阅读说明：本技术 一种非对称稠环苯并三氮唑类受体及其制备方法和应用 (Asymmetric fused ring benzotriazole receptor and preparation method and application thereof ) 是由 邹应萍 蔡方方 李哲 袁俊 彭红建 于 2019-10-17 设计创作，主要内容包括：本发明公开了一种非对称稠环苯并三氮唑类受体的结构式如式Ⅰ所示：<Image he="423" wi="700" file="DDA0002237487700000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中R<Sub>1</Sub>和R<Sub>2</Sub>均为C<Sub>1</Sub>-C<Sub>20</Sub>的烷基中的一种。本发明中的非对称稠环苯并三氮唑类受体的成膜性和稳定性好,光学带隙窄,短路电流密度高,光电转换效率较高。本发明中非对称稠环苯并三氮唑类受体的合成发应条件温和,操作简单,易实现扩大化生产。本发明中的非对称稠环苯并三氮唑类受体小分子在紫外-可见区域(600-900nm)具有更强的吸收,及具有较高的光电转换效率,且与现有的常见PBDB-T-2F等给体材料具有更加匹配的能级和具有高而平衡的载流子迁移率,在制备高短路电流和能量转换效率的有机太阳能电池领域有很好的应用前景。(The invention discloses an asymmetric condensed ring benzotriazole receptor, which has a structural formula shown as a formula I: wherein R is 1 And R 2 Are all C 1 ‑C 20 One of the alkyl groups of (1). The asymmetric condensed ring benzotriazole receptor has the advantages of good film forming property and stability, narrow optical band gap, high short-circuit current density and higher photoelectric conversion efficiency. The synthesis of the asymmetric fused ring benzotriazole receptor has mild reaction conditions, simple operation and easy realization of expanded production. Asymmetric fused ring benzols in the present inventionThe triazole acceptor micromolecules have stronger absorption in an ultraviolet-visible region (600-900nm), higher photoelectric conversion efficiency, more matched energy level and high and balanced carrier mobility with the existing common donor materials such as PBDB-T-2F and the like, and have good application prospect in the field of preparing organic solar cells with high short-circuit current and energy conversion efficiency.)

1. The structural formula of the asymmetric condensed ring benzotriazole receptor is shown as the formula I:

wherein R is₁And R₂Are all C₁-C₂₀One of the alkyl groups of (a);

ar1 and Ar 2; x1 and X2 cannot be the same group at the same time;

ar1 and Ar2 are both one of a thiophene group, a thiophene derivative group, a bithiophene derivative group, a benzodithiophene derivative group, a pyrrolobithiophene derivative group, a pyrrolodiphenyl group, and a pyrrolodiphenyl derivative group;

x1 and X2 are both any one of the following groups

R in the X1 and X2 groups is hydrogen, halogen and C₁-C₆Alkyl radical, C₁-C₆Or an alkoxy group, an ester group or a cyano group.

2. The asymmetric fused ring benzotriazol receptor of claim 1, wherein Ar1 and Ar2 are one of the following groups:

wherein R is₃Is C₁-C₂₀One of the alkyl groups of (1).

3. A method for preparing an asymmetric fused ring benzotriazol receptor according to claim 1, comprising the steps of:

1) placing the compound A, the compound B1 and the compound B2 in a solvent, adding a catalyst, and then carrying out Stille coupling reaction to obtain a compound C;

2) carrying out condensation ring-closure reaction on the compound C in the step 1), triethyl phosphite and a solvent under the protection of argon to obtain an intermediate product C1, and then carrying out condensation ring-closure reaction on the intermediate product C1 and halogenated alkane R₂Carrying out substitution reaction on the X to obtain a compound D;

3) dissolving the compound D in the step 2) in a solvent, then dropwise adding a formylation reagent at a set temperature, reacting for a set time, and heating to carry out Vilsmeier-Haack reaction to obtain a compound E;

4) carrying out Knoevenagel reaction on the compound E in the step 3), X1 ketone, X2 ketone, a solvent and an acid-binding agent to obtain an asymmetric fused ring benzotriazole receptor shown as a formula I;

when the compound B1 and the compound B2 are not the same compound, X1 ketone and X2 ketone may be the same compound; when compound B1 and compound B2 are the same compound, X1 ketone and X2 ketone must be different compounds;

the synthetic route is as follows:

4. the preparation method of the asymmetric fused ring benzotriazol receptor as claimed in claim 3, wherein in the step 1), the ratio of the molar amount of the compound A to the total molar amount of the compound B1 and the compound B2 is 1 (1-4.0); when the compound B1 and the compound B2 are different compounds, the molar ratio of the compound B1 to the compound B2 is 1: 1; the solvent is tetrahydrofuran, and the molar volume ratio of the compound A to the solvent is (5-6): 20-90) mmol/mL; the catalyst is bis (triphenylphosphine) palladium dichloride, and the addition amount of the catalyst is 2-20% of the total molar amount of the compound A, the compound B1 and the compound B2; the reaction temperature is 65-80 ℃, the stille coupling reaction is a reflux reaction, and the reaction time is 24-48 h.

5. The method for preparing the asymmetric fused ring benzotriazol receptor as claimed in claim 3, wherein in the step 2), the molar ratio of the compound C to the triethyl phosphite is (8-10): 40-100, the solvent is o-dichlorobenzene, and the molar volume ratio of the compound C to the solvent is (8-9): 80-11 mmol/mL; the ring-closing reaction is a reflux reaction, the reaction temperature is 160-180 ℃, and the reaction time is 12-28 h; halogenated alkanes R₂The molar ratio of X to the compound C is (9-10) to 1; the substitution reaction is a reflux reaction, the reaction temperature is 80-100 ℃, and the reaction time is 12-24 hours.

6. The preparation method of the asymmetric fused ring benzotriazol receptor as claimed in claim 3, wherein in the step 3), the formylation reagent is phosphorus oxychloride, and the molar ratio of the compound D to the phosphorus oxychloride is 1 (15-40); the solvent is N, N-dimethylformamide, and the molar volume ratio of the compound D to the N, N-dimethylformamide is (1-2) to (20-60) mmol/mL; setting the temperature to be 0 ℃; setting the time to be 1.5-3 h; the Vilsmeier-Haack reaction is a reflux reaction, the reaction temperature is 80-90 ℃, and the reaction time is 12-24 hours.

7. The preparation method of the asymmetric fused ring benzotriazol receptor as claimed in claim 3, wherein in the step 4), the molar ratio of the compound E to the total molar ratio of the X1 ketone and the X2 ketone is 1 (4-6); when X1 ketone and X2 ketone are not the same compound, the molar ratio of X1 ketone to X2 ketone is 1: 1; the solvent is chloroform, and the molar volume ratio of the compound E to the chloroform is (0.15-0.4) to (20-40) mmol/mL; the acid binding agent is pyridine, and the molar volume ratio of the compound E to the pyridine is (0.15-0.4) to (0.8-1.5) mmol/mL; the Knoevenagel reaction is a reflux reaction, the reaction time is 8-24 hours, and the reaction temperature is 60-70 ℃.

8. Use of the asymmetric fused ring benzotriazole receptor of claim 1 or 3 in an organic solar cell material.

9. A method of preparing an organic solar cell device according to the asymmetric fused ring benzotriazole receptor of claim 8 comprising the steps of: preparing a hole transport layer on conductive glass, preparing a film active layer on the hole transport layer, dissolving asymmetric condensed ring benzotriazole small molecules and an electron donor material in a solvent to obtain a solution, and preparing a metal electrode on the film to obtain the polymer solar cell device.

10. The method for preparing the organic solar cell device by using the asymmetric fused ring benzotriazole acceptor according to claim 9 is characterized in that the molar ratio of the symmetric fused ring benzotriazole acceptor micromolecules to the electron donor material is 1 (1-1.5), the electron donor material is one or more of PBDB-D, PBDB-T, and the solvent is chloroform.

Technical Field

The invention belongs to the technical field of organic synthesis and solar cell materials, and particularly relates to an asymmetric fused ring benzotriazole receptor and a preparation method and application thereof.

Background

With the development of economy, the demand for energy is getting bigger and bigger, a large amount of fossil fuels are combusted, the environment is threatened greatly, so that the development of novel energy is urgent, and solar energy has great development prospect due to the advantages of cleanness, no pollution, inexhaustibility and the like. How to better utilize solar energy is a key solution for dealing with energy crisis. The organic solar cell has flexibility and low price, and can be prepared at low cost, so that the organic solar cell has attracted extensive attention of researchers. After more than twenty years of development, the efficiency of the current single-layer heterojunction organic solar cell reaches 16%, and the traditional silicon-based cell is likely to be replaced in the future.

In the literature [ Advanced Energy materials.2013,3(1):54-59]The absorption of the most commonly used donor material PTB7-Th (PCE10) for organic solar cells and the optical band gap (Eg) at 550-780nm are disclosed^opt1.59eV) and thus has more overlap with the commonly used non-fullerene acceptor materials, and therefore, a narrower band gap (Eg) is designed and synthesized^opt<1.5eV) non-fullerene acceptors matched with low or medium band gap donor polymers would be a new direction of development.

Disclosure of Invention

The invention aims to provide an asymmetric condensed ring benzotriazole receptor with a narrower band gap, and a preparation method and application thereof.

The structural formula of the asymmetric condensed ring benzotriazole receptor is shown as a formula I:

wherein R is₁And R₂Are all C₁-C₂₀One of the alkyl groups of (a);

ar1 and Ar 2; x1 and X2 cannot be the same group at the same time;

ar1 and Ar2 are both one of a thiophene group, a thiophene derivative group, a bithiophene derivative group, a benzodithiophene derivative group, a pyrrolobithiophene derivative group, a pyrrolodiphenyl group, and a pyrrolodiphenyl derivative group;

x1 and X2 are both any one of the following groups:

r in the X1 and X2 groups is hydrogen, halogen and C₁-C₆Alkyl radical, C₁-C₆Or an alkoxy group, an ester group or a cyano group.

Said R₁And R₂Preferably C₁-C₁₁One of the alkyl groups of (1).

Ar1 and Ar2 are preferably one of the following groups:

wherein R is₃Is C₁-C₂₀One of the alkyl groups of (1).

The preparation method of the asymmetric fused ring benzotriazole receptor comprises the following steps:

1) placing the compound A, the compound B1 and the compound B2 in a solvent, adding a catalyst, and then carrying out Stille coupling reaction to obtain a compound C;

2) carrying out condensation ring-closure reaction on the compound C in the step 1), triethyl phosphite and a solvent under the protection of argon to obtain an intermediate product C1, and then carrying out condensation ring-closure reaction on the intermediate product C1 and halogenated alkane R₂Carrying out substitution reaction on the X to obtain a compound D;

3) dissolving the compound D in the step 2) in a solvent, then dropwise adding a formylation reagent at a set temperature, reacting for a set time, and heating to carry out Vilsmeier-Haack reaction to obtain a compound E;

4) carrying out Knoevenagel reaction on the compound E in the step 3), X1 ketone, X2 ketone, a solvent and an acid-binding agent to obtain an asymmetric fused ring benzotriazole receptor shown as a formula I;

when the compound B1 and the compound B2 are not the same compound, X1 ketone and X2 ketone may be the same compound; when compound B1 and compound B2 are the same compound, X1 ketone and X2 ketone must be different compounds;

the synthetic route is as follows:

in the step 1), the ratio of the molar amount of the compound A to the total molar amount of the compound B1 and the compound B2 is 1 (1-4.0); when the compound B1 and the compound B2 are different compounds, the molar ratio of the compound B1 to the compound B2 is 1: 1; the solvent is tetrahydrofuran, and the molar volume ratio of the compound A to the solvent is (5-6): 20-90) mmol/mL; the catalyst is bis (triphenylphosphine) palladium dichloride, and the addition amount of the catalyst is 2-20% of the total molar amount of the compound A, the compound B1 and the compound B2; the reaction temperature is 65-80 ℃, the stille coupling reaction is a reflux reaction, and the reaction time is 24-48 h.

In the step 2), the molar ratio of the compound C to triethyl phosphite is (8-10): 40-100, the solvent is o-dichlorobenzene, and the molar volume ratio of the compound C to the solvent is (8-9): 80-11) mmol/mL; the ring-closing reaction is a reflux reaction, the reaction temperature is 160-180 ℃, and the reaction time is 12-28 h; halogenated alkanes R₂The molar ratio of X to the compound C is (9-10) to 1; the substitution reaction is a reflux reaction, the reaction temperature is 80-100 ℃, and the reaction time is 12-24 hours.

In the step 3), the formylation reagent is phosphorus oxychloride, and the molar ratio of the compound D to the phosphorus oxychloride is 1 (15-40); the solvent is N, N-dimethylformamide, and the molar volume ratio of the compound D to the N, N-dimethylformamide is (1-2) to (20-60) mmol/mL; setting the temperature to be 0 ℃; setting the time to be 1.5-3 h; the Vilsmeier-Haack reaction is a reflux reaction, the reaction temperature is 80-90 ℃, and the reaction time is 12-24 hours.

In the step 4), the molar ratio of the compound E to the total molar amount of the X1 ketone and the X2 ketone is 1 (4-6); when X1 ketone and X2 ketone are not the same compound, the molar ratio of X1 ketone to X2 ketone is 1: 1; the solvent is chloroform, and the molar volume ratio of the compound E to the chloroform is (0.15-0.4) to (20-40) mmol/mL; the acid binding agent is pyridine, and the molar volume ratio of the compound E to the pyridine is (0.15-0.4) to (0.8-1.5) mmol/mL; the Knoevenagel reaction is a reflux reaction, the reaction time is 8-24 hours, and the reaction temperature is 60-70 ℃.

The asymmetric condensed ring benzotriazole acceptor is applied to organic solar cell materials.

The method for preparing the organic solar cell device by using the asymmetric condensed ring benzotriazole receptor comprises the following steps: preparing a hole transport layer on conductive glass, preparing a film active layer on the hole transport layer, dissolving asymmetric condensed ring benzotriazole small molecules and an electron donor material in a solvent to obtain a solution, and preparing a metal electrode on the film to obtain the polymer solar cell device.

The molar ratio of the symmetric condensed ring benzotriazole small molecules to the electron donor material is 1 (1-1.5), the electron donor material is one or more of PBDB-D-2F, PBDB-T, and the solvent is chloroform.

The principle of the invention is as follows: the asymmetric condensed ring benzotriazole acceptor micromolecule is asymmetric hexatomic condensed ring Benzotriazole (BZTTC)₆) As intermediate nucleus, 5, 6-difluoro-3- (dicyanomethylene) inden-1-one (2 FI)C) And the n-type non-fullerene acceptor material as the electron-withdrawing unit has the following characteristics: (1) has stronger absorption (Eg) in the ultraviolet-visible region (600-900nm)^opt1.35 eV). Adjacent electron-rich donors (having alkyl chain thienothiophene units) and electron-deficient acceptors (benzotriazole units) are embedded in the coplanar D-A structure, which may increase the interaction between the donor and acceptor unit electrons. (2) Electron affinity and ionization are modulated by the introduction of an acceptor internuclear core. The electron-deficient part is the middle part (benzotriazole), which belongs to a weak electron-withdrawing structural unit in a typical D-A polymer, but the structure has a higher LUMO energy level; (3) the nitrogen atom in the six-membered fused ring not only serves as a coplanar heteroatom bridge, but also can be introduced into a side chain to increase the solubility of the non-fullerene micromolecular acceptor. (4) Due to the fact that different groups are closed on two sides of the intermediate nucleus benzotriazole, the asymmetric condensed ring benzotriazole acceptor micromolecules generate large polar dipole moment in the molecules, Jsc is increased, and charge migration is facilitated. (5) The asymmetric condensed ring benzotriazole acceptor micromolecule of the invention leads the micromolecule to form definite conformation and better solubility by introducing alkyl chain to a terminal electron donor (TT).

The invention has the beneficial effects that: 1) the asymmetric condensed ring benzotriazole receptor has the advantages of good film forming property and stability, narrow optical band gap, high short-circuit current density and higher photoelectric conversion efficiency. 2) The synthesis of the asymmetric fused ring benzotriazole receptor has mild reaction conditions, simple operation and easy realization of expanded production. 3) The asymmetric condensed ring benzotriazole small molecule of the invention has stronger absorption (Eg) in an ultraviolet-visible region (600-900nm)^opt1.35eV), and has a high photoelectric conversion efficiency (inverted device efficiency PCE)>15%), has more matched energy level and high and balanced carrier mobility with the existing common donor materials such as PBDB-D-2F and the like, and has good application prospect in the field of preparing organic solar cells with high short-circuit current and energy conversion efficiency. 4) Compared with the prior asymmetric fullerene and derivative material thereof, the asymmetric fused ring benzotriazole acceptor micromolecule of the invention can regulate and control the energy level and hasGood film forming property, good absorption strength, good stability, and narrower optical band gap (Eg)^opt1.35eV), has a high short-circuit current density (Jsc > 24mA cm)^-2) Has higher Photoelectric Conversion Efficiency (PCE) of an inverted device>15%) and the finished product can be made into a flexible solar cell panel.

Drawings

FIG. 1 hydrogen spectrum of Compound 4 prepared in example 1;

FIG. 2 the hydrogen spectrum of Compound 5 prepared in example 1;

FIG. 3 the hydrogen spectrum of Compound 6 prepared in example 1;

FIG. 4 BICT hydrogen spectrum prepared in example 1;

FIG. 5 carbon spectrum of BICT prepared in example 1;

FIG. 6 is a graph of the UV-vis absorption spectrum of BICT prepared in example 1;

FIG. 7 electrochemical diagram of BICT prepared in example 1;

FIG. 8 is a BICT-Cl hydrogen spectrum prepared in example 2;

FIG. 9 the hydrogen spectrum of compound 5' prepared in example 3;

FIG. 10 the hydrogen spectrum of Compound 6' prepared in example 3;

FIG. 11 hydrogen spectrum of Cff11 prepared in example 3;

figure 12 hydrogen spectrum of compound 4 "prepared in example 4;

figure 13 hydrogen spectrum of compound 5 "prepared in example 4;

figure 14 hydrogen spectrum of compound 6 "prepared in example 4;

FIG. 15 the hydrogen spectrum of Compound Y9-2F prepared in example 4;

FIG. 16 Performance graph of a solar cell device prepared by A-1 in example 5;

Detailed Description