CN115785693B - N-type organic dye of 1, 2-benzothiazine, preparation method and application - Google Patents
N-type organic dye of 1, 2-benzothiazine, preparation method and application Download PDFInfo
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Abstract
The invention relates to an n-type organic dye based on 1, 2-benzothiazine, a preparation method and application thereof. The molecule adopts triphenylamine, carbazole, indole units and the like as electron donating groups, 1, 2-benzothiazine as pi conjugated bridges, furan groups as auxiliary connecting groups, and cyanoacrylate as acceptor groups and anchoring groups. The invention is mainly characterized in that 1, 2-benzothiazine is adopted as a donor or pi conjugated bridge, furan and benzothiazine can form an intramolecular hydrogen bond with the same, so that intramolecular planeness is increased, intramolecular charge transfer is effectively improved, energy gaps are regulated, spectral response range is improved, light capturing efficiency is enhanced, device performance is improved, and the invention has important application prospect in preparing dye sensitized solar cells.
Description
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to an n-type organic dye based on 1, 2-benzothiazine and a preparation method and application thereof.
Background
New energy is receiving increasing attention, solar energy being the fastest growing technology in renewable energy, with the potential to supply a significant portion of the global energy demand in the future. Silicon (Si) solar cell technology currently dominates the photovoltaic market. This technology has become very mature in the last decade, and occupies a large market. Although the future prospects of crystalline silicon solar cells are clear, problems such as their complex manufacturing processes, the use of hazardous chemicals, etc., may open up opportunities for future development of other photovoltaic technologies.
Third generation solar cells mainly include dye sensitized solar cells, organic solar cells and perovskite solar cells. Among them, dye-sensitized solar cells are easy and simple to manufacture, low in cost, high in stability, and have high industrial scale manufacturing potential because they can be produced while using established scalable manufacturing methods (e.g., screen printing, inkjet printing, etc.). The working principle of the dye sensitized solar cell is as follows: when absorbing sunlight, electrons are excited to a high-energy gap layer, but the excited state is an unstable state, so that the electrons must be transmitted into a conductive layer of the dye molecules in the close vicinity at the highest speed, and meanwhile, the electrons lost by the dye molecules can be fed back from the electrolyte at the first time. Electrons in the conduction band of the dye molecule are eventually transported through the electrode to the external circuit to generate a photo-generated current.
Sensitizers are a critical part of dye sensitized solar cells. The light absorption efficiency and the electron injection rate are improved by designing different structures of the solar cell, so that the cell efficiency is improved. Therefore, from the standpoint of improving the battery efficiency and the cost of the photosensitizers, widening the photoresponse range and developing novel dyes are the focus of research.
Disclosure of Invention
The invention aims to provide an n-type organic dye based on 1, 2-benzothiazine, which has the advantages of stable structure, common and easily available raw materials, low production cost, proper energy gap and high absorption coefficient.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
an n-type organic dye based on 1, 2-benzothiazine has a structural general formula shown in formula I or formula II:
wherein R is a straight or branched alkyl chain having 1 to 12 carbon atoms, orWherein R is 2 Is a straight or branched alkyl chain having 1 to 12 carbon atoms;
selected from any one of the following:
wherein R is 1 Is hydrogen, a straight or branched alkyl chain having 1 to 12 carbon atoms, or a straight or branched alkyl chain having 1 to 12 carbon atoms containing an oxygen atom or a sulfur atom.
The synthesis method of the formula I comprises the following steps:
adding 2-aminobenzene mercaptan and 4-tetrahydrocyclic ketone into dimethyl sulfoxide, and stirring in air at 110 ℃ for 24 hours to obtain a compound 1;
mixing the compound 1, R-Br, KOH, TBAB and dimethyl sulfoxide, and reacting for 10 hours at room temperature under the nitrogen atmosphere to obtain a compound 2;
mixing the compound 2 with chloroform, stirring in an ice-water bath under nitrogen atmosphere for reaction for 6 hours, and adding N-bromosuccinimide into a reaction bottle three times in the first two hours to obtain a compound 3;
3, 5-Formylfuran-2-boronic acid, K 2 CO 3 、Pd[P(C 6 H 5 ) 3 ] 4 Putting TBAB and THF into a three-neck flask, and heating and refluxing in a dark and nitrogen atmosphere at 85 ℃ for 13h to obtain a compound 4;
compound 4, cyanoacetic acid, ammonium acetate and acetic acid were mixed and heated to reflux at 110 ℃ for 12 hours under nitrogen atmosphere, and purified to give the product of formula I.
The synthetic route of the formula I is as follows:
preferably, the molar ratio of 2-aminobenzenethiol to 4-tetrahydrocyclic ketone is 1.5:1.
preferably, the molar ratio of compound 1, R-Br, KOH, tetrabutylammonium bromide (TBAB) is 1:1.3:3:0.3.
preferably, the compound 3, 5-formylfuran-2-boronic acid, K 2 CO 3 、Pd[P(C 6 H 5 ) 3 ] 4 The mole ratio of TBAB is 1:1.2:2.5:0.05:0.3.
preferably, the molar ratio of compound 4, cyanoacetic acid, ammonium acetate is 1:2:1.
wherein, the synthesis method of the formula II is as follows:
mixing the compound 4 with chloroform, stirring in an ice-water bath under nitrogen atmosphere for reaction for 6 hours, and adding N-bromosuccinimide into a reaction bottle three times in the first two hours to obtain a compound 5;
compound 5, compoundK 2 CO 3 、Pd[P(C 6 H 5 ) 3 ] 4 Mixing TBAB and THF, heating and refluxing in dark and nitrogen atmosphere at 85deg.C for 13h, and purifying to obtain compound 6;
compound 6, cyanoacetic acid, ammonium acetate and acetic acid were mixed and heated to reflux at 90 ℃ under nitrogen for 24 hours and purified to give the product of formula II.
The synthetic route of the formula II is as follows:
preferably, compound 5, compoundK 2 CO 3 、Pd[P(C 6 H 5 ) 3 ] 4 The molar ratio of TBAB is 1:1.2:2.5:0.05:0.3。
The invention also provides application of the n-type organic dye of the 1, 2-benzothiazine as a sensitizer in dye-sensitized solar cells.
Compared with the prior art, the invention has the beneficial technical effects that:
the invention relates to an n-type organic dye based on 1, 2-benzothiazine, which adopts 1, 2-benzothiazine as pi conjugated bridge, triphenylamine, carbazole, indole and the like as donor groups, furan as a connecting unit and cyanoacrylate as an anchoring group, and is characterized in that the benzophenothiazine is adopted as a core pi conjugated bridge so as to improve charge transfer in the molecule and improve spectral response range. Furan has electron-rich characteristic as a connecting unit, and furan and benzothiazine can form intramolecular field effect by connecting, so that the flatness of molecules is improved, the charge transfer in molecules is effectively improved, and the harmful charge recombination in devices is reduced, thereby improving the performance of the devices. Further, the introduced triphenylamine, carbazole, indole and other groups are used as donor structures, so that the spectral response range can be further widened, the triphenylamine, carbazole, indole and other groups can be moved to a near infrared region, intramolecular charge transfer is enhanced, light capturing efficiency is enhanced, and device performance is improved.
The n-type organic dye based on the 1, 2-benzothiazine has the advantages of stable structure, proper energy gap, high absorption coefficient, common and easily obtained raw materials in the preparation method, low production cost and capability of being used for preparing a dye-sensitized solar cell.
Drawings
FIG. 1 is a graph of UV-vis absorption spectra of dye PP-OX;
FIG. 2 is a graph of UV-vis absorption spectra of dye CZ-PP-OX;
FIG. 3 is a graph of UV-vis absorption spectra of dye TAP-PP-OX;
FIG. 4 is a J-V profile of a DSSC device fabricated with the dye PP-OX;
FIG. 5 is a J-V profile of a DSSC device fabricated with the dye CZ-PP-OX;
FIG. 6 is a J-V profile of a DSSC device fabricated with the dye TAP-PP-OX.
Detailed Description
The invention is further described below in connection with specific embodiments. The following examples are only for more clearly illustrating the technical aspects of the present invention, and are not intended to limit the scope of the present invention.
Example 1:
the synthetic route is as follows:
preparation of Compound 1 2-aminobenzenethiol (0.375 mmoL) and 4-tetrahydrocyclic ketone (0.250 mmoL) (1.5:1) were added to 1.0mL of dimethyl sulfoxide and stirred in air at 110℃for 24 hours. After completion, the reaction mixture was diluted with ethyl acetate and filtered through a layer of silica gel over wollastonite. Volatiles were removed in vacuo to give the crude product. Further silica gel column chromatography (dichloromethane/petroleum ether) was required to give pure compound 1 in 70% yield. 1 H NMR(400MHz,DMSO-d 6 )δ8.66(s,1H),8.35(dd,J＝8.5,1.3Hz,1H),7.80(dd,J＝8.1,1.4Hz,1H),7.52(ddd,J＝8.4,6.8,1.4Hz,1H),7.48–7.37(m,2H),7.13(dd,J＝8.0,1.4Hz,1H),7.10–7.02(m,2H),6.97(dd,J＝7.6,1.5Hz,1H),6.84(td,J＝7.4,1.4Hz,1H).
Preparation of Compound 2 Compound 1, bromohexane, KOH, TBAB (1:1.3:3:0.3) were added to dimethyl sulfoxide and placed in a three-necked flask, and reacted under a nitrogen atmosphere at room temperature for 10 hours. When the reaction time reached, water was added to the reaction solution to terminate the reaction. The reaction was then washed three times with Dichloromethane (DCM) and brine and with anhydrous sodium sulfate (Na 2 SO 4 ) And (5) drying. Finally, the crude product was purified by column chromatography using Petroleum Ether (PE)/DCM (15:1) as eluent to give compound 2 in 70% yield. 1 H NMR(400MHz,DMSO-d6)δ8.07(d,J＝8.5Hz,1H),7.85(dd,J＝8.2,1.3Hz,1H),7.60(d,J＝8.5Hz,1H),7.53(ddd,J＝8.4,6.8,1.4Hz,1H),7.44(ddd,J＝8.0,6.8,1.2Hz,1H),7.30(dd,J＝8.0,1.4Hz,1H),7.26–7.14(m,3H),7.00(td,J＝7.5,1.3Hz,1H),4.11–3.54(m,2H),1.57–1.34(m,2H),1.32–0.90(m,6H),0.66(t,J＝7.0Hz,3H).
Preparation of compound 3: compound 2 (333 mg,1 mmol) and chloroform (CHCl) 3 10 mL) was added to a three-necked flask, the reaction was stirred in an ice-water bath under nitrogen atmosphere for 6 hours, and N-bromosuccinimide (NBS, 534mg,3 mmol) was added to the reaction flask three times in the first two hours. When the reaction was complete, water was added to stop the reaction. The reaction was then extracted 3 times with DCM and brine and dried over anhydrous Na 2 SO 4 And (5) drying. The crude product was then purified by column chromatography using PE/DCM (1:1) as eluent to give compound 3 in 70% yield. 1 H NMR(400MHz,DMSO-d 6 )δ8.16–8.08(m,1H),8.08–8.00(m,1H),7.68–7.57(m,3H),7.32(dd,J＝8.0,1.4Hz,1H),7.24(td,J＝7.7,1.5Hz,1H),7.18(dd,J＝7.7,1.5Hz,1H),7.03(td,J＝7.5,1.3Hz,1H),4.18–3.48(m,2H),1.58–1.34(m,2H),1.33–0.82(m,6H),0.65(t,J＝7.0Hz,3H).
Preparation of Compound 4: compound 3 (412 mg,1 mmol), 5-formylfuran-2-boronic acid (168 mg,1.2 mmol), K 2 CO 3 (345mg,2.5mmol)、Pd[P(C 6 H 5 ) 3 ] 4 (57 mg,0.05 mmol), TBAB (96.5 mg,0.3 mmol) and THF (15 mL) were placed in a three-necked flask and heated under reflux in the dark at 85℃for 13h under nitrogen atmosphere. When this is to be done, water is added to quench the reaction. After the reaction solution was cooled to room temperature, it was extracted 3 times with DCM and brine, and was extracted with NaSO 4 And (5) drying. The crude product was then purified by column chromatography using PE/DCM (2:1) as eluent to give compound 4 as a yellow solid in 71% yield. 1 H NMR(400MHz,DMSO-d 6 )δ9.67(s,1H),8.41–8.32(m,1H),8.21–8.12(m,1H),7.73(d,J＝3.7Hz,1H),7.69–7.55(m,3H),7.38(dd,J＝8.1,1.3Hz,1H),7.31–7.23(m,2H),7.20(dd,J＝7.8,1.5Hz,1H),7.05(td,J＝7.5,1.3Hz,1H),4.20(s,1H),3.72(s,1H),1.51(dq,J＝14.6,7.2Hz,2H),1.35–0.92(m,6H),0.68(t,J＝7.0Hz,3H).
Preparation of Compound PP-OX: compound 4, cyanoacetic acid, ammonium acetate and acetic acid were placed in a three-necked flask,and the purified PP-OX was purified by column chromatography under reflux at 110℃for 12 hours under nitrogen atmosphere in a yield of 70%. 1 H NMR(400MHz,DMSO-d 6 )δ8.56(d,J＝8.4Hz,1H),8.18(d,J＝8.4Hz,1H),8.12(s,1H),7.80(s,1H),7.64(d,J＝3.8Hz,2H),7.61(dd,J＝6.2,1.5Hz,1H),7.61–7.54(m,1H),7.42(d,J＝3.9Hz,2H),7.38(s,1H),7.27(td,J＝7.6,1.5Hz,1H),7.22(dd,J＝7.8,1.5Hz,1H),7.05(t,J＝7.5Hz,1H),4.24(s,1H),3.74(s,1H),1.52(t,J＝7.4Hz,2H),1.34–0.96(m,6H),0.69(t,J＝7.0Hz,3H).
Example 2:
the synthetic route is as follows:
preparation of Compound 6: compound 4 (427 mg,1 mmol) and chloroform (CHCl) 3 10 mL) was added to a three-necked flask, the reaction was stirred in an ice-water bath under nitrogen atmosphere for 6 hours, and N-bromosuccinimide (NBS, 534mg,3 mmol) was added to the reaction flask three times in the first two hours. When the reaction was complete, water was added to stop the reaction. The reaction was then extracted 3 times with DCM and brine and dried over anhydrous Na 2 SO 4 And (5) drying. The crude product was then purified by column chromatography using PE/DCM (1:1) as eluent to give compound 6 in 70% yield. 1 H NMR(400MHz,DMSO-d 6 )δ9.69(s,1H),8.10(dd,J＝8.1,1.6Hz,1H),7.97–7.92(m,1H),7.60(td,J＝8.0,1.3Hz,1H),7.53(td,J＝7.5,1.3Hz,1H),7.53(s,1H),7.48–7.41(m,2H),7.38(d,J＝1.9Hz,1H),7.09–7.02(m,2H),4.20(s,1H),3.72(s,1H),1.51(dq,J＝14.6,7.2Hz,2H),1.35–0.92(m,6H),0.68(t,J＝7.0Hz,3H).
Preparation of Compound 8: compound 6 (505 mg,1 mmol), 4- (9H-carbazol-9-yl) phenylboronic acid (344 mg,1.2 mmol), K 2 CO 3 (345mg,2.5mmol)、Pd[P(C 6 H 5 ) 3 ] 4 (57 mg,0.05 mmol), TBAB (96.6 mg,0.3 mmol) and THF (15 mL) were placed in a three-necked flask and heated under reflux in the dark at 85℃for 13h under nitrogen atmosphere. When this is to be done, water is added to quench the reaction. After the reaction solution was cooled to room temperature, it was extracted 3 times with DCM and brine, and was extracted with NaSO 4 And (5) drying. The crude product was then purified by column chromatography using PE/DCM (2:1) as eluent to give compound 8 as a yellow solid in 71% yield. 1 H NMR(400MHz,DMSO-d 6 )δ9.69(s,1H),8.17–8.11(m,2H),8.10(dd,J＝8.1,1.6Hz,1H),7.97–7.92(m,1H),7.69–7.50(m,10H),7.46(d,J＝5.3Hz,1H),7.39–7.24(m,5H),7.16(d,J＝7.3Hz,1H),7.07(d,J＝5.3Hz,1H),4.21(s,1H),3.76(s,1H),1.58(q,J＝6.2Hz,2H),1.40–1.25(m,6H),0.94–0.84(m,3H).
Preparation of Compound CZ-PP-OX: compound 8, cyanoacetic acid, ammonium acetate and acetic acid were placed in a three-necked flask and heated under reflux at 90 ℃ for 24 hours under nitrogen atmosphere, and purified by column chromatography to give compound CZ-PP-OX in 70% yield. 1 H NMR(400MHz,DMSO-d 6 )δ8.17–8.11(m,2H),8.10(dd,J＝8.2,1.4Hz,1H),8.05(s,1H),7.97–7.92(m,1H),7.69–7.62(m,4H),7.62–7.55(m,4H),7.57–7.50(m,2H),7.41(d,J＝5.5Hz,1H),7.39–7.24(m,5H),7.16(d,J＝7.3Hz,1H),7.08(d,J＝5.3Hz,1H),4.38(s,1H),3.82(s,1H),1.88(q,J＝6.2Hz,2H),1.43–1.05(m,6H),0.84–0.70(m,3H).
Example 3:
the synthetic route is as follows:
preparation of compound 7: compound 6 (505 mg,1 mmol), 4- (diphenylamino) phenylboronic acid (346 mg,1.2 mmol), K 2 CO 3 (345mg,2.5mmol)、Pd[P(C 6 H 5 ) 3 ] 4 (57 mg,0.05 mmol), TBAB (96.6 mg,0.3 mmol) and THF (15 mL) was placed in a three-necked flask and heated at 85℃under reflux in a dark, nitrogen atmosphere for 13h. When this is to be done, water is added to quench the reaction. After the reaction solution was cooled to room temperature, it was extracted 3 times with DCM and brine, and was extracted with NaSO 4 And (5) drying. The crude product was then purified by column chromatography using PE/DCM (2:1) as eluent to give compound 7 as a yellow solid in 71% yield. 1 H NMR(400MHz,DMSO-d 6 )δ9.69(s,1H),8.09(dd,J＝8.4,1.4Hz,1H),8.00–7.95(m,1H),7.77(dd,J＝7.1,1.8Hz,1H),7.64–7.57(m,1H),7.57–7.50(m,2H),7.50(s,1H),7.45(d,J＝5.2Hz,1H),7.40(s,1H),7.34(d,J＝1.9Hz,1H),7.32–7.25(m,4H),7.23–7.15(m,3H),7.14–7.08(m,4H),7.08–6.98(m,3H),4.31(s,1H),3.80(s,1H),1.65-1.55(q,J＝6.2Hz,2H),1.34–1.05(m,6H),0.84–0.70(m,3H).
Preparation of compound TAP-PP-OX: compound 7, cyanoacetic acid, ammonium acetate and acetic acid were placed in a three-necked flask and heated under reflux at 90 ℃ for 24 hours under nitrogen atmosphere, and purified by column chromatography to give compound TAP-PP-OX in 70% yield. 1 H NMR(400MHz,DMSO-d 6 )δ8.09(dd,J＝8.4,1.4Hz,1H),8.05(s,1H),8.00–7.95(m,1H),7.78(dd,J＝7.1,1.8Hz,1H),7.64–7.57(m,1H),7.57–7.50(m,2H),7.50(s,1H),7.42–7.34(m,4H),7.32–7.25(m,4H),7.23–7.15(m,3H),7.14–7.08(m,2H),7.04(tt,J＝7.7,1.4Hz,2H),4.36(s,1H),3.78(s,1H),1.63-1.54(q,J＝7.5Hz,2H),1.38–1.07(m,6H),0.75–0.71(m,3H).
Example 4
Absorption spectral properties of 3 dyes PP-OX, CZ-PP-OX, TAP-PP-OX:
the absorption spectra of PP-OX, CZ-PP-OX, TAP-PP-OX dyes are shown in FIGS. 1-3: the three dyes show strong absorption in the ultraviolet and visible light regions 220-650nm, and the redest absorption peaks are respectively positioned at 480nm, 487nm and 486nm.
Example 5
Device properties of 3 dyes PP-OX, CZ-PP-OX, TAP-PP-OX:
FIGS. 4, 5, and 6 are J-V spectra of devices fabricated with dyes PP-OX, CZ-PP-OX, TAP-PP-OX under standard AM 1.5G simulated sunlight.
The preparation method of the n-type organic dye sensitized solar cell based on the benzothiazine comprises the following steps: ultrasonically cleaning an FTO glass sheet in acetone and ethanol for 15 minutes, and drying under the protection of nitrogen; then preparing TiO by an electrostatic spraying process 2 The nanocrystalline film is about 16 microns thick. After the nanocrystalline film is subjected to heat sintering treatment, immersing the nanocrystalline film into dichloromethane solution containing dye (generally, the immersing time is not less than 24 hours); tiO having adsorbed dye 2 The nanocrystalline thin film serves as a photoanode. And cleaning and drying the other FTO glass sheet in the mode, punching a small hole in the middle of the non-FTO surface, sticking an adhesive tape on the non-FTO surface, suspending and coating chloroplatinic acid on a table type refiner for two times, and then carrying out heat sintering treatment to manufacture the platinum counter electrode. Then assembling the photo-anode and the platinum counter electrode together to form an electrode assembly of the solar cell, packaging the two electrodes by using AB glue, and finally injecting electrolyte solution on the platinum counter electrode with the small holes, wherein the electrolyte solution enters the electrode assembly through the small holes on the platinum counter electrode by virtue of capillary action; and finally, sealing the small holes by using a heat sealing film to obtain the dye-sensitized solar cell.
In standard AM 1.5G simulated sunlight, the light intensity is 100mW/cm 2 The test temperature was 25℃under simulated sunlight, and the short-circuit current density J of the PP-OX organic dye-sensitized solar cell of the present example was measured sc ＝14.88mA/cm 2 Open circuit voltage V oc =0.84V, the fill factor is ff=0.51, the photovoltaic cell efficiency pce=6.41%. Short-circuit current density J of CZ-PP-OX-based organic dye sensitized solar cell sc ＝18.05mA/cm 2 Open circuit voltage V oc =0.76V, the fill factor is ff=0.56, the photovoltaic cell efficiency pce=7.68%. Short-circuit current density J of organic dye sensitized solar cell based on TAP-PP-OX sc ＝19.25mA/cm 2 Open circuit voltage V oc =0.84V, the fill factor is ff=0.55, the photovoltaic cell efficiency pce=8.85%.
The present invention has been disclosed in the preferred embodiments, but the invention is not limited thereto, and the technical solutions obtained by adopting equivalent substitution or equivalent transformation fall within the protection scope of the present invention.
Claims (7)
1. An n-type organic dye based on 1, 2-benzothiazine is characterized in that the structural general formula is shown in formula I or formula II:
wherein R is a straight or branched alkyl chain having 1 to 12 carbon atoms, orWherein R is 2 Is a straight or branched alkyl chain having 1 to 12 carbon atoms;
selected from any one of the following:
wherein R is 1 Is hydrogen, a straight or branched alkyl chain having 1 to 12 carbon atoms, or a straight or branched alkyl chain having 1 to 12 carbon atoms containing an oxygen atom or a sulfur atom.
2. The method for preparing the n-type organic dye based on the 1, 2-benzothiazine, as recited in claim 1, wherein the synthetic route of the formula I is as follows:
the synthesis method of the formula I comprises the following steps:
adding 2-aminobenzene mercaptan and 4-tetrahydrocyclic ketone into dimethyl sulfoxide, and stirring in air at 110 ℃ for 24 hours to obtain a compound 1;
mixing the compound 1, R-Br, KOH, TBAB and dimethyl sulfoxide, and reacting for 10 hours at room temperature under the nitrogen atmosphere to obtain a compound 2;
mixing the compound 2 with chloroform, stirring in an ice-water bath under nitrogen atmosphere for reaction for 6 hours, and adding N-bromosuccinimide into a reaction bottle three times in the first two hours to obtain a compound 3;
3, 5-Formylfuran-2-boronic acid, K 2 CO 3 、Pd[P(C 6 H 5 ) 3 ] 4 Putting TBAB and THF into a three-neck flask, and heating and refluxing in a dark and nitrogen atmosphere at 85 ℃ for 13h to obtain a compound 4;
compound 4, cyanoacetic acid, ammonium acetate and acetic acid were mixed and heated to reflux at 110 ℃ for 12 hours under nitrogen atmosphere, and purified to give the product of formula I.
3. The process according to claim 2, wherein the compound 3, 5-formylfuran-2-boronic acid, K 2 CO 3 、Pd[P(C 6 H 5 ) 3 ] 4 The mole ratio of TBAB is 1:1.2:2.5:0.05:0.3.
4. the preparation method according to claim 2, wherein the molar ratio of the compound 4 to the cyanoacetic acid to the ammonium acetate is 1:2:1.
5. the method of claim 2, wherein the synthetic route of formula II is:
the synthesis method of the formula II is as follows:
mixing the compound 4 with chloroform, stirring in an ice-water bath under nitrogen atmosphere for reaction for 6 hours, and adding N-bromosuccinimide into a reaction bottle three times in the first two hours to obtain a compound 5;
will be combinedCompound 5, compoundK 2 CO 3 、Pd[P(C 6 H 5 ) 3 ] 4 Mixing TBAB and THF, heating and refluxing in dark and nitrogen atmosphere at 85deg.C for 13h, and purifying to obtain compound 6;
compound 6, cyanoacetic acid, ammonium acetate and acetic acid were mixed and heated to reflux at 90 ℃ under nitrogen for 24 hours and purified to give the product of formula II.
6. The preparation method according to claim 5, wherein the compound 5 is a compoundK 2 CO 3 、Pd[P(C 6 H 5 ) 3 ] 4 The molar ratio of TBAB is 1:1.2:2.5:0.05:0.3.
7. Use of an n-type organic dye of a 1, 2-benzothiazine as defined in claim 1 as sensitizer in dye sensitized solar cells.
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