from a compound shown in a formula VII (named as a 4, 4-dialkyl-cyclopentane dithiophene trimethyl tin compound), and the reactant 2 is selected from a compound shown in a formula VIII (named as a 4, 9-dihalo-6, 7-dialkyl-thiadiazole quinoxaline);
2) dissolving the intermediate P1 and N, N-dimethylformamide in an organic solvent b, and dropwise adding trioxy phosphine under an ice bath condition for acylation reaction to obtain an intermediate P2;
3) dropwise adding alkaline liquid into an organic solvent c to perform condensation reaction on the intermediate P2 and a compound (named as 5, 6-disubstituted-3- (dicyanomethylene) indolone) shown in the formula IX or a compound (named as 2- (6-oxo-5, 6-dihydro-4H-cyclopenta [ c ] thiophene-4-ylidene) malononitrile) shown in the formula X to obtain a compound shown in the formula I;
in the formula VII, R1The same as defined in formula I;
in the formula VIII, R and pi are the same as those in the formula I; b is a halogen atom, and the halogen atom can be selected from any one of the following: cl, Br or I;
in formula IX, X is as defined for formula IV.
In the above method, in step 1), the Pd catalyst is selected from at least one of: pd (Ph)3)2Cl2、Pd(OAc)2And Pd (PPh)3)4In particular Pd (Ph)3)2Cl2；
The mole ratio of the Pd catalyst to the reactant 1 to the reactant 2 is 1: (50-250): (20-100), which may be 1: 186.2: 78.1;
the organic solvent a is at least one selected from toluene, xylene, dioxane and tetrahydrofuran, and can be tetrahydrofuran specifically;
the coupling reaction is a reflux reaction carried out under an inert gas (such as nitrogen) atmosphere;
the reaction temperature of the coupling reaction can be 60-140 ℃, specifically the temperature for refluxing tetrahydrofuran, and the reaction time can be 12-36 hours, specifically 24 hours, 12-24 hours, 24-36 hours or 20-30 hours.
In the above method, in the step 2), the molar ratio of the N, N-dimethylformamide, the intermediate P1 and the trialkoxyphosphine may be (0.8 to 1.5): 1: (0.8-5.2), specifically 1.2: 1: 1.6, (0.8-1.2): 1: (0.8-1.6), (1.2-1.5): 1: (1.6-5.2) or (1-1.5): 1: (1-4.5);
the reaction temperature of the acylation reaction can be 0-60 ℃, specifically 0 ℃, 0-20 ℃, 0-40 ℃ or 0-50 ℃, and the reaction time can be 5-20 hours, specifically 6 hours, 5-6 hours, 6-20 hours or 5-10 hours;
the organic solvent b is at least one of N, N-dimethylformamide, dichloromethane and dichloroethane, and specifically is dichloroethane.
In the above method, in step 3), the molar ratio of the intermediate P2 to the compound represented by formula IX may be 1: (2-20), specifically 1: 4.5, 1: (2-4.5) and 1: (4.5-20) or 1: (4-10);
the reaction temperature of the condensation reaction can be 60-100 ℃, specifically the temperature for refluxing the chloroform, and the reaction time can be 12-36 h, specifically 24h, 12-24 h, 24-36 h or 20-30 h;
the alkaline liquid is at least one of alkyl amine compounds, aromatic amine compounds and pyridine: the alkylamine compound is specifically methylamine, and the aromatic amine compound is specifically aniline;
the organic solvent c is at least one selected from chloroform, dichloromethane and dichloroethane, and specifically chloroform (i.e. chloroform).
The invention also provides a method for preparing the compound shown in the formula I, when in the compound shown in the formula I, pi is the structure shown in the formula III, and A is the structure shown in the formula VI, the method comprises the following steps:
a) dissolving a compound shown as a formula XI and a reactant 3 in an organic solvent 1 in the presence of a Pd catalyst to react to obtain an intermediate P3, wherein the reactant 3 is the compound shown as the formula VIII;
b) dissolving the intermediate P3 in an organic solvent 2, and dropwise adding strong base and N, N-dimethylformamide to carry out acylation reaction to obtain an intermediate P4;
c) dropwise adding alkaline liquid into the intermediate P4 and the compound shown in the formula XII (named as 2- (3-ethyl-4-oxothiazolidine-2-ethylidene) -malononitrile) in an organic solvent 3, and carrying out condensation reaction to obtain the compound shown in the formula I;
in said formula XI, R2And R in the formula I1The same definition is applied.
In the above method, in step a), the Pd catalyst is selected from at least one of: pd (Ph)3)2Cl2、Pd(OAc)2And Pd (PPh)3)4Specifically, Pd (PPh)3)4；
The mole ratio of the Pd catalyst, the reactant 3, the compound of formula XI can be 1: (20-100): (40-250), which may be 1: 73: 172. 1: (20-73): (40-172), 1: (73-100): (172-250) or 1: (50-100): (100-200);
the organic solvent 1 is at least one or a mixed system of toluene, xylene and trimethylbenzene, and can be toluene specifically;
the reaction is a reflux reaction carried out under an inert gas (such as nitrogen) atmosphere;
the reaction temperature of the reaction can be 100-150 ℃, and the reaction time can be 12-36 h, specifically 24h, 12-24 h, 24-36 h or 20-30 h.
In the above process, in step b), the molar ratio of the intermediate P3, the strong base and the N, N-dimethylformamide may be 1: (0.8-1.5): (0.8 to 1.6), specifically 1.16: 1: 1.07;
the reaction temperature of the acylation reaction can be-78-0 ℃, the reaction time can be 5-20 h, and in particular, the reaction can be carried out overnight (namely 12 h);
the strong base used in the acylation reaction is n-butyllithium and/or isobutyllithium, in particular n-butyllithium;
the organic solvent 2 is tetrahydrofuran.
In the above process, in step c), the molar ratio of intermediate P4 to the compound represented by formula XII may be 1: (2.5-10.0), specifically 1: 8.28, 1: (2.5-8.28), 1: (8.28-10.0) or 1: (5-10.0);
the reaction temperature of the condensation reaction can be 60-100 ℃, and the reaction time can be 12-36 h, specifically 36h, 15-24 h, 20-36 h or 20-36 h;
the alkaline liquid is selected from at least one of methylamine, aniline and pyridine, and specifically can be pyridine;
the organic solvent 3 is chloroform and/or dichloromethane, and specifically can be dichloromethane.
The compound shown in the formula I is an electron acceptor organic solar cell material based on a thiadiazole quinoxaline structure.
The compound shown in the formula I is applied to the preparation of solar cells.
In the above application, the solar cell may be an organic solar cell.
The invention has the following advantages:
the thiadiazole quinoxaline structure is used as an aromatic heterocyclic structure, so that the thiadiazole quinoxaline structure can be widely applied to the field of organic photoelectric materials. Two nitrogen atoms in a thiadiazole quinoxaline structure have lone pair electron energy to form a certain non-covalent interaction with hydrogen and sulfur atoms, and the molecular skeleton of the thiadiazole quinoxaline is a tricyclic conjugated structure system, has good electron conduction capability and is an excellent electron acceptor candidate structural unit; the organic material molecule has large delocalized pi bonds, and light-excited electrons transit through pi-pi anti-bonds, so that the organic material molecule has higher absorption coefficient, and has higher absorption utilization rate on light in a semiconductor film with the same thickness; compared with dye molecules of an A-D-A type electron acceptor with an aromatic condensed ring as a core structure, the dye molecules have the advantages of simple structure, lower synthesis cost, higher photoelectric conversion efficiency and potential for manufacturing organic solar cells in large-area printing.
Drawings
Fig. 1 is a flow chart of the preparation of the organic solar cell acceptor small molecule material based on thiadiazole quinoxaline as an electron acceptor in example 1 of the present invention.
Fig. 2 is a flow chart of the preparation of the organic solar cell acceptor small-molecule material based on thiadiazole quinoxaline as an electron acceptor in example 2 of the present invention.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1 preparation of organic solar cell acceptor small molecule material A1 based on thiadiazole quinoxaline as electron acceptor (wherein, in formula I, π is represented by formula II, A is represented by formula IV, X is fluorine atom, R is octyl, R1 is hexyl)
The preparation flow chart of the organic solar cell receptor small molecular material based on thiadiazole quinoxaline as the electron receptor is shown in figure 1, and the preparation method comprises the following specific steps:
1) reactant 1 (dihexylcyclopentane dithienyl trimethyltin) (118mg,0.186mmol), reactant 2(4, 9-dibromo-6, 7-bis (5-octylthiophene) -thiadiazoloquinoxaline) (57.3mg,0.078mmol), Pd (PPh)3)2Cl2(7mg,0.01mol), tetrahydrofuran (20mL) was refluxed under nitrogen for 24 hours. The reaction solution was poured into methylene chloride (50mL), washed with water, and the organic phase was collected and dried over anhydrous sodium sulfate. The solvent is distilled off under reduced pressure, the residue is passed through a silica gel column, and the mobile phase is a mixed solvent of dichloromethane and petroleum ether with the volume ratio of 1:4, so as to obtain an intermediate compound P1.
2) The intermediate compound P1(82.3mg,0.065mmol) prepared in step 1) was dissolved in dry dichloroethane (50mL), and 10mL of anhydrous phosphorus oxychloride and N, N-dimethylformamide (5.69mg,0.065mmol) were added dropwise at 0 ℃. After stirring for 20 minutes, the temperature was raised to room temperature and stirring was continued for 6 hours. After the reaction, the reaction solution was dropped with an aqueous solution of potassium hydroxide (10 mL). The organic phase was collected, washed with saturated sodium bicarbonate solution and water, respectively, and dried over anhydrous sodium sulfate. The solvent is distilled off under reduced pressure, the residue is passed through a silica gel column, and the mobile phase is a mixed solvent of dichloromethane and petroleum ether with the volume ratio of 1:1, so as to obtain an intermediate compound P2.
3) Intermediate compound P2(75.3mg,0.057mmol) and Compound A1(5, 6-difluoro 3- (dicyanomethylene) indone) (59mg,0.256mmol) was dissolved in a dry chloroform solvent, 0.lml pyridine was added dropwise, and the reaction was refluxed for 24 hours. Cooling to room temperature, and removing the solvent by evaporation under reduced pressure. The residue was extracted with chloroform, washed with a 10% sodium hydrogencarbonate solution and saturated brine, respectively, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was passed through a silica gel column and a mobile phase was a mixed solvent of methylene chloride and petroleum ether in a volume ratio of 1:1, whereby 82% of the small organic molecule acceptor material A1 was obtained in a yield of 82% and 1H NMR (400MHz, CDCl3):8.94(s,2H),8.56(d,2H),8.10(s,2H),7.65-7.74(m,4H),7.34(d,2H),2.77(m,4H),2.01-2.33(m,8H),1.76(t,4H),1.38-1.42(m,14H),0.93-0.97(m,38H),0.74-0.75(m, 26H).
Example 2 preparation of organic solar cell acceptor small molecule material A2 based on thiadiazole quinoxaline as electron acceptor (wherein, in formula I, pi is a structure shown in formula III; A is a structure shown in formula V; R2 is octyl; R3 is hexyl)
The preparation flow chart of the organic solar cell receptor small molecular material based on thiadiazole quinoxaline as the electron receptor is shown in figure 2, and the preparation method comprises the following specific steps:
a) dioctylcyclopentanedithiophenetributylstannide (97.2mg,0.172mmol),4, 9-dibromo-6, 7-bis (5-hexylothiophene) -thiadiazoloquinoxaline (57.7mg,0.073mmol), Pd (PPh)3)4(7mg,0.01mol), toluene (20mL) was refluxed under nitrogen for 24 hours. The reaction mixture was poured into dichloromethane (40mL), washed with water, and the organic phase was collected and dried over anhydrous sodium sulfate. The solvent is distilled off under reduced pressure, the residue is filtered through a silica gel column, and the mobile phase is a mixed solvent of dichloromethane and petroleum ether with the volume ratio of 3:4, so that the intermediate compound P3 is obtained.
b) Dissolving the intermediate compound P3(87.4mg,0.061mmol) prepared in the step a) in dry tetrahydrofuran (40mL) at the temperature of minus 78 ℃, slowly dropwise adding N-butyllithium (0.43mL, 1.6M in hexane) under the protection of nitrogen, stirring for one half hour, then heating to 0 ℃, continuing stirring for half hour, then cooling to minus 78 ℃, slowly dropwise adding N, N-dimethylformamide (4.75mg,0.065mmol), and finally reacting overnight at the room temperature. After the reaction was complete, an aqueous ammonium chloride solution (10mL) was added dropwise to the reaction. The organic phase was collected, washed with saturated sodium bicarbonate solution and water, respectively, and dried over anhydrous sodium sulfate. The solvent is distilled off under reduced pressure, the residue is passed through a silica gel column, and the mobile phase is a mixed solvent of dichloromethane and petroleum ether with the volume ratio of 1:1, so as to obtain an intermediate compound P4.
c) Intermediate Compound P4(74.5mg,0.050mmol) and Compound A2((2- (3-ethyl-4-oxothiazolidine-2-ethylidene) -malononitrile)) (80mg,0.414mmol) was dissolved in a dry chloroform solvent, and 0.lml pyridine was added dropwise thereto, followed by reflux reaction for 36 hours. Cooling to room temperature, and removing the solvent by evaporation under reduced pressure. The residue was extracted with chloroform, washed with a 10% sodium hydrogencarbonate solution and saturated brine, respectively, and dried over anhydrous sodium sulfate. Distilling off solvent under reduced pressure, passing the residue through silica gel column, mobile phase is mixed solvent of dichloromethane and petroleum ether with volume ratio of 1.2:1, correspondingly obtaining organic micromolecule acceptor material A2 with yield of 79%,1HNMR(400MHz,CDCl3):8.76(s,2H),8.09(s,2H),7.93(s,2H),7.64(d,2H),7.34(d,2H),2.75(s,4H),2.05(s,8H),1.73(t,4H),1.37(s,14H),0.93-1.0(m,38H),0.65-0.75(m,26H)。
example 3 preparation and performance measurement of solar cell devices:
1) the preparation process comprises the following steps: washing ITO glass with detergent, distilled water, acetone and isopropanol, removing solvent at 100 deg.C in oven, and removing O3UV treatment for 30 minutes; then a layer of PEDOT, PSS modified layer material (the material is purchased from Shenzhen Rui Xue science and technology Co., Ltd.) is coated, and after thermal annealing is carried out for 30 minutes at 150 ℃, the material is moved into a glove box; cooling to room temperature, and spin-coating a layer of organic solar cell active layer material, wherein the material is a solution (solvent is one of chloroform or chlorobenzene) with a concentration of about 8-10mol/mL formed by mixing a polymer donor material, specifically PCE10, and an acceptor small molecule material a1 or a2 prepared in embodiments 1 and 2 of the present invention at a certain mass ratio (e.g., 1: 1); after the active layer is subjected to solvent annealing treatment,
spin-coating a PDINO electronic modification layer material, and transferring into an evaporation box to evaporate an Al electrode. And a standard sunlight source AMG1.5 is used as a light source, and a current density-voltage J-V curve is tested through a source meter and software configured by a computer.
The organic solar cell acceptor micromolecule material A1 or A2 is replaced by the ITIC electron acceptor material with excellent efficiency, and the rest is prepared into the solar cell device according to the preparation process to be used as a comparative solar cell device.
ITIC is a recognized target-type molecule in the field of organic solar cells, but it also has its own drawbacks, such as: such as: high price, long synthetic route, difficult large-scale preparation, complex synthetic purification process and the like.
2) And (3) performance measurement: the prepared solar cell device a1, solar cell device a2 and comparative solar cell device were subjected to photoelectric property test under a xenon lamp with a light source of 300W, and the test results are shown in table 1:
TABLE 1 Experimental data Table for two organic materials and ITIC materials
| Dye material | Jsc(mA/cm2) | Voc(mV) | FF | η(％) |
| A1 | 12.5 | 768 | 0.65 | 6.24 |
| A2 | 13.4 | 773 | 0.60 | 6.21 |
| ITIC | 14.3 | 810 | 0.59 | 6.83 |
Note: j. the design is a squaresc: short circuit current; voc: an open circuit voltage; FF: injection efficiency; eta: conversion efficiency, eta is Jsc×Voc×FF。
From table 1 it can be seen that: the photoelectric conversion efficiencies of the solar cell device A1, the solar cell device A2 and a comparison solar cell device obtained by using the materials A1, A2 and the ITIC material are respectively 6.24%, 6.21% and 6.83%, and the two materials A1 and A2 have good absorption in visible and near infrared spectral regions and have shorter synthetic routes compared with the traditional fused ring nuclear-based material (such as the ITIC material). The two materials have excellent intersolubility with a polymer donor material, can generate higher photoelectric conversion efficiency (A1: 6.24%, A2: 6.21% and ITIC: 6.83), and have application prospect as a non-condensed ring nuclear-based micromolecule acceptor solar cell material.
Claims (10)
1. A compound having a structural formula shown in formula I:
in the formula I, pi is selected from any one of a non-structure, a structure shown in a formula II and a structure shown in a formula III;
in the formula I, A is selected from any one of a structure shown in a formula IV, a structure shown in a formula V and a structure shown in a formula VI;
in the formula IV, X is at least one of hydrogen, fluorine, chlorine and methyl;
in the formula I, R and R1Both are C1-C8 alkyl or alkoxy, and R1The alkyl or alkoxy of C1-C8 is straight chain or branched chain, which are the same or different.
2. The compound of claim 1, wherein: the compound shown in the formula I is selected from any one of the following compounds (A1) and (A2):
(A1) pi is the structure shown in the formula II; a is the structure shown in the formula IV, X is fluorine atom, R is octyl, R1Is hexyl;
(A2) pi is the structure shown in the formula III; a is the structure shown in the formula VI, and R is hexyl, R1Is octyl.
3. A process for the preparation of a compound of formula I as defined in claim 1 or 2, wherein in said compound of formula I, pi is the structure of said formula II; when A is the structure shown in the formula IV, the method comprises the following steps:
1) carrying out coupling reaction on a reactant 1 and a reactant 2 in an organic solvent a under the action of a Pd catalyst to obtain an intermediate P1, wherein the reactant 1 is selected from a compound shown in a formula VII, and the reactant 2 is selected from a compound shown in a formula VIII;
2) dissolving the intermediate P1 and N, N-dimethylformamide in an organic solvent b, and dropwise adding trioxy phosphine under an ice bath condition for acylation reaction to obtain an intermediate P2;
3) dropwise adding alkaline liquid into the intermediate P2 and the compound shown in the formula IX or the compound shown in the formula X in an organic solvent c for condensation reaction to obtain the compound shown in the formula I;
in the formula VII, R1The same as defined in formula I;
in the formula VIII, R and pi are the same as those in the formula I; b is a halogen atom, and the halogen atom can be selected from any one of the following: cl, Br or I;
in formula IX, X is as defined for formula IV.
4. The method of claim 3, wherein: in step 1), the Pd catalyst is selected from at least one of: pd (Ph)3)2Cl2、Pd(OAc)2And Pd (PPh)3)4；
The mole ratio of the Pd catalyst to the reactant 1 to the reactant 2 is 1: (50-250): (20-100);
the organic solvent a is at least one selected from toluene, xylene, dioxane and tetrahydrofuran, and can be tetrahydrofuran specifically;
the coupling reaction is a reflux reaction carried out under an inert gas atmosphere;
the reaction temperature of the coupling reaction is 60-140 ℃, and the reaction time is 12-36 h.
5. The method according to claim 3 or 4, characterized in that: in the step 2), the molar ratio of the N, N-dimethylformamide to the intermediate P1 to the trialkoxyphosphine is (0.8-1.5): 1: (0.8-5.2);
the reaction temperature of the acylation reaction is 0-60 ℃, and the reaction time is 5-20 h;
the organic solvent b is at least one of N, N-dimethylformamide, dichloromethane and dichloroethane.
6. The method according to any one of claims 3-5, wherein: in step 3), the molar ratio of the intermediate P2 to the compound of formula IX is 1: (2.2-20);
the reaction temperature of the condensation reaction is 60-100 ℃, and the reaction time is 12-36 h;
the alkaline liquid is at least one of alkyl amine compounds, aromatic amine compounds and pyridine: the alkylamine compound is specifically methylamine, and the aromatic amine compound is specifically aniline;
the organic solvent c is at least one selected from chloroform, dichloromethane and dichloroethane, and specifically is chloroform.
7. A process for the preparation of a compound of formula I according to claim 1 or 2, when in said compound of formula I, pi is said structure of formula III and a is said structure of formula VI, comprising the steps of:
a) dissolving a compound shown as a formula XI and a reactant 3 in an organic solvent 1 in the presence of a Pd catalyst to react to obtain an intermediate P3, wherein the reactant 3 is a compound shown as a formula VIII in claim 3;
b) dissolving the intermediate P3 in an organic solvent 2, and dropwise adding strong base and N, N-dimethylformamide to carry out acylation reaction to obtain an intermediate P4;
c) dropwise adding alkaline liquid into the intermediate P4 and the compound shown in the formula XII in an organic solvent 3, and carrying out condensation reaction to obtain the compound shown in the formula I;
in said formula XI, R2And R in the formula I1The same definition is applied.
8. The method of claim 7, wherein: in step a), the Pd catalyst is selected from at least one of: pd (Ph)3)2Cl2、Pd(OAc)2And Pd (PPh)3)4；
The mole ratio of the Pd catalyst, reactant 3, the compound of formula XI is 1: (20-100): (40-250);
the organic solvent 1 is at least one or a mixed system of toluene, xylene and trimethylbenzene;
the reaction is a reflux reaction carried out under an inert gas atmosphere;
the reaction temperature is 100-150 ℃, and the reaction time is 12-36 h.
9. The method according to claim 7 or 8, characterized in that: in step b), the molar ratio of the intermediate P3, the strong base and the N, N-dimethylformamide is 1: (0.8-1.5): (0.8-1.6);
the reaction temperature of the acylation reaction is-78-0 ℃, and the reaction time is 5-20 h;
the strong base used in the acylation reaction is n-butyllithium and/or isobutyllithium;
the organic solvent 2 is tetrahydrofuran;
in step c), the molar ratio of the intermediate P4 to the compound shown in formula XII is 1: (2.5-10.0);
the reaction temperature of the condensation reaction is 60-100 ℃, and the reaction time is 12-36 h;
the alkaline liquid is selected from at least one of methylamine, aniline and pyridine;
the organic solvent 3 is chloroform and/or dichloromethane.
10. Use of a compound of formula I according to claim 1 or 2 for the preparation of a solar cell:
the solar cell is specifically an organic solar cell.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115286644A (en) * | 2022-08-12 | 2022-11-04 | 电子科技大学 | Organic photoelectric small molecule containing [1,2,5] thiadiazole [3,4-g ] quinoxaline structure, and preparation method and application thereof |
| WO2023012365A1 (en) * | 2021-08-06 | 2023-02-09 | Cambridge Display Technology Ltd. | Photoresponsive asymmetric nonfullerene acceptors of the a-d-a'-d-a type for use in optoelectronic devices |
| KR20230084033A (en) * | 2021-11-30 | 2023-06-12 | 한국화학연구원 | Effective near-infrared absorbing electron acceptor material and near-infrared sensitive organic electronic device using thereof |
| US11925101B2 (en) | 2021-09-15 | 2024-03-05 | Raynergy Tek Incorporation | Organic semiconducting compound and the organic photoelectric components using the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206329A (en) * | 2010-03-31 | 2011-10-05 | 海洋王照明科技股份有限公司 | Dithiophene silole-quinoxalines conjugated polymer, and its preparation method and application |
| WO2018039347A2 (en) * | 2016-08-23 | 2018-03-01 | Azoulay Jason D | Narrow band gap conjugated polymers employing cross-conjugated donors useful in electronic devices |
| CN110312708A (en) * | 2016-12-15 | 2019-10-08 | 香港科技大学 | Luminescent material for biologic applications |
| WO2020072100A1 (en) * | 2018-05-05 | 2020-04-09 | Azoulay Jason D | Open-shell conjugated polymer conductors, composites, and compositions |
-
2021
- 2021-02-08 CN CN202110180820.3A patent/CN112920204A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206329A (en) * | 2010-03-31 | 2011-10-05 | 海洋王照明科技股份有限公司 | Dithiophene silole-quinoxalines conjugated polymer, and its preparation method and application |
| WO2018039347A2 (en) * | 2016-08-23 | 2018-03-01 | Azoulay Jason D | Narrow band gap conjugated polymers employing cross-conjugated donors useful in electronic devices |
| CN110312708A (en) * | 2016-12-15 | 2019-10-08 | 香港科技大学 | Luminescent material for biologic applications |
| WO2020072100A1 (en) * | 2018-05-05 | 2020-04-09 | Azoulay Jason D | Open-shell conjugated polymer conductors, composites, and compositions |
Non-Patent Citations (7)
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023012365A1 (en) * | 2021-08-06 | 2023-02-09 | Cambridge Display Technology Ltd. | Photoresponsive asymmetric nonfullerene acceptors of the a-d-a'-d-a type for use in optoelectronic devices |
| WO2023012366A1 (en) * | 2021-08-06 | 2023-02-09 | Cambridge Display Technology Ltd. | Photoresponsive nonfullerene acceptors of the a-d-a'-d-a type for use in optoelectronic devices |
| WO2023012364A1 (en) * | 2021-08-06 | 2023-02-09 | Cambridge Display Technology Ltd. | Photoresponsive nonfullerene acceptors of the a-d-a'-d-a type for use in optoelectronic devices |
| WO2023012363A1 (en) * | 2021-08-06 | 2023-02-09 | Cambridge Display Technology Ltd. | Photoactive nonfullerene acceptors of the a-d-a'-d-a type for use in optoelectronic devices |
| US11925101B2 (en) | 2021-09-15 | 2024-03-05 | Raynergy Tek Incorporation | Organic semiconducting compound and the organic photoelectric components using the same |
| KR20230084033A (en) * | 2021-11-30 | 2023-06-12 | 한국화학연구원 | Effective near-infrared absorbing electron acceptor material and near-infrared sensitive organic electronic device using thereof |
| KR102701909B1 (en) | 2021-11-30 | 2024-09-02 | 한국화학연구원 | Effective near-infrared absorbing electron acceptor material and near-infrared sensitive organic electronic device using thereof |
| CN115286644A (en) * | 2022-08-12 | 2022-11-04 | 电子科技大学 | Organic photoelectric small molecule containing [1,2,5] thiadiazole [3,4-g ] quinoxaline structure, and preparation method and application thereof |
| CN115286644B (en) * | 2022-08-12 | 2023-09-01 | 电子科技大学 | Organic photoelectric small molecule containing [1,2,5] thiadiazole [3,4-g ] quinoxaline structure, and preparation method and application thereof |
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