CN105238092B - A kind of organic dye sensitized dose of BODIPY classes of 2,6 substitutions and preparation method thereof - Google Patents

Abstract

The invention relates to a 2,6-position substituted BODIPY organic dye sensitizer and a preparation method thereof. The organic dye sensitizer is a kind of organic photovoltaic material with D-π-A structure, the BODIPY core substituted by meso position is the π bridge skeleton, and the 2 and 6 positions of the BODIPY core are respectively substituted by donating-withdrawing electron units. The invention also discloses the preparation method of the above-mentioned dye sensitizer, which uses 2,4-dimethylpyrrole as the initial reaction raw material, undergoes a series of simple synthesis reactions, and finally obtains the dye through classic Suzuki coupling and Knoevenagel condensation reactions Molecule, general structure see I. The synthesis method of the dye sensitizer is simple, easy to control, high in yield and universally applicable. Applying it to the preparation of dye-sensitized solar cells can obtain dye-sensitized solar cell materials with high filling factor and ideal photoelectric conversion efficiency.

Description

A kind of 2,6-position substituted BODIPY type organic dye sensitizer and preparation method thereof

Technical field:

The invention relates to the field of dye-sensitized solar cell materials, in particular to a 2,6-substituted BODIPY organic dye sensitizer.

Background technique:

Switzerland since 1991 Since the team first prepared dye-sensitized solar cells (DSSCs) by using bipyridyl ruthenium as a dye and nanoporous TiO ₂ film, dye-sensitized nanocrystalline TiO ₂ solar cells have become nearly two It has been a research hotspot in the field of solar photoelectric conversion in the past ten years. Photosensitive dyes mainly include metal complexes and pure organic dyes. At present, metal complexes mainly based on polypyridine ruthenium complexes have been extensively and deeply studied because of their good stability and high energy conversion efficiency. However, ruthenium dyes have disadvantages such as limited resources and high price, which limit its application. Compared with ruthenium dyes, pure organic dyes have become a hot research direction of DSSCs due to their low raw material cost, flexible structure design, easy synthesis, and easy purification.

Fluorine-boron complexed dipyrrole (BODIPY) derivatives are a kind of good photosensitizing dyes with good stability, good modifiability, high molar extinction coefficient (1×10 ⁵ M ^-1 ·cm ^-1 ) and comparative High oxidation potential, its application to dye-sensitized solar cells has been reported in the literature. The spectral absorption of BODIPY is relatively narrow, but its good modifiability can overcome this shortcoming, realize the red shift and broadening of spectral absorption, and help improve the Jsc of the battery, showing a good application prospect. Carbazole derivatives are another class of compounds with good optoelectronic properties. It has strong spectral absorption and emission properties, high hole transport ability and wide band gap, and has a wide range of applications in the field of optoelectronic materials. In view of the outstanding optoelectronic properties of the two types of materials, the combination of BODIPY and carbazole compounds for dye-sensitized solar cells has aroused our research interest.

The present invention designs and synthesizes a class of novel D-π-A dye sensitizers whose 2,6-positions of BODIPY are respectively replaced by donor and acceptor units, and optimizes the synthesis method of this class of dyes, improving the BODIPY of this class. The dye synthesis yield effectively improves the photovoltaic performance of this type of BODIPY dye.

Invention content:

The purpose of this invention is to provide a kind of 2,6-position substituted BODIPY class organic dye sensitizer, it has novel molecular structure, has lower energy gap value, wide spectral absorption range

Another object of the present invention is to provide a preparation method of this kind of dye sensitizer, the reaction condition of the method is easy to control, the product purification is simple, the yield is high, and it has universal applicability.

To achieve the above object, the present invention adopts the following technical solutions:

A 2,6-position substituted BODIPY organic dye sensitizer has a chemical structure of general formula I:

In formula I, D is a donor unit, which is one of the following structural units:

Wherein, R is H or alkyl or alkoxy, and _n is 5;

A is an acceptor unit, which is one of the following structural units:

A preparation method of a 2,6-position substituted BODIPY organic dye sensitizer, comprising the following steps:

(1) Condensation reaction of 2,4-dimethylpyrrole and acid chloride, and complexation reaction with boron trifluoride ether to obtain intermediate 1, whose structure is:

(2) Intermediate 1 undergoes Weissmeier formylation reaction to obtain intermediate 2, whose structure is:

(3) Intermediate 2 and iodine monochloride undergo an electrophilic substitution reaction to obtain intermediate 3, whose structure is:

(4) react carbazole and n-octane bromide under the effect of alkali to obtain intermediate 4, whose structure is:

(5) Intermediate 4 reacts with N-bromosuccinimide at room temperature to obtain Intermediate 5, whose structure is:

(6) Intermediate 5 and double-linked pinacol boroester are catalyzed by a catalyst, and through a Suzuki coupling reaction, intermediate 6 is obtained, and its structure is:

(7) 2-Bromocarbazole reacts with bromo-n-octane under the action of alkali to obtain intermediate 7, whose structure is:

(8) Intermediate 7 and double-linked pinacol borate are catalyzed by a catalyst, and through Suzuki coupling reaction, intermediate 8 is obtained, and its structure is:

(9) With p-iodoanisole and carbazole under the catalysis of catalyst, through Ullman condensation reaction, make intermediate 10, its structure is:

(10) intermediate 9 is reacted with N-bromosuccinimide to obtain intermediate 9, its structure is:

(11) With p-iodoanisole and 2-bromocarbazole under the catalysis of catalyst, through Ullman condensation reaction, intermediate 11 is obtained, and its structure is:

(12) Intermediate 10 and double pinacol borate are catalyzed by a catalyst, and through Suzuki coupling reaction, intermediate 12 is obtained, and its structure is:

(13) Intermediate 11 and double pinacol borate are catalyzed by a catalyst through Suzuki coupling reaction to obtain intermediate 13, which has the following structure:

(14) 4-(9H-carbazol-9-yl)phenylboronic acid and intermediate 3 are catalyzed by a catalyst, and undergo a Suzuki coupling reaction to obtain intermediate 14, whose structure is:

(15) Intermediates 6, 8, 12, 13 and intermediates 3 are respectively catalyzed by a catalyst, and undergo Suzuki coupling reaction to obtain intermediates 15, 16, 17, 18, the structures of which are:

(16) Intermediates 14-18 reacted with cyanoacetic acid respectively through Knoevenagel condensation reaction to obtain the target dye molecule Dye 1-5, whose structure is:

As a preference of the above technical solution, in steps (1)-(15), the reaction medium of the reaction is N,N-dimethylformamide, tetrahydrofuran, dichloromethane, ethyl acetate, toluene, chloroform, ethanol One or a mixture of several.

As a preference of the above technical solution, in steps (6), (8), (11), (12), (13), (14), and (15), the catalyst is Pd(PPh ₃ ) ₄ , Pd( dppf) one of Cl ₂ and CuI.

As the preference of the above technical solution, in the steps (2), (6), (8), (9), (11), (12), (13), (14), (15), (16) The reaction temperature is 75-120°C, and the reaction time of steps (1)-(15) is 5-48h.

Compared with the prior art, the present invention has the following beneficial effects:

(1) In the synthesis method, the raw materials of this method are common and easy to obtain, the production cost is low, the reaction conditions are easier to control, the product purification is simple, universal, and the yield of the product is greatly improved;

(2) Through the analysis of the spectral data of the dye, we can see that this kind of dye has a good photon capture ability, compared with the dyes reported in the literature, it has a wide ultraviolet absorption range, and it is used in dye-sensitized solar cells. Photovoltage and fill factor.

Description of drawings:

Figure 1 is the H NMR spectrum of Dye 1.

Figure 2 is the carbon NMR spectrum of Dye 1.

Figure 3 is the H NMR spectrum of Dye 2.

Figure 4 is the carbon NMR spectrum of Dye 2.

Figure 5 is the H NMR spectrum of Dye 3.

Figure 6 is the C NMR spectrum of Dye 3.

Figure 7 is the H NMR spectrum of Dye 4.

Figure 8 is the carbon NMR spectrum of Dye 4.

Figure 9 is the H NMR spectrum of Dye 5.

Figure 10 is the C NMR spectrum of Dye 5.

Figure 11 is the ultraviolet absorption spectrum of Dye 1-5 in dichloromethane solution.

Figure 12 is the cyclic voltammetry curve of Dye 1-5 in dichloromethane solution.

Fig. 13 is the I-V curve of organic dye-sensitized solar cells prepared by Dye 1-5.

detailed description:

In order to better understand the present invention, the present invention will be further described through the following examples, which are only used to explain the present invention and will not constitute any limitation to the present invention.

(1) Synthesis of Intermediate 1

In a 250mL three-necked flask, add 2,4-dimethylpyrrole (3.3g, 35mmol) and 40mL of freshly distilled dichloromethane, and install a reflux condenser. Vacuum, argon protection. N-hexanoyl chloride (2.5 mL, 18 mmol) was added dropwise with a syringe, and the mixture was heated to reflux for 3 h. Cool to room temperature, dilute with n-hexane, stir overnight, and remove the solvent under reduced pressure. Add 80 mL of freshly distilled toluene, stir evenly, add triethylamine (15 mL, 113 mmol), and after 20 min, add boron trifluoride ether (20 mL, 163 mmol) dropwise, continue to react at room temperature for 1 h, and evaporate the solvent from the reaction mixture under reduced pressure , diluted with dichloromethane solution, washed with saturated brine (3×50 mL), and dried over anhydrous magnesium sulfate. The crude product was subjected to silica gel column chromatography to obtain a reddish-brown solid. ¹ H NMR (400MHz, CDCl ₃ )δ6.05(s,1H),2.96–2.90(m,1H),2.51(s,3H),2.41(s,3H),1.62(d,J＝6.6Hz, 1H), 1.46(d, J＝6.8Hz, 1H), 1.42–1.35(m, 1H), 0.93(t, J＝6.7Hz, 2H). ¹³ C NMR (101MHz, CDCl ₃ )δ: 153.70, 146.74 ,140.32,131.45,121.55,32.59,31.65,28.46,22.53,16.36,14.47,14.45,14.42,14.06.

(2) Synthesis of Intermediate 2

In a 100mL three-neck flask, add 10mL of N,N-dimethylformamide, vacuumize, protect with argon, place the reaction bottle in an ice-water bath, slowly add POCl ₃ (6.5mL, 7.00mmol) dropwise, dropwise for 5min After completion, the reaction bottle was placed at room temperature for 30 min. Dissolve 0.524g of intermediate 1 in 30mL of 1,2-dichloroethane. After the dropwise addition, the temperature is raised to 50°C for 2h. After cooling to room temperature, the reaction solution was slowly poured into saturated potassium carbonate solution. Extract with dichloromethane solution, wash the organic phase three times with water, and dry over anhydrous magnesium sulfate. The crude product was subjected to silica gel column chromatography to obtain a yellow solid. ¹ H NMR (400MHz, CDCl ₃ ) δ: 10.05(s,1H),6.18(s,1H),3.03–2.93(m,2H),2.72(s,3H),2.69(s,3H),2.52( s,3H),2.43(s,3H),1.48(s,2H),1.44(d,J＝6.7Hz,2H),1.39–1.34(m,2H),0.89(t,J＝6.9Hz,3H ).

(3) Synthesis of intermediate 3

Add intermediate 2 (226mg, 0.6mmol) and 20mL methanol/DMF (V/V=1:1) into a 50mL three-neck flask. Vacuumize, under the protection of argon, slowly dropwise add iodine monochloride methanol solution. Stirring was continued for half an hour at room temperature, and TLC detected that all the raw materials had reacted. Add 20 mL of water to the reaction flask, extract 3×30 mL with dichloromethane, combine the organic phases, and wash the organic phases with saturated sodium thiosulfate solution 3 times. The organic phase was dried over anhydrous magnesium sulfate, and the crude product was subjected to silica gel column chromatography to obtain a red solid with a yield of 65%. ¹ HNMR (400MHz, CDCl ₃ ) δ: 10.13(s, 1H), 3.08(d, J=7.1Hz, 2H), 2.79(s, 3H), 2.77(s, 3H), 2.67(s, 3H), 2.54(s,3H),1.71–1.61(m,2H),1.51(d,J=7.6Hz,2H),1.41(dd,J=14.0,7.1Hz,2H),0.95(t,J=7.0Hz ,3H). ¹³ C NMR (101MHz, CDCl ₃ )δ: 186.06, 159.10, 156.79, 149.26, 144.90, 141.91, 133.66, 130.14, 126.54, 32.45, 31.48, 29.15, 22.50, 19.40, 16.028, 13 .

(4) Synthesis of intermediate 4 (9-octylcarbazole)

In a 250mL three-necked flask, add 5g (15.4mmol) carbazole, 100mL DMSO, 0.25g (1.1mmol) TEBA and 25mL sodium hydroxide solution (50wt%) in sequence, and drop (3.3g, 16.9mmol) of 1-bromo-n-octane, reacted at room temperature for 8h, stopped the reaction, added hydrochloric acid to the reaction solution to adjust the pH=7, extracted with ethyl acetate (3×50mL), combined the organic layers and washed 3 times with saturated brine, no Magnesium sulfate water was dried overnight, and the solvent was distilled off after filtration. The residue was separated by column chromatography using petroleum ether as eluent to obtain light yellow oily liquid with a yield of 80%. ¹ H NMR (400MHz, CDCl ₃ ), δ: 8.15(d, J=1.5Hz, J=8Hz, 2H), 7.50(d, 2H), 7.45(d, J=8Hz, 2H), 7.26(d, 2H), 4.35(t, J=8Hz, 2H), 1.95-1.85(m, 2H), 1.50-1.20(m, 10H), 0.92(t, J=6.5Hz, 3H).

(5) Synthesis of intermediate 5 (9-octyl-3-bromocarbazole)

In a 250mL single-necked bottle, sequentially add 4g (24.0mmol) of 9-octylcarbazole, 8.5g (48.0mmol) of NBS, and 80mL of anhydrous tetrahydrofuran. Under the protection of argon, heat to 80°C with magnetic stirring for 24 hours, then stop the reaction , the reaction mixture was cooled to room temperature and poured into 300 mL of distilled water, extracted 3 times with ethyl acetate, and the organic layer was washed 3 times with saturated brine, the combined organic phases were dried overnight over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was separated by silica gel column chromatography to obtain a light yellow oil with a yield of 70%. ¹ H NMR (400MHz, CDCl ₃ ), δ: 8.21(s, 1H), 8.05(d, 1H), 7.53(d, 1H), 7.48(d, J=7.2Hz, 1H), 7.40(d, 1H ), 7.27(t, J=12.0Hz, 2H), 4.26(t, 2H), 1.84(m, 2H), 1.25(m, 10H), 0.85(t, 3H).

(6) Synthesis of intermediate 6 (3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)-9-octylcarbazole)

Add 2g (5.6mmol) of 3-bromo-9-octylcarbazole, 1.7g (6.7mmol) of bis-pinacol borate, 2.7g (28mmol) of potassium acetate, and Pd(dppf)Cl in a 100mL three-necked flask. ₂ 150mg (0.21mmol) and 80mL DMF, vacuumize, under the protection of argon, control the temperature of the oil bath at 95°C, and magnetically stir the reaction for 24h. The reaction was stopped, and the reaction mixture was cooled to room temperature and poured into 200 mL of water, extracted three times with dichloromethane (50 mL×3), washed several times with saturated brine, combined the organic phases, and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure, and the residue was separated by silica gel (200-300 mesh) column chromatography using petroleum ether: ethyl acetate = 20:1 as the eluent to obtain a yellow oily liquid with a yield of 70%. ¹ H NMR (400MHz, CDCl ₃ ), δ: 8.60(s, 1H), 8.13(d, J=7.6Hz, 1H), 7.92(d, J=8.1Hz, 1H), 7.45(d, J=7.3 Hz,1H),7.40(t,J=9.5Hz,2H),7.23(d,J=7.0Hz,1H),4.30(t,J=6.9Hz,2H),1.90-1.86(m,2H), 1.44 (s, 12H), 1.36-1.28 (m, 10H), 0.85 (t, J=13.6Hz, 3H).

(7) Synthesis of intermediate 7 (9-octyl-2-bromocarbazole)

In a 250mL three-necked flask, add 3.8g (15.4mmol) 2-bromocarbazole, 100mL DMSO, 0.25g (1.1mmol) TEBA and 25mL sodium hydroxide solution (50wt%) in sequence, and add dropwise within 0.5h under magnetic stirring 3.3 g (16.9 mmol) of 1-bromo-n-octane was reacted at room temperature for 8 h, and the reaction was stopped. Hydrochloric acid was added to the reaction solution to adjust the pH to 7, extracted with ethyl acetate (3×50 mL), and the organic layers were combined and washed with saturated brine for 3 Once, dried over anhydrous magnesium sulfate overnight, filtered and distilled off the solvent, and the residue was separated by column chromatography using petroleum ether as the eluent to obtain a yellow oily liquid with a yield of 65%. ¹ H NMR (400MHz, CDCl ₃ , TMS), δ: 8.06(d, J=7.2Hz, 1H), 7.94(d, J=7.9Hz, 1H), 7.54(s, 1H), 7.48(t, J =6.7Hz,1H),7.40(d,J=7.5Hz,1H),7.33(d,J=8.0Hz,1H),7.28–7.20(s,1H),4.24(t,J=6.2Hz,2H ),1.97–1.77(m,2H),1.35–1.25(m,10H),1.01–0.75(t,3H).

(8) Synthesis of intermediate 8 (2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)-9-octylcarbazole)

In a 100mL three-necked flask, 2-bromo-9-octylcarbazole 2g (5.6mmol), double pinacol boronate 1.7g (6.7mmol), potassium acetate 2.7g (28mmol), Pd(dppf)Cl ₂ 150mg (0.21mmol) and 80mL DMF, vacuumize, under the protection of argon, control the temperature of the oil bath at 95°C, and magnetically stir the reaction for 24h. A light yellow oily liquid was obtained in a similar manner to the synthesis of Intermediate 6. ¹ H NMR (400MHz, CDCl ₃ , TMS), δ: 8.19-8.02(m, 2H), 7.88(s, 1H), 7.69(d, J=4.6Hz, 1H), 7.55-7.36(m, 2H) .,7.30–7.13(m,1H),4.47–4.24(m,2H),2.00–1.76(m,2H),1.50–1.30(m,12H),1.30–1.14(m,10H),0.96–0.76 (t,3H).

(9) Synthesis of intermediate 9 (9-(4-methoxyphenyl)carbazole)

In a 100mL three-necked flask, add carbazole (1.67g, 10mmol), p-iodoanisole (2.57g, 11mmol), cuprous iodide (0.19g, 1mmol), potassium carbonate (2.76g, 20mmol), L - Proline (0.23g, 2mmol) DMSO 30mL, heated to 90°C for 40h. Cool to room temperature, dilute with water, and extract with ethyl acetate. The organic layer was washed three times with saturated brine, and dried over anhydrous magnesium sulfate. The crude product was subjected to silica gel column chromatography to obtain white crystals with a yield of 68%. ¹ H NMR (400MHz, CDCl ₃ ) δ: 8.14(d, J=7.6Hz, 2H), 7.45-7.37(m, 4H), 7.33-7.24(m, 4H), 7.10(d, J=8.8Hz, 2H), 3.90(s, 3H), ppm; ¹³ C NMR (100MHz, CDCl ₃ ) δ: 158.83, 141.35, 130.28, 128.55, 125.81, 123.08, 120.22, 119.61, 115.04, 109.67, 55.58.

(10) Synthesis of intermediate 10 (9-(4-methoxyphenyl)-3-bromocarbazole)

In a 100mL single-necked bottle, the intermediate 9 (2.71g, 10mmol) was dissolved in 30mL N,N-dimethylformamide, under ice-water bath conditions, NBS (1.96g, 11mmol) was added in batches, under the protection of argon , react overnight at room temperature, stop the reaction, pour the reaction mixture into 200mL distilled water, extract 3 times with dichloromethane, wash the organic layer 3 times with saturated brine, combine the organic phases, and dry overnight over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography using petroleum ether as the eluent to separate a white solid with a yield of 90%. ¹ H NMR (400MHz, CDCl ₃ ) δ8.22(d, J=21.4Hz, 1H), 8.08(d, J=6.8Hz, 1H), 7.48–7.39(m, 4H), 7.33–7.27(m, 2H), 7.19(d, J=7.2Hz, 1H), 7.11(d, J=7.0Hz, 2H), 3.92(s, 3H).

(11) Synthesis of intermediate 11 (9-(4-methoxyphenyl)-2-bromocarbazole)

Add 2-bromocarbazole (2.45g, 10mmol), p-iodoanisole (2.58g, 11mmol), cuprous iodide (190mg, 1mmol), L-proline (230mg, 2mmol) into a 100mL three-necked flask successively ), potassium carbonate (2.76g, 20mmol), DMSO30mL. White crystals were obtained by a method similar to the synthesis of intermediate 9 with a yield of 65%. ¹ H NMR (400MHz, CDCl ₃ ) δ8.13(d, J=7.1Hz, 1H), 8.01(d, J=7.9Hz, 1H), 7.51–7.38(m, 5H), 7.32(d, J= 7.9Hz, 2H), 7.15(d, J=7.1Hz, 2H), 3.95(s, 3H).

(12) Intermediate 12(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)-9-(4-methoxyphenyl)carbazole )Synthesis

Add intermediate 10 (0.65g, 1.85mmol), double pinacol boroester (0.80g, 2.80mmol), potassium acetate (0.73g, 7.40mmol), Pd(dppf)Cl ₂ 150mg in a 100mL three-necked flask (0.21mmol) and 20mL DMF, vacuumize, under the protection of argon, control the temperature of the oil bath at 95°C, and magnetically stir the reaction for 24h. White crystals were obtained by a method similar to the synthesis of intermediate 6 with a yield of 72%. ¹ H NMR (400MHz, CDCl ₃ ) δ8.25 (d, J=21.4Hz, 1H), 8.18 (d, J=6.8Hz, 1H), 7.44 (dd, J=21.1, 7.8Hz, 4H), 7.29 (dd,J=14.5,8.6Hz,2H),7.19(d,J=7.2Hz,1H),7.11(d,J=7.1Hz,2H),3.92(s,3H),1.36(s,12H) .

(13) Intermediate 13 (2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)-9-(4-methoxyphenyl)carbazole )Synthesis

Add intermediate 11 (0.54g, 1.54mmol), double pinacol boroester (0.57g, 2.31mmol), potassium acetate (0.59g, 6.20mmol), Pd(dppf)Cl ₂ 100mg in a 100mL three-necked flask (0.18mmol) and 20mL DMF, vacuumize, under the protection of argon, control the temperature of the oil bath at 95°C, and react with magnetic stirring for 24h. White crystals were obtained by a method similar to the synthesis of intermediate 6 with a yield of 67%. ¹ H NMR (400MHz, CDCl ₃ ) δ8.19–8.13(m,2H),7.80–7.72(m,2H),7.46(d,J=8.7Hz,2H),7.41(d,J=7.4Hz, 1H), 7.30(d, J=8.6Hz, 2H), 7.13(d, J=8.6Hz, 2H), 3.94(s, 3H), 1.36(s, 12H).

(14) Synthesis of Intermediate 14

Add 4-(9H-carbazol-9-yl)phenylboronic acid (0.27g, 0.94mmol), intermediate 3 (0.43g, 0.78mmol), tetrakistriphenylphosphine palladium 20mg, 20mL into a 100mL three-necked flask successively Tetrahydrofuran/toluene (V/V=1:1), potassium carbonate (1.38g, 10mmol). Vacuum, argon protection, reflux reaction at 80°C for 24h. Cool to room temperature, dilute with water, extract with dichloromethane, wash the organic phase three times with water, and dry over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, and the residue was subjected to silica gel column chromatography to obtain a red solid with a yield of 72%. ¹ H NMR (400MHz, CDCl ₃ ) δ10.15(s, 1H), 8.17(d, J=7.4Hz, 2H), 7.70(d, J=7.2Hz, 2H), 7.52(d, J=7.3Hz ,2H),7.46(d,J＝6.5Hz,4H),7.35–7.30(m,2H),3.22–3.12(m,2H),2.83(s,3H),2.81(s,3H),2.63( s,3H),2.50(s,3H),1.84–1.66(m,2H),1.54(d,J＝4.6Hz,2H),1.47–1.40(m,2H),0.96(t,J＝6.7Hz ,3H). ¹³ C NMR(101MHz,CDCl ₃ )δ:186.34,158.42,149.58,140.67,137.39,131.73,128.76,127.08,126.08,125.86,123.58,120.48,120.26,119.64,116.62,109.78,109.73,32.53 ,31.66,28.92,22.57,15.09,14.10,14.01,13.10,12.79.

(15) Synthesis of intermediate 15

Intermediate 3 (0.24g, 0.50mmol) and Intermediate 6 (0.24g, 0.60mmol) potassium carbonate (1.1g, 8.0mmol) were dissolved in 15mL of toluene and 15mL of tetrahydrofuran in a 100mL three-necked flask. Vacuum, under the protection of argon, add tetrakis triphenylphosphine palladium. Heat up to 80°C and reflux overnight, cool to room temperature, and spin off the solvent. Washed several times with water, and dried the organic phase with anhydrous magnesium sulfate. The crude product was subjected to silica gel column chromatography to obtain a reddish-brown solid with a yield of 70%. ¹ H NMR (400MHz, CDCl ₃ ) δ: 10.14(s, 1H), 8.10(d, J=7.0Hz, 1H), 7.91(s, 1H), 7.57–7.43(m, 3H), 7.28(d, J＝18.7Hz, 2H), 4.33(d, J＝6.0Hz, 2H), 3.21–3.07(m, 2H), 2.80(d, J＝10.0Hz, 6H), 2.56(s, 3H), 2.43( s, 3H), 1.91(d, J=6.4Hz, 2H), 1.77–1.68(m, 2H), 1.53(d, J=3.9Hz, 2H), 1.45–1.35(m, 6H), 1.26(s ,6H),0.94(t,J=6.0Hz,3H),0.87(s,3H). ¹³ C NMR(101MHz,CDCl ₃ )δ:186.30,160.12,155.21,148.52,140.80,139.91,127.61,126.12, 123.06,122.65,122.48,121.97,120.42,119.14,108.97,108.84,61.91,32.50,31.83,31.61,29.41,29.22,29.06,28.82,27.37,22.65,22.57,144.9

(16) Synthesis of Intermediate 16

Intermediate 3 (0.32g, 0.70mmol) and Intermediate 8 (0.33g, 0.80mmol) potassium carbonate (1.1g, 8.0mmol) were dissolved in 20mL of toluene and 20mL of tetrahydrofuran in a 100mL three-necked flask. Vacuum, under the protection of argon, add tetrakis triphenylphosphine palladium. Heat up to 80°C and reflux overnight, cool to room temperature, and spin off the solvent. Washed several times with water, and dried the organic phase with anhydrous magnesium sulfate. The crude product was subjected to silica gel column chromatography to obtain a reddish-brown solid with a yield of 70%. ¹ H NMR (400MHz, CDCl ₃ ) δ: 10.15(s, 1H), 8.19–8.08(m, 2H), 7.46(dd, J=21.6, 7.5Hz, 2H), 7.26(s, 2H), 7.04( d,J=7.6Hz,1H),4.31(d,J=12.9Hz,2H),3.14(s,2H),2.80(d,J=9.9Hz,6H),2.57(s,3H),2.44( s,3H),1.87(d,J=6.6Hz,2H),1.78–1.63(m,2H),1.52(d,J=7.1Hz,2H),1.43–1.22(m,12H),0.95(t , J＝7.0Hz, 3H), 0.84(d, J＝6.6Hz, 3H). ¹³ C NMR (101MHz, CDCl ₃ ) ¹³ C NMR (101MHz, CDCl ₃ ) δ: 186.23, 150.53, 148.91, 140.90, 140.55 .

(17) Synthesis of intermediate 17

Intermediate 3 (0.35g, 0.50mmol) and intermediate 12 (0.24g, 0.60mmol) potassium carbonate (1.1g, 8.0mmol) were dissolved in 15mL of toluene and 15mL of tetrahydrofuran in a 100mL three-necked flask. Vacuum, under the protection of argon, add tetrakis triphenylphosphine palladium. Heat up to 80°C and reflux overnight, cool to room temperature, and spin off the solvent. Washed several times with water, and dried the organic phase with anhydrous magnesium sulfate. The crude product was subjected to silica gel column chromatography to obtain a reddish-brown solid with a yield of 70%. ¹ H NMR (400MHz, CDCl ₃ ) δ10.14(s, 1H), 8.14(d, J=7.6Hz, 1H), 7.96(s, 1H), 7.49(d, J=8.6Hz, 2H), 7.45 –7.34(m,3H),7.30(t,J=7.3Hz,1H),7.21(d,J=8.3Hz,1H),7.14(d,J=8.5Hz,2H),3.94(s,3H) ,3.24–3.07(m,2H),2.81(s,3H),2.79(s,3H),2.57(s,3H),2.44(s,3H),1.80–1.67(m,2H),1.55–1.49 (m,2H),1.45–1.40(m,2H),0.95(t,J＝7.1Hz,3H). ¹³ C NMR(101MHz,DMSO)δ:186.29,159.08,148.64,141.78,140.87,130.02,128.55 , 127.90,126.39,125.85,123.70,123.40,122.77,121.89,120.34,120.07,110.01,77.39,76.75,551.63,28.8.8.5.07,15.07,5.07,07,07,07,07,07,07,07,07,07.07,07,07,07,07,07,07,07,07,07,07.07.

(18) Synthesis of intermediate 18

Intermediate 3 (0.15g, 0.50mmol) and intermediate 13 (0.24g, 0.60mmol) potassium carbonate (1.1g, 8.0mmol) were dissolved in 15mL of toluene and 15mL of tetrahydrofuran in a 100mL three-necked flask. Vacuum, under the protection of argon, add tetrakis triphenylphosphine palladium. Heat up to 80°C and reflux overnight, cool to room temperature, and spin off the solvent. Washed several times with water, and dried the organic phase with anhydrous magnesium sulfate. The crude product was subjected to silica gel column chromatography to obtain a reddish-brown solid with a yield of 70%. ¹ H NMR (400MHz, CDCl ₃ ) δ: 10.13(s, 1H), 8.20(d, J=7.9Hz, 2H), 7.45(dd, J=12.6, 8.3Hz, 3H), 7.38–7.28(m, 2H), 7.15–7.08(m, 4H), 3.91(s, 3H), 3.11(d, J=5.6Hz, 2H), 2.80(s, 3H), 2.77(s, 3H), 2.52(s, 3H ),2.39(s,3H),1.77–1.61(m,2H),1.53–1.48(m,2H),1.40(dd,J＝14.3,7.1Hz,2H),0.93(t,J＝7.1Hz, 3H). ¹³ C NMR(101MHz,DMSO)δ:186.26,159.06,155.48,148.87,141.86,141.48,130.15,129.97,128.50,126.33,122.76,121.83,120.39,120.08,115.26,111.21,109.90,77.39,77.07 ,76.76,55.64,32.49,31.56,28.81,22.53,15.00,14.06,13.00,12.65.

Example 1

(1) Synthesis of Dye 1:

Intermediate 14 (180mg, 0.3mmol), cyanoacetic acid (50mg, 0.6mmol), acetonitrile (20mL), chloroform (20mL) and piperidine (0.2mL) were sequentially added to a 100mL three-neck flask, and under argon protection, Reflux at 80°C for 24h. After cooling to room temperature, the reaction solution was poured into 50 mL of dichloromethane for dilution, washed 3 times with water (3×50 mL), and the organic phase was dried over anhydrous MgSO4. The solvent was removed by rotary evaporation, and the crude product was subjected to silica gel column chromatography (dichloromethane:methanol=10:1) to obtain 156 mg of dark red solid powder with a yield of 80%. ¹ H NMR (400MHz, CDCl ₃ ) δ10.15(s, 1H), 8.17(d, J=7.4Hz, 2H), 7.70(d, J=7.2Hz, 2H), 7.51(s, 2H), 7.46 (d,J=6.5Hz,4H),7.32(s,2H),3.17(t,2H),2.83(s,3H),2.81(s,3H),2.63(s,3H),2.50(s, 3H), 1.74(s, 2H), 1.54(d, J=4.6Hz, 2H), 1.43(d, J=6.5Hz, 2H), 0.96(t, 3H). ¹³ C NMR (101MHz, CDCl ₃ ) δ:186.34,158.42,149.58,140.67,137.39,131.73,128.76,127.08,126.08,125.86,123.58,120.48,120.26,119.64,116.62,109.78,109.73,32.53,31.66,28.92,22.57,15.09,14.10,14.01, 13.10,12.79.MALDI-TOF-MS,m/z:calcdfor C ₃₉ H ₃₅ BF ₂ N ₄ O ₂ [M] ⁺ :654.300,found:654.318.

Example 2

(2) Synthesis of Dye 2:

150 mg of purple-red solid powder was obtained by a method similar to that of dye 1, and the yield was 78%. ¹ H NMR (600MHz, DMSO) δ: 8.21(d, J=7.7Hz, 2H), 8.12(s, 1H), 7.67-7.69(d, J=7.7Hz, 2H), 7.62(d, J=7.7 Hz,2H),7.47(d,J=9.8Hz,2H),7.36(d,J=7.2Hz,2H),7.19-7.24(t,J=7.3Hz,2H),3.12(s,2H), 2.47(s,3H),2.46(s,3H),2.43(s,3H),2.41(s,3H),1.79(m,2H),1.65(m,2H),1.49(m,2H),0.90 (t, J=7.0Hz, 3H). ¹³ C NMR (151MHz, DMSO) δ: 174.83, 172.89, 140.75, 140.49, 137.63, 133.49, 132.47, 131.41, 131.32, 130.12, 126.81, 126.68, 126.409, 123.2 ,120.93,120.32,110.29,110.23,32.94,31.75,29.49,22.56,15.43,14.49,14.42,13.64,13.22.MALDI-TOF-MS,m/z: calcd for C ₄₂ H ₄₉ BF ₂ N ₄ O ₂ [ M] ⁺ :690.400,found:690.251.

Example 3

Synthesis of Dye 3

145 mg of purple-red solid powder was obtained by a method similar to that of dye 1, and the yield was 75%. ¹ H NMR (600MHz, DMSO) δ: 8.20(d, J=6.5Hz, 1H), 8.17(d, J=6.8Hz, 1H), 7.91(s, 1H), 7.60–7.55(m, 2H), 7.46(t, J=7.3Hz, 1H), 7.21(t, J=7.1Hz, 1H), 7.09(d, J=6.7Hz, 1H), 4.41(s, 2H), 3.09(s, 2H), 2.48(s,6H),2.41(s,6H),1.76(s,2H),1.65(s,2H),1.48(s,2H),1.37(d,J=6.6Hz,2H),1.23–1.13 (m,10H),0.90(t,J=6.8Hz,3H),0.78(t,J=6.6Hz,3H). ¹³ C NMR(151MHz,DMSO)δ:155.41,151.10,148.38,140.81,140.66, 139.06,137.58,135.96,132.25,131.06,130.20,126.32,126.03,122.34,121.75,121.27,120.83,120.72,119.31,111.52,109.77,51.60,32.81,32.35,31.57,29.26,29.23,29.11,29.08,27.05, 22.50, 22.29, 15.40, 14.77, 14.35, 14.32, 13.92, 13.13. MALDI-TOF-MS, m/z: calcd for C ₄₂ H ₄₉ BF ₂ N ₄ O ₂ [M] ⁺ :690.400,found: 690.612.

Example 4

Synthesis of Dye 4

160 mg of red solid powder was obtained by a method similar to that of dye 1, and the yield was 82%. ¹ H NMR (600MHz, DMSO) δ: 8.30(s, 1H), 8.24(s, 1H), 7.79(s, 1H), 7.59(d, J=8.7Hz, 2H), 7.46(t, J=7.7 Hz,1H),7.38(t,J=6.5Hz,2H),7.31(dd,J=13.0,7.9Hz,2H),7.25(d,J=8.8Hz,2H),3.90(s,3H), 3.21–3.09(m,1H),2.47(s,3H),2.46(s,3H),2.44(s,3H),2.43(s,3H),1.69(dd,J＝15.7,7.8Hz,2H) ,1.55–1.49(m,2H),1.40(dd,J=14.7,7.3Hz,2H),0.92(t,J=7.3Hz,3H). ¹³ C NMR(151MHz,DMSO)δ:166.51,162.78, 159.11,155.30,148.24,141.46,140.37,138.98,137.39,132.10,130.16,129.70,128.78,126.94,126.30,124.39,123.24,122.87,120.41,119.93,119.53,115.83,112.56,110.11,110.03,109.82,109.31, 55.97,33.00,32.37,31.56,22.33,15.38,14.82,14.43,14.39,13.19.MALDI-TOF-MS,m/z: calcd for C ₄₁ H ₃₉ BF ₂ N ₄ O ₃ [M] ⁺ :684.300,found: 684.700.

Example 5

Synthesis of Dye 5:

148 mg of reddish-brown solid powder was obtained by a method similar to that of dye 1, and the yield was 78%. ¹ H NMR (600MHz, DMSO) δ: 8.35(d, J=7.9Hz, 1H), 8.30(d, J=7.6Hz, 1H), 7.78(s, 1H), 7.57(d, J=8.8Hz, 2H), 7.46(t, J=7.9Hz, 1H), 7.32(dd, J=16.0, 7.9Hz, 2H), 7.22(d, J=8.7Hz, 3H), 7.15(s, 1H), 3.87( s,3H),3.11(t,J＝10.4Hz,1H),2.44(s,3H),2.41(s,6H),2.38(s,3H),1.69–1.61(m,2H),1.49–1.45 (m,2H),1.38(dd,J＝13.7,6.4Hz,2H),0.90(t,J＝7.3Hz,3H). ¹³ C NMR(151MHz,DMSO)δ:162.63,160.84,159.03,156.18, 151.35,148.58,141.52,141.13,137.77,135.55,130.84,129.97,129.60,128.68,126.90,122.73,122.53,122.30,121.12,120.50,115.87,111.45,110.10,55.92,32.34,31.41,29.50,22.28,15.46, 14.77,14.37,14.26,13.89.MALDI-TOF-MS,m/z:calcd for C ₄₁ H ₃₉ BF ₂ N ₄ O ₃ [M] ⁺ :684.300,found:684.699.

The relevant data of the ultraviolet absorption spectrum and electrochemical properties of the target dyes Dye 1-5 in dichloromethane solution in the above examples are shown in Table 1, and the photoelectric performance parameters of the target dyes Dye 1-5 in the examples are shown in Table 2.

Table 1 Photophysical and electrochemical data of Dye 1～5

[a]In CHCl ₃ solutions.

[b]Absorption maximum on TiO ₂ was obtained through measuring the dye absorbed on 3μm TiO ₂ nanoparticles films in a CHCl ₃ solution.

[c]E _OX was measured in CH ₂ Cl ₂ and calibrated with ferrocene as an external reference.

[d]E _0,0 was estimated from the absorption thresholds from absorption spectrum of dyes absorbed on the TiO ₂ film.

[e]Computed from the formula E ^* _ox ＝E _OX -E _0,0 .

It can be seen from Table 1 that the maximum UV absorption peaks of the five dyes all appear at around 530nm, compared with the BODIPY core structure (498nm), there is an obvious red shift phenomenon, which shows that the effective conjugation length of the molecule increases, Electron mobility within the molecule is enhanced. When the dye molecules were adsorbed on the TiO ₂ film, the maximum ultraviolet absorption peaks showed a weak basket shift, which indicated that the dye molecules had deprotonation effect and H-aggregation on the surface of nanocrystalline TiO ₂ . It can be seen from Figure 11 that the absorption spectra of Dye 4 and Dye 5 are wider and the absorption intensity is greater, which shows that the N-phenyl substituted carbazole is connected to the BODIPY core to produce a stronger conjugation effect, and the effective molecular As the conjugation length increases, the intramolecular electron migration is enhanced, and the electron-donating ability of the D structure is enhanced. The above results show that this type of BODIPY dye molecule has good photon-harvesting ability and has the necessary spectral conditions as a dye sensitizer. It can also be seen from Table 1 that the ground state oxidation potentials (E _ox vs. NHE) of the five dyes are all more positive than the oxidation/reduction potentials (0.42V vs. NHE) of the I ³ - /I ^- pair, that is, the electron loss Oxidized dye molecules can be effectively reduced by I- ^; the excited state reduction potential of the dye molecules is more negative than the energy level of the conduction band of titanium dioxide (-0.5V vs. NHE), so that the excited state electrons can be effectively injected into the conduction band of the semiconductor. band, such that the dye cell-based electron cycle is fully utilized, and thus these BODIPY dyes can be used as sensitizers for TiO electrodes.

Table 2 Photoelectric performance parameters of Dye 1-5

The current-voltage (JV) curves of five dye molecules under the simulated sunlight of AM1.5 (100mW·cm ^-2 ) based on Dye 1-5 sensitized solar cells are shown in Figure 13, and the corresponding short-circuit current ( The battery parameters such as J _sc ), open circuit voltage (V _oc ), and fill factor (FF) are listed in Table 2. The Dye 4 sensitized solar cell device has a J _sc of 5.40mA·cm ^-2 , a Voc of 600mV, and an FF value of 0.70. The reason for the higher battery parameters of Dye 4 may be that the 3-position of the carbazole ring is connected to the BODIPY unit, and the electron-donating center is closer to the acceptor unit, which is more conducive to the intramolecular migration of photoelectrons; secondly, due to the N-methoxy The phenyl-substituted carbazole has stronger electron-donating ability, so Dye 4 has higher photocurrent and photovoltage values.

The present invention illustrates the detailed synthesis method through the above examples, but the present invention is not limited to the above method, that is, it does not mean that the present invention must rely on the above reaction conditions to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of the reaction solvent catalyst of the present invention and the change of specific reaction conditions, etc., all fall within the scope of protection and disclosure of the present invention.

Claims (5)

1. one kind 2,6- organic dye sensitized dose of the BODIPY class of substitution, it is characterised in that the chemical constitution with formula I：

In formula I, D is donor monomer, is the one kind in following construction unit：

Wherein, R₁It is H or alkyl or alkoxy, n is 5；

A is receptor unit, is the one kind in following construction unit：

2. 2,6- preparation method of organic dye sensitized dose of the BODIPY classes for replacing of one kind as claimed in claim 1, its spy Levy and be, comprise the following steps：

(1) be there is into condensation reaction in 2,4- dimethyl pyrroles and acyl chlorides, then complex reaction is carried out with BFEE, in being obtained Mesosome 1, its structure is：

(2) intermediate 1 obtains intermediate 2 by dimension David Smail formylation reaction, and its structure is：

(3) intermediate 2 is obtained intermediate 3 with iodine monochloride by electrophilic substitution reaction, and its structure is：

(4) carbazole and n-octane bromide are reacted in the presence of alkali, intermediate 4 is obtained, its structure is：

(5) intermediate 4 reacts at room temperature with N- bromo-succinimides, obtains intermediate 5, and its structure is：

(6) intermediate 5, by Suzuki coupling reactions, obtains intermediate with duplex pinacol boron ester under the catalysis of catalyst 6, its structure is：

(7) 2- bromines carbazole reacts with n-octane bromide in the presence of alkali, and intermediate 7 is obtained, and its structure is：

(8) intermediate 7, by Suzuki coupling reactions, obtains centre with duplex pinacol borate under the catalysis of catalyst Body 8, its structure is：

(9) by paraiodoanisole and carbazole under the catalysis of catalyst, by Liv Ullmann condensation reaction, intermediate 9 is obtained, its knot Structure is：

(10) intermediate 9 and N- bromo-succinimides are reacted, obtains intermediate 10, its structure is：

(11) by paraiodoanisole and 2- bromines carbazole under the catalysis of catalyst, by Liv Ullmann condensation reaction, intermediate is obtained 11, its structure is：

(12) by intermediate 10 and duplex pinacol borate under the catalysis of catalyst, by Suzuki coupling reactions, it is obtained Intermediate 12, its structure is：

(13) by intermediate 11 and duplex pinacol borate under the catalysis of catalyst, by Suzuki coupling reactions, it is obtained Intermediate 13, its structure is：

(14) by 4- (9H- carbazole -9- bases) phenyl boric acids and intermediate 3 under the catalysis of catalyst, by Suzuki coupling reactions, Intermediate 14 is obtained, its structure is：

(15) respectively by intermediate 6,8,12,13 and intermediate 3 under the catalysis of catalyst, by Suzuki coupling reactions, system Intermediate 15,16,17,18 is obtained, its structure is：

(16) intermediate 14~18 is obtained target dye molecule Dye1- respectively with cyanoacetic acid by Knoevenagel condensation reactions 5, its structure is：

Wherein, n is 5.

3. 2,6- preparation method of organic dye sensitized dose of the BODIPY classes for replacing of one kind as claimed in claim 2, its spy Levy and be, in step (1)-(15), the reaction medium of the reaction is DMF, tetrahydrofuran, dichloromethane, One or more mixing of ethyl acetate, toluene, chloroform, ethanol.

4. 2,6- preparation method of organic dye sensitized dose of the BODIPY classes for replacing of one kind as claimed in claim 2, its spy Levy and be, in step (6), (8), (11), (12), (13), (14), (15), the catalyst is Pd (PPh₃)₄、Pd(dppf) Cl₂, one kind in CuI.

5. 2,6- preparation method of organic dye sensitized dose of the BODIPY classes for replacing of one kind as claimed in claim 2, its spy Levy and be, the reaction temperature in the step (2), (6), (8), (9), (11), (12), (13), (14), (15), (16) is 75- 120 DEG C, the reaction time of step (1)-(15) is 5-48h.