N,N-diethylaminocoumarin compounds and preparation methods and applications thereof

Abstract

The invention discloses an N,N-diethylaminocoumarin compound and a preparation method and application thereof. The molecular structure of the N,N-diethylaminocoumarin compound is shown in formula (C-4), formula (C-5) or formula (C-6). The invention uses N,N-diethylaminocoumarin as a donor, thiophene, furan and benzene ring of bithiophene as bridge bonds, and cyanoacetic acid as an acceptor to synthesize the N,N-diethylaminocoumarin compound. The N,N-diethylaminocoumarin compound can be used as a dye sensitizer for co-sensitization with a classic metal sensitizer Z907. A dye-sensitized solar cell assembled by using the compound as a dye sensitizer and Z907 has good photoelectric conversion efficiency, thereby adding a new applicable substance to the screening of dye sensitizers.

Description

Technical Field

[0001] The invention relates to N,N-diethylaminocoumarin compounds and a preparation method and application thereof. Background Art

[0002] Dye-sensitized solar cells (DSSCs) have attracted extensive attention due to their advantages of low production cost and simple manufacturing process. As a key component of DSSCs, dye sensitizers absorb light and generate electrons, which determines the photoelectric performance of DSSCs.

[0003] At present, the light capture ability of a single dye is weak and the highest photoelectric conversion efficiency of DSSCs based on a single dye has been difficult to break through. In order to overcome these problems, more and more researchers are focusing on co-sensitization. Co-sensitization of organic dyes and metal dyes can broaden the spectral absorption range and improve the molar extinction coefficient. The ideal dye co-sensitization effect is that the absorption spectra of the two dyes can achieve full-color absorption complementarity, improve their light capture ability, and thus improve the photoelectric performance of DSSCs. Summary of the invention

[0004] The purpose of the present invention is to provide N,N-diethylaminocoumarin compounds and preparation methods and applications thereof. The N,N-diethylaminocoumarin compounds can be used as dye sensitizers for co-sensitization with the classic metal sensitizer Z907. The assembled dye-sensitized solar cells have good photoelectric conversion efficiency, which adds new applicable substances to the screening of dye sensitizers.

[0005] The present invention discloses N,N-diethylaminocoumarin compounds, including compounds with the following three structures, wherein the molecular structures of the three compounds are shown in formula (C-4), formula (C-5) or formula (C-6);

[0006]

[0007] The present invention also discloses a method for preparing N,N-diethylaminocoumarin compounds, which specifically comprises: dissolving a compound represented by formula (II-1), formula (II-2) or formula (II-3) and cyanoacetic acid in a solvent, adding an alkaline substance, heating under reflux and stirring to react under the protection of a nitrogen atmosphere, and after the reaction is completed, concentrating the reaction solution to remove the solvent, dissolving the obtained concentrate in an eluent, separating and purifying it through column chromatography silica gel, collecting the eluent and evaporating the eluent to obtain the target product;

[0008] The structural formulas of the compounds represented by formula (II-1), formula (II-2) and formula (II-3) are as follows:

[0009]

[0010] Furthermore, the present invention also discloses that the time of the heating reflux stirring reaction is 8-12 hours.

[0011] Furthermore, the present invention also discloses that the solvent is a mixed solvent consisting of chloroform and acetonitrile, and the volume ratio of chloroform to acetonitrile is 1:1-3, preferably 1:2.

[0012] Furthermore, the present invention also discloses that the eluent is a mixed solvent consisting of dichloromethane and methanol, and the volume ratio of dichloromethane to methanol is 10-30:1, preferably 20:1.

[0013] Furthermore, the present invention also discloses that the molar ratio of the compound represented by formula (II-1), formula (II-2) or formula (II-3), cyanoacetic acid and the alkaline substance is 1:2-4:8-12, preferably 1:3:10.

[0014] Furthermore, the present invention also discloses that the alkaline substance is piperidine.

[0015] Furthermore, the present invention also discloses that the ratio of the amount of substance of the compound represented by formula (II-1), formula (II-2) or formula (II-3) to the volume of the solvent is 1:30-60, the unit of the amount of substance is mmol, and the unit of volume is mL.

[0016] Furthermore, the present invention also discloses a method for synthesizing the compound represented by formula (II-1), formula (II-2) or formula (II-3), which is as follows:

[0017] 3-(5-bromo-thiophene-2-yl)-7-N,N-diethylaminocoumarin, tetrakistriphenylphosphine palladium and potassium carbonate are added to a Shrek tube, and any one of 5-formyl-2-thiopheneboric acid, 5-formyl-2-furanboric acid or 4-formylphenylboric acid is added to the Shrek tube, tetrahydrofuran and water are added under nitrogen protection, and the mixture is heated to reflux for reaction. After the reaction is completed, the mixture is cooled to room temperature, poured into water, extracted with dichloromethane, washed with saturated brine, the organic phase is dried over anhydrous sodium sulfate, and the solvent is dried by spin drying; the residue is purified by column chromatography to obtain a compound of formula (II-1), formula (II-2) or formula (II-3).

[0018] Furthermore, the present invention also discloses the synthesis of the compound represented by formula (II-1), formula (II-2) or formula (II-3), wherein the eluent is petroleum ether and dichloromethane in a volume ratio of 1:1, wherein the column chromatography separation process comprises: the concentrate is dissolved in the eluent and then separated and purified by column chromatography silica gel, the eluent is collected and the eluent is evaporated to remove the eluent, and then dried to obtain a solid powder product.

[0019]

[0020] Furthermore, the present invention also discloses the application of N,N-diethylaminocoumarin compounds in dye sensitizers.

[0021] By adopting the above technology, compared with the prior art, the beneficial effects of the present invention are as follows: the present invention synthesizes N,N-diethylaminocoumarin compounds by using N,N-diethylaminocoumarin as a donor, thiophene, furan and benzene ring of bithiophene as bridge bonds, and cyanoacetic acid as an acceptor. The N,N-diethylaminocoumarin compounds can be used as dye sensitizers for co-sensitization with the classic metal sensitizer Z907. The dye-sensitized solar cells assembled by using the compounds as dye sensitizers and Z907 have good photoelectric conversion efficiency, which adds new applicable substances to the screening of dye sensitizers. DETAILED DESCRIPTION

[0022] The present invention will be further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited thereto.

[0023] Example 1 Synthesis of the compound represented by formula (C-4):

[0024]

[0025] 1) Synthesis of the compound represented by formula (II-1)

[0026] Weigh 3-(5-bromo-thiophene-2-yl)-7-N,N-diethylaminocoumarin (0.8mmol), 5-formyl-2-thiopheneboric acid (1.6mmol), tetratriphenylphosphine palladium (0.04mmol) and potassium carbonate (4.0mmol) into a Shrek tube, add tetrahydrofuran (12mL) and water (2mL) under nitrogen protection, heat to reflux, and react for 12h. After the reaction solution is cooled, pour it into water, extract it with dichloromethane several times, combine the organic phases, wash them with saturated brine, dry the organic phases with anhydrous sodium sulfate, and spin dry the solvent. The residue is purified by column chromatography to obtain 0.14g of red solid II-1 with a yield of 42.7%.

[0027] The eluent is petroleum ether and dichloromethane in a volume ratio of 1:1, and the column chromatography separation process is as follows: the concentrate is dissolved in the eluent and then separated and purified by column chromatography silica gel, the eluent is collected and the eluent is evaporated to remove the eluent, and then dried to obtain a solid powder product. The steps in the following Examples 2 and 3 are equivalent.

[0028] Compound represented by formula (II-1): melting point: 209-211°C. 1H NMR (500MHz, CDCl3) δ9.87(s,1H),7.96(s,1H),7.69(d,J=3.9Hz,1H),7.57(d,J=4.0Hz,1H),7.40-7.35(m,2H),7.31(d,J= 3.9Hz,1H),6.65(dd,J=8.8,2.4Hz,1H),6.56(d,J=2.2Hz,1H),3.46(q,J=7.0Hz,4H),1.25(t,J=7.0Hz,6H).HRMS(ESI)m / z calcd for C 22 H 20 NO3S2 + (M+H) + 410.0885, found 410.0881.

[0029] 2) Synthesis of the compound represented by formula (C-4):

[0030] Add compound II-1 (0.3 mmol) and cyanoacetic acid (0.6 mmol) to a Shrek tube, add chloroform (3 mL) and acetonitrile (6 mL) under nitrogen protection, then slowly add piperidine (0.24 mL) dropwise, and heat under reflux for 12 h. After the reaction is complete, remove the solvent. The residue is purified by column chromatography (V DCM :V MeOH =20:1) to obtain 0.07 g of dark red solid C-4 with a yield of 48.9%.

[0031] Compound represented by formula (C-4): melting point: 60-63°C. 1 H NMR (500MHz, DMSO) δ8.54(s,1H),7.96(s,1H),7.79(d,J=4.1Hz,1H),7.63(d,J=4.0Hz,1H),7.55(d,J=9.0Hz,1H),7.49(d,J=3.8Hz,1H ),7.14(d,J=3.8Hz,1H),6.80(dd,J=9.0,2.4Hz,1H),6.63(d,J=2.3Hz,1H),3.47(q,J=7.0Hz,4H),1.15(t,J=7.0Hz,6H).HRMS(ESI)m / z calcd for C 25 H 21 N2O4S2 + (M+H) + 477.0943, found 477.0939.

[0032] Example 2 Synthesis of the compound represented by formula (C-5):

[0033]

[0034] 1) Synthesis of the compound represented by formula (II-2)

[0035] Weigh 3-(5-bromo-thiophene-2-yl)-7-N,N-diethylaminocoumarin (0.8mmol), 5-formyl-2-furanboronic acid (1.6mmol), tetratriphenylphosphine palladium (0.04mmol) and potassium carbonate (4.0mmol) into a Shrek tube, add tetrahydrofuran (12mL) and water (2mL) under nitrogen protection, heat to reflux, and react for 12h. After the reaction solution is cooled, pour it into water, extract it with dichloromethane several times, combine the organic phases, wash with saturated brine, dry the organic phase with anhydrous sodium sulfate, and spin dry the solvent. The residue is purified by column chromatography (V PE :V DCM =1:1) to obtain 0.18 g of red solid II-2 with a yield of 57.2%.

[0036] Compound represented by formula (II-2): melting point: 150-153°C. 1 H NMR (500MHz, DMSO) δ9.56(s,1H),8.55(s,1H),7.77(d,J=4.1Hz,1H),7.68(d,J=4.1Hz,1H),7.65(d,J=3.8Hz,1H),7.53(d,J=9.0Hz,1H ),7.10(d,J=3.7Hz,1H),6.80(dd,J=9.0,2.4Hz,1H),6.61(d,J=2.3Hz,1H),3.47(q,J=7.0Hz,4H),1.15(t,J=7.0Hz,6H).HRMS(ESI)m / z calcd for C 22 H 20 NO4S + (M+H) + 394.1113, found 394.1114.

[0037] 2) Synthesis of the compound represented by formula (C-5)

[0038] Compound II-2 (0.3 mmol) and cyanoacetic acid (0.9 mmol) were added to a Shrek tube, and a mixed solution of chloroform (5 mL) and acetonitrile (10 mL) was added under nitrogen protection, and then 0.3 mL of piperidine was slowly added dropwise, and the mixture was heated under reflux for 10 h. After the reaction was completed, the solvent was dried by spin drying. The residue was purified by column chromatography (V DCM :V MeOH =20:1) to obtain 0.10 g of dark red solid C-5 with a yield of 72.5%.

[0039] Compound represented by formula (C-5): melting point: 225-227°C. 1 H NMR (500MHz, DMSO) δ8.48(s,1H),7.73(d,J=4.0Hz,1H),7.68(s,1H),7.54(d,J=9.0Hz,1H),7.52(d,J=4.0Hz,1H),7.20(d,J=3.7Hz,1H ),6.99(d,J=3.7Hz,1H),6.78(dd,J=9.0,2.3Hz,1H),6.60(d,J=2.1Hz,1H),3.45(q,J=7.0Hz,4H),1.14(t,J=7.0Hz,6H).HRMS(ESI)m / z calcd for C 25 H 21 N2O5S + (M+H) + 461.1171, found 461.1167.

[0040] Example 3 Synthesis of the compound represented by formula (C-6):

[0041]

[0042] 1) Synthesis of the compound represented by formula (II-3)

[0043] Weigh 3-(5-bromo-thiophene-2-yl)-7-N,N-diethylaminocoumarin (0.8mmol), 4-formylphenylboronic acid (1.6mmol), tetrakistriphenylphosphine palladium (0.04mmol) and potassium carbonate (4.0mmol) into a Shrek tube, add tetrahydrofuran (10mL) and water (2mL) under nitrogen protection, heat to reflux, and react for 12h. After the reaction solution is cooled, pour it into water, extract it with dichloromethane several times, combine the organic phases, wash with saturated brine, dry the organic phase with anhydrous sodium sulfate, and spin dry the solvent. The residue is purified by column chromatography (V PE :V DCM =1:1) to obtain 0.17 g of orange-red solid II-3 with a yield of 52.7%.

[0044] Compound represented by formula (II-3): melting point: 153-155°C. 1H NMR (500MHz, CDCl3) δ10.01(s,1H),7.95(s,1H),7.89(d,J=7.5Hz,2H),7.81(d,J=8.3Hz,2H),7.66(d,J=4.0Hz,1H),7.47(t,J=5.6Hz ,1H),7.36(d,J=8.8Hz,1H),6.67(d,J=8.6Hz,1H),6.58(d,J=1.5Hz,1H),3.46(q,J=7.1Hz,4H),1.25(t,J=7.3Hz,6H).HRMS(ESI)m / z calcd for C 24 H 22 NO3S + (M+H) + 404.1320, found 404.1317.

[0045] 2) Synthesis of the compound represented by formula (C-6)

[0046] Weigh compound II-3 (0.3 mmol) and cyanoacetic acid (0.12 mmol), then add chloroform (6 mL) and acetonitrile (12 mL) under nitrogen protection, then slowly add piperidine (0.36 mL) dropwise, heat to 80°C and react for 8 h. After the reaction solution is cooled, remove the solvent. The residue is purified by column chromatography (V DCM :V MeOH =20:1) to obtain 0.08 g of red solid C-6 with a yield of 56.6%.

[0047] Compound represented by formula (C-6): melting point: 208-211°C. 1 H NMR (500MHz, DMSO) δ8.51(s,1H),8.27(s,1H),8.08(d,J=8.6Hz,2H),7.89(d,J=8.5Hz,2H),7.80-7.75(m,2H),7.55(d,J= 9.0Hz,1H),6.81(dd,J=9.0,2.4Hz,1H),6.63(d,J=2.3Hz,1H),3.48(q,J=7.0Hz,4H),1.16(t,J=7.0Hz,6H).HRMS(ESI)m / z calcd for C 27 H 23 N2O4S + (M+H) + 471.1379, found 471.1382.

[0048] Example 4 Application of N,N-diethylaminocoumarin compounds as dye sensitizers:

[0049] When used as a dye sensitizer, the application includes the following steps:

[0050] N,N-diethylaminocoumarin compounds and dye Z907 were dissolved in a CH3Cl-CH3OH mixed solvent to obtain a mixed solution of N,N-diethylaminocoumarin compounds and Z907 (the concentration of N,N-diethylaminocoumarin compounds was 2×10 -4 mol·L -1 ; The concentration of Z907 is 3×10 -4 mol·L -1 ); the volume ratio of CH3Cl and CH3OH in the CH3Cl-CH3OH mixed solvent is 10:1.

[0051] The double-layer TiO2 nanoparticle film prepared by screen printing was used as the photoelectrode: First, a layer of 20nm TiO2 particles with a thickness of 12μm was printed on the conductive glass FTO, and calcined in a muffle furnace at 450℃ for 30min. After cooling to room temperature, the calcined film was immersed in 0.04mol·L -1 The film was pretreated with TiCl4 aqueous solution at 70℃ for 30min, then taken out from the TiCl4 aqueous solution and rinsed with water and ethanol respectively, and dried with a hair dryer. After calcination again at 450℃ in a muffle furnace for 30min, a double-layer TiO2 nanoparticle film photoelectrode was obtained.

[0052] The double-layer TiO2 nanoparticle film photoelectrode obtained by calcination was cooled to 80°C and then immersed in the mixed solution of N,N-diethylaminocoumarin compounds and Z907 obtained above, and sensitized at room temperature for 24 hours to obtain a TiO2 electrode loaded with N,N-diethylaminocoumarin compounds and Z907 compounds.

[0053] Preparation of platinum counter electrode: The H2PtCl6 aqueous solution is printed on the FTO conductive glass by screen printing. The H2PtCl6 aqueous solution wets the surface of the FTO conductive glass, dries it, and then sinters it at 400°C in a muffle furnace for 20 minutes to obtain the platinum counter electrode.

[0054] The double-layer TiO2 nanoparticle film photoelectrode and the platinum counter electrode prepared above were assembled into a sandwich structure, and an electrolyte (containing 0.07 mmol / L - The electrolyte comes from Yingkou Aopivite New Energy Technology Co., Ltd., and is introduced into the battery using the capillary permeation principle to form a dye-sensitized solar cell. 2 Under light intensity irradiation, the current-voltage curve of the DSSC assembled by N,N-diethylaminocoumarin compounds and Z907 was measured, and the performance parameter results are shown in Table 1:

[0055] Table 1 Performance parameters of DSSCs assembled from N,N-diethylaminocoumarin compounds

[0056]

[0057] It can be seen from Table 1 that the dye-sensitized solar cells assembled with the N,N-diethylaminocoumarin compounds of the present invention and Z907 as dye sensitizers have good photoelectric conversion efficiency, which is 5.97-6.77%, and most of them are higher than the solar cells sensitized by Z907 alone, adding new applicable substances to the screening of co-sensitizers of Z907.

[0058] The contents described in this specification are merely an enumeration of the implementation forms of the inventive concept. The protection scope of the present invention should not be regarded as limited to the specific forms described in the embodiments. The protection scope of the present invention is also limited to the equivalent technical means that can be thought of by those skilled in the art based on the inventive concept.

Claims

1. An application of an N,N-diethylaminocoumarin compound as a dye sensitizer, characterized in that The molecular structure of N,N-diethylaminocoumarin compounds is shown in formula (C-6); ； When used as a dye sensitizer, the application includes the following steps: dissolving N,N-diethylaminocoumarin compounds and dye Z907 in a CH3Cl-CH3OH mixed solvent to obtain a mixed solution of N,N-diethylaminocoumarin compounds and Z907, wherein the concentration of the N,N-diethylaminocoumarin compounds is 2×10 -4 mol•L -1 , the concentration of Z907 is 3×10 -4 mol•L -1 ; The volume ratio of CH3Cl and CH3OH in the CH3Cl-CH3OH mixed solvent is 10:

1.

2. The use according to claim 1, characterized in that The preparation method of N,N-diethylaminocoumarin compounds is as follows: the compound represented by formula (II-3) and cyanoacetic acid are dissolved in a solvent, an alkaline substance is added, and the mixture is heated under reflux with stirring under the protection of a nitrogen atmosphere. After the reaction is completed, the reaction solution is concentrated to remove the solvent, the obtained concentrate is dissolved in an eluent, and then separated and purified by column chromatography on silica gel, the eluent is collected, and the eluent is evaporated to remove the eluent, thereby obtaining the target product; The structural formula of the compound represented by formula (II-3) is as follows: 。 3. The use according to claim 2, characterized in that The heating reflux reaction time is 8-12 h.

4. The use according to claim 2, characterized in that The solvent is a mixed solvent consisting of chloroform and acetonitrile, and the volume ratio of chloroform to acetonitrile is 1:1-3.

5. The use according to claim 4, characterized in that The solvent is a mixed solvent consisting of chloroform and acetonitrile, and the volume ratio of chloroform to acetonitrile is 1:

2.

6. The use according to claim 2, characterized in that The molar ratio of the compound represented by formula (II-3), cyanoacetic acid and the alkaline substance is 1:2-4:8-12.

7. The use according to claim 6, characterized in that The molar ratio of the compound represented by formula (II-3), cyanoacetic acid and the alkaline substance is 1:3:

10.

8. The use according to claim 6, characterized in that The alkaline substance is piperidine.

9. The use according to claim 2, characterized in that The ratio of the amount of substance of the compound represented by formula (II-3) to the volume of the solvent is 1:30-60, the unit of the amount of substance is mmol, and the unit of volume is mL.

10. The use according to claim 2, characterized in that The eluent is a mixed solvent consisting of dichloromethane and methanol, and the volume ratio of the dichloromethane to methanol is 10-30:

1.

11. The use according to claim 10, characterized in that The volume ratio of dichloromethane to methanol is 20:1.

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