CN113755024B - Pure organic photosensitive dye with stepped energy transfer structure, and preparation method and application thereof - Google Patents
Pure organic photosensitive dye with stepped energy transfer structure, and preparation method and application thereof Download PDFInfo
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- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
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- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
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Abstract
The invention discloses a pure organic photosensitive dye with a stepped energy transfer structure, a preparation method and application thereof, wherein N, N '-diphenyl-N, N' -di (4-methylphenyl) -4,4 '-biphenyl diamine (TPB) is taken as an electron donor, pyrrolo-pyrrole-Dione (DPP) is taken as a first electron acceptor, cyanoacetic acid is taken as a second electron acceptor, and the space structure of a double screw of N, N' -diphenyl-N, N '-di (4-methylphenyl) -4,4' -biphenyl diamine (TPB) can effectively inhibit dye accumulation, and the dye is taken as an electron donor silver day to the dye structure, so that dye accumulation and interface electron recombination can be effectively prevented. Meanwhile, TPB groups have stronger electron donating ability, and can effectively improve the photoelectric property of the dye. The solar cell prepared by the organic photosensitive dye is beneficial to industrialization and large-scale popularization of sensitized solar cells.
Description
Technical Field
The invention belongs to the technical field of dye-sensitized solar cell sensitizers, and particularly relates to a pure organic photosensitive dye with a stepped energy transmission structure, and a preparation method and application thereof.
Background
Dye sensitized solar cells (dye-sensitized solar cells, DSCs) are one of the important research directions of solar cells, and the working principle and basic structure thereof are
Professor et al first proposed in 1991, developed over twenty years so far, with the highest efficiency of 14.3%, and was a solar cell with a relatively great development potential. The battery has simple manufacturing process, no need of expensive industrial equipment and high-cleanliness factory buildings, low cost and nano TiO used for the battery photo-anode 2 The materials such as the semiconductor film, the electrolyte and the like are safe and nontoxic. These advantages, which meet the trend of solar cells, make DSCs increasingly attractive to domestic and foreign scientists. With the research of base materials mature, the preparation process of the device is perfected, and DSCs are expected to become one of main solar cell products in the near future and are widely applied.
DSCs are structurally composed mainly of permeabilitiesTransparent conductive glass and nano TiO 2 The porous semiconductor film, dye photosensitizing agent, electrolyte and counter electrode. In the battery, the dye sensitizer plays a role in collecting energy, and as a sunlight capturing agent, the performance of the dye sensitizer plays an important role in the photoelectric conversion efficiency of DSCs.
Through more than 20 years of research, the photoelectric conversion efficiency of photosensitive dyes is continuously refreshed. Photosensitive dyes are mainly classified into two major classes, namely metal complex dyes and pure organic dyes. The metal complex dye has the characteristics of higher chemical stability, outstanding redox performance, good spectral response characteristic and the like. In the year of 1993,
the red dye-N3 is formed by the small combination, the photoelectric conversion efficiency of DSCs based on N3 reaches 10%, and the dye which breaks through 10% of photoelectric conversion efficiency is formed on the first research history of sensitized solar cells. On the basis of further optimizing the N3 structure, the N719 dye is synthesized, and the photoelectric conversion efficiency reaches 11.18% of the original record. N3 and N719 were the two earlier studies and were the most used dyes in the study of dye sensitized solar cells. 2009, japan>
The dye CYC-B11 is prepared by introducing two thiophene groups into a dye auxiliary ligand, and the molar extinction coefficient of the dye at 554nm of the maximum absorption peak reaches 2.42 multiplied by 10 3 m 2 ·mol -1 The dye showed jsc=20.05ma·cm under AM1.5 light -2 Voc=743 mV, the photoelectric conversion efficiency reaches 11.5%. In 2011, there is->
The group synthesizes dye YD2-o-C8 by introducing long-chain alkoxy to YD-2 and optimizing the structure, and DSCs photoelectric conversion efficiency based on YD2-o-C8 reaches 12.3%.
Compared with metal complex dye, the pure organic dye has the advantages of various molecular structures, high molar extinction coefficient, easily available raw materials, low cost and easy degradation, and is a photosensitive dye hopefully applied in practice. Recent studies have greatly improved the photoelectric conversion efficiency of solar cells prepared using organic dyes as sensitizers. In 2009, zhang J L synthesized triarylamine dye C217 with 4,4' -dialkoxytriphenylamine groups as electron donors and EDOT-linked benzothiophenes as pi bridges. In 2010, zeng W D further optimized the structure of C217, a triarylamine dye C219 was synthesized. In 2015, kenji Kakiage et al designed and synthesized ADEKA-1 and a triphenylamine pure organic dye-LEG 4, and prepared a battery device by a co-sensitization method, which is the photosensitive dye with highest efficiency so far. It can be seen that the pure organic photosensitive dye containing triphenylamine groups has excellent sensitization performance, and compared with the disadvantages of long synthetic route, difficult purification, high price and the like of the metal complex, the organic dye overcomes the disadvantages, and especially the application of the dye is more beneficial to the industrialization and large-scale popularization of sensitized solar cells. Therefore, the development of pure organic dyes is more and more paid attention to by researchers, and has good development potential.
Disclosure of Invention
The invention aims to provide a pure organic photosensitive dye with a stepped energy transfer structure, which solves the problems in the prior art, and is a novel D-pi-A pure organic photosensitive dye with N, N ' -diphenyl-N, N ' -di (4-methylphenyl) -4,4' -biphenyldiamine (TPB) as an electron donor, pyrrolopyrroldione (DPP) as a first electron acceptor and cyanoacetic acid as a second electron acceptor, and a solar cell prepared from the organic photosensitive dye is favorable for industrialization and large-scale popularization of sensitized solar cells.
The invention relates to a pure organic photosensitive dye with a stepped energy transfer structure, which has the following structural formula:
another object of the present invention is to provide a method for preparing pure organic photosensitive dye with a stepped energy transfer structure, comprising the following specific steps:
step one, slowly dropwise adding phosphorus oxychloride into dry N, N' -dimethylformamide under the protection of nitrogen to prepare a Vilsmeier reagent, then dropwise adding a mixed solution of a compound 1 and a reaction solvent into the Vilsmeier reagent, and carrying out a Vilsmeier reaction to obtain a compound 2; the synthetic route is as follows:
step two, under the protection of nitrogen, in the presence of tetrahydrofuran and strong alkali, the compound 2 and the compound 3 are dissolved in dry dimethyl sulfoxide, and the compound 4 is obtained through a Wittig reaction, wherein the synthetic route is as follows:
step three, adding the compound 4 and the compound 5 into a tertiary amyl alcohol solvent under the catalysis of ferrous chloride in the presence of the tertiary amyl alcohol solvent and metallic sodium, and carrying out reflux reaction to obtain a compound 6, wherein the synthetic route is as follows:
step four, slowly dropwise adding phosphorus oxychloride into dry N, N' -dimethylformamide under the protection of nitrogen to prepare a Vilsmeier reagent, dropwise adding a dichloromethane solution of the compound 6 into the Vilsmeier reagent, and carrying out Vilsmeier reaction to obtain a compound 7, wherein the synthetic route is as follows:
step five, under the protection of nitrogen, in the presence of acetonitrile, mixing the compound 7 with cyanoacetic acid, adding a catalyst piperidine into the mixture, and carrying out Knoevenagel condensation reaction to obtain a target dye compound 8: TPB-DPP-S-1, the synthetic route is as follows:
firstly, slowly dropwise adding phosphorus oxychloride into dry N, N' -dimethylformamide under the protection of nitrogen to prepare a first Vilsmeier reagent, then dropwise adding a mixed solution of a compound 1 and a reaction solvent into the first Vilsmeier reagent, and reacting for 10-16 hours at the reaction temperature of 0-45 ℃ to obtain a compound 2; compound 1: phosphorus oxychloride: the molar ratio of N, N' -dimethylformamide is 1: 1-2: 2 to 4;
step two, under the protection of nitrogen, in the presence of tetrahydrofuran and strong alkali, dissolving the compound 2 and the compound 3 in a dry reaction solvent, and carrying out a Wittig reaction for 4-10 h to obtain a compound 4, wherein the molar ratio of the compound 2 to the compound 3 is 1:1 to 5;
step three, adding the compound 4 and the compound 5 into a solvent under the catalysis of ferrous chloride in the presence of the solvent tertiary amyl alcohol and metallic sodium, and carrying out reflux reaction for 1-5 h to obtain a compound 6, wherein the molar ratio of the compound 4 to the compound 5 is 1:1 to 4;
step four, slowly dropwise adding phosphorus oxychloride into dry N, N' -dimethylformamide under the protection of nitrogen to prepare a second Vilsmeier reagent, then dropwise adding a mixed solution of the compound 6 and a reaction solvent into the second Vilsmeier reagent, and reacting for 8-16 hours at the reaction temperature of 0-45 ℃ to obtain a compound 7;
step five, under the protection of nitrogen, mixing the compound 7 with cyanoacetic acid in the presence of acetonitrile, adding a catalyst piperidine into the mixture, and carrying out Knoevenagel condensation reaction for 8-10 h to obtain a target dye compound 8, wherein the molar ratio of the compound 7 to the cyanoacetic acid is 1:1 to 5.
In the second step, the reaction solvent is dimethyl sulfoxide, N' -dimethylformamide or chloroform.
Preferably, in the second step, the strong base is sodium hydride or potassium tert-butoxide.
Preferably, in the first and fourth steps, the reaction solvent is dichloromethane or 1, 2-dichloroethane or chloroform.
In a preferred embodiment, in the fifth step, the target product compound 8 is subjected to a post-treatment by: and after the reaction is completed, steaming to obtain a crude product, separating by adopting a rapid column chromatography, wherein the eluent is a mixed solution of dichloromethane and ethanol, and obtaining the organic dye.
Preferably, the eluent is prepared from dichloromethane and ethanol, wherein the dichloromethane: the volume ratio of the ethanol is 15-40: 1.
a third object of the present invention is to provide an application of pure organic photosensitive dye of a stepped energy transfer structure in the preparation of dye sensitized solar cells, the preparation steps of the cells: preparation of TiO by knife coating 2 Film, FTO conductive glass with substrate of sheet resistance 15 omega and TiO 2 The film is composed of an upper layer and a lower layer, and comprises a transparent layer of a bottom layer and a scattering layer of an upper layer, and is calcined at 450 ℃ for 30 minutes, and is soaked into dye bath of the synthesized dye when the temperature is reduced to 80 ℃; the dye bath adopts ethanol: DMF volume ratio was 4:1 as a solvent, wherein the dye concentration is 0.25mM, and the concentration of the co-adsorbent cholic acid is 10mM; the electrolyte adopts 3-methoxy propionitrile: the volume ratio of acetonitrile is 4:1 as a solvent, wherein the concentration of the components is respectively 1.0M 1-hexyl-3-methylimidazole iodized salt, 30mM lithium iodide, 30mM iodine, 0.1M guanidine thiocyanate and 0.5M 4-tert-butylpyridine; the synthesized organic dye compound 8 and the reference dye were used as photosensitizing dyes, respectively, and the batteries were assembled according to the above-described battery preparation steps, and then the photoelectric properties of the batteries were tested according to the same conditions.
Compared with the prior art, the invention has at least the following beneficial effects:
the space structure of the double propellers of the first, N ' -diphenyl-N, N ' -di (4-methylphenyl) -4,4' -biphenyl diamine (TPB) can effectively inhibit dye accumulation, and the space structure is taken as an electron donor silver day to the dye structure, so that dye accumulation can be effectively prevented, and interface electron recombination can be inhibited. Meanwhile, TPB groups have stronger electron donating ability, and can effectively improve the photoelectric property of the dye.
Secondly, TPB is used as an electron donor, cyanoacetic acid is used as an electron acceptor, DPP derivatives with different structures are introduced to serve as pi bridges, so that photochemical band gaps of the dye are regulated, the spectral response range of the dye is widened, multi-stage electron transfer in molecules is realized, and therefore, the electron transmission efficiency and the photoelectric conversion efficiency of a battery device are improved.
Thirdly, the application of the organic dye in the dye sensitized solar cell provided by the invention shows that the test result shows that: the short-circuit current of the battery device is 11.15mA/cm 2 The open-circuit voltage is 684mV, the filling factor is 0.74, and the photoelectric conversion efficiency reaches 5.21%, so that the method has practical significance on the efficiency of the dye-sensitized solar cell.
Drawings
FIG. 1 shows the organic dye prepared in example 1 dissolved in methylene chloride solution (concentration 1X 10 -5 The ultraviolet visible absorption spectrum in M).
FIG. 2 shows the organic dye prepared in example 1 in TiO 2 Ultraviolet spectrum on film.
Fig. 3 is a J-V curve of the dye prepared in example 1 applied to a dye-sensitized solar cell.
Fig. 4 is an IPCE curve of the dye prepared in example 1 applied to a dye sensitized solar cell.
Detailed Description
The present invention will be explained in more detail with reference to the following examples, but it should be noted that the present invention is not limited to the following examples.
The scheme provides a pure organic photosensitive dye with a stepped energy transmission structure, which has the following structure:
the scheme also provides a preparation method of the pure organic photosensitive dye with the stepped energy transfer structure,
step one, slowly dropwise adding phosphorus oxychloride into dry N, N' -dimethylformamide under the protection of nitrogen to prepare a first Vilsmeier reagent, then dropwise adding a mixed solution of a compound 1 and a reaction solvent into the first Vilsmeier reagent, reacting at a temperature of between 0 and 45 ℃ for 10 to 16 hours to obtain a compound 2; pouring the mixture into a certain amount of ice water after the reaction is finished, regulating the pH value to be neutral by using an aqueous solution of NaOH, stirring for 0.5h, adding dichloromethane with the same volume as the ice water for extraction, combining the organic layers for water washing, adding anhydrous magnesium sulfate for drying, and purifying by adopting column chromatography; wherein compound 1: phosphorus oxychloride: the molar ratio of N, N' -dimethylformamide is 1: 1-2: 2-4, wherein the Vilsmeier reaction temperature is 0-45 ℃ and the reaction time is 10-16 h; the reaction solvent used in this step is methylene chloride or 1, 2-dichloroethane or chloroform. Preferably, dichloromethane is used. Preferably, the concentration of the dichloromethane solution of compound 1 is 0.8mol/L.
Step two, under the protection of nitrogen, the compound 2 and the compound 3 are dissolved in a dry reaction solvent in the presence of tetrahydrofuran and strong alkali, the compound 4 is obtained through Wittig reaction for 4-10 hours at normal temperature, after the reaction is finished, the reaction solution is poured into a certain amount of ice water to be stirred for 1 hour, after the dichloromethane is used for merging an organic layer, anhydrous magnesium sulfate is added for drying, and the solvent is removed through reduced pressure distillation, so that a yellow solid crude product containing cis-trans isomers is obtained. The crude product was dissolved in tetrahydrofuran, a small amount of iodine was added, and the reaction was refluxed for 9 hours. Adding a certain amount of 15% NaOH solution by mass fraction, stirring for 1h, removing residual iodine, extracting and combining organic layers with dichloromethane, adding anhydrous magnesium sulfate for drying, distilling under reduced pressure to remove solvent to obtain yellow solid, and purifying the crude product by column chromatography, wherein in the step, the molar ratio of the compound 2 to the compound 3 is 1:1 to 5. The Wittig reaction time is 4-10 h. The strong base used in the reaction is sodium hydride or potassium tert-butoxide. The reaction solvent in the step is dimethyl sulfoxide or N, N' -dimethylformamide or trichloromethane. Preferably, dimethyl sulfoxide may be used.
And thirdly, adding the compound 4 and the compound 5 into the solvent under the catalysis of ferrous chloride in the presence of the solvent tertiary amyl alcohol and metallic sodium, carrying out reflux reaction for 1-5 h to obtain the compound 6, pouring the solution into a certain amount of deionized water after the reaction is finished, and filtering to obtain a crude product. Purifying by column chromatography, and separating to obtain compound 6. In this step, the molar ratio of compound 4 to compound 5 was 1:1 to 4.
Step four, slowly dropwise adding phosphorus oxychloride into dry N, N' -dimethylformamide under the protection of nitrogen to prepare a second Vilsmeier reagent, then dropwise adding a mixed solution of the compound 6 and a reaction solvent into the second Vilsmeier reagent, and reacting for 8-16 hours at the reaction temperature of 0-45 ℃ to obtain a compound 7; pouring the mixture into a certain amount of ice water after the reaction is finished, regulating the pH value to be neutral by using an aqueous solution of NaOH, stirring for 0.5h, adding dichloromethane with the same volume as the ice water for extraction and separation, mixing the organic layers, adding anhydrous magnesium sulfate for drying, and purifying by adopting column chromatography, wherein in the step, the compound 6: phosphorus oxychloride: the molar ratio of N, N' -dimethylformamide is 1:1 to 12:1 to 12. The reaction solvent used in this step is methylene chloride or 1, 2-dichloroethane or chloroform, preferably methylene chloride.
Step five, under the protection of nitrogen, mixing the compound 7 with cyanoacetic acid in the presence of acetonitrile, adding a catalyst piperidine into the mixture, heating and refluxing the mixture, and carrying out Knoevenagel condensation reaction for 8-10 hours to obtain a target dye compound 8, wherein the target product compound 8 is subjected to post-treatment through the following steps: after the reaction is completed, evaporating to obtain a crude product, separating by adopting a rapid column chromatography, wherein the eluent is a mixed solution of dichloromethane and ethanol, and obtaining the organic dye. In this step, the molar ratio of compound 7 to cyanoacetic acid was 1:1 to 5. The Knoevenagel condensation reaction time is 8-10 h. The volume ratio of the eluent is methylene dichloride: ethanol=15 to 40:1.
the synthetic route of the invention is as follows:
the design thought of the technical scheme is as follows: the design of the scheme synthesizes the novel D-pi-A pure organic photosensitive dye with TPB as an electron Donor (Donor, D), DPP as a first electron Acceptor (accepter, A) and cyanoacetic acid as a second electron Acceptor, wherein N, N ' -diphenyl-N, N ' -di (4-methylphenyl) -4,4' -biphenyl diamine (TPB) and derivatives thereof are used as important triphenylamine derivatives, and the novel D-pi-A pure organic photosensitive dye has the advantages of higher molar extinction coefficient, excellent hole transmission performance, stronger electron donating ability and the like, and can be used as an electron donating group to be applied to the structural design of the sensitized dye, so that the performance of the sensitized dye can be improved.
Among them, pyrrolopyrrole Dione (DPP) is a typical electron-deficient nitrogen heterocyclic compound having a planar bicyclic conjugated structure, and its derivatives have unique optical stability and thermal stability. As bridge group, the planar bicyclic conjugated structure with electron deficiency can realize multi-stage electron transfer inside molecules, effectively broaden the absorption spectrum of the donor-acceptor dye, and increase the absorption range of the device to sunlight and the photocurrent and photoelectric conversion efficiency of the device.
The scheme also provides application of the pure organic photosensitive dye with the stepped energy transfer structure in preparing the dye-sensitized solar cell, which specifically comprises the following steps:
the preparation method comprises the following steps: preparation of TiO by knife coating 2 Film, FTO conductive glass with substrate of sheet resistance 15 omega and TiO 2 The film is composed of an upper layer film and a lower layer film, wherein the upper layer film comprises a transparent layer of a bottom layer and a scattering layer of an upper layer, the transparent layer and the scattering layer are calcined at 450 ℃ for 30 minutes, and when the temperature is reduced to 80 ℃, the transparent layer and the scattering layer are soaked into dye bath of the synthesized dye; the dye bath adopts ethanol: DMF volume ratio was 4:1 as a solvent, wherein the dye concentration is 0.25mM, and the concentration of the co-adsorbent cholic acid is 10mM; the electrolyte adopts 3-methoxy propionitrile: the volume ratio of acetonitrile is 4:1 as a solvent, wherein the concentration of the components is respectively 1.0M 1-hexyl-3-methylimidazole iodized salt, 30mM lithium iodide, 30mM iodine, 0.1M guanidine thiocyanate and 0.5M 4-tert-butylpyridine;
and (3) battery testing: the synthesized organic dye compound 8 and the reference dye were used as photosensitizing dyes, respectively, and the batteries were assembled according to the above-described battery preparation steps, and then the photoelectric properties of the batteries were tested according to the same conditions.
It is noted that compound 1, compound 3 and compound 5 used in the following examples are prepared by the prior art, wherein compound 1 can be prepared according to the patent (grant number: CN 108276300A); compound 3 was prepared according to the patent (grant number: US 4256878A); compound 5 was according to literature "Wang, xiaohua; jiang, bin; du, chenchen, et al, fluorinated dithiinyl-diketopropyrrrole, a new building block for organic optoelectronic materials, new Journal of Chemistry2019,43 (41), 16411-16420 ".
Example 1
In the first step, dry N, N' -dimethylformamide DMF (6.24 g,85.28 mmol) was added to a 100mL four-necked flask under nitrogen protection, phosphorus oxychloride (9.87 g,64.38 mmol) was slowly added dropwise, and the temperature was controlled below 0deg.C. After the completion of the dropwise addition, the ice bath was removed, and the mixture was stirred at room temperature for 1 hour to obtain a Vilsmeier reagent. A solution containing 50mL of 1, 2-dichloroethane of Compound 1 (20.00 g,38.74 mmol) was added dropwise to the reaction flask. The temperature was controlled at 15℃and the reaction was stirred for 14h. After the reaction is finished, pouring the mixture into 400mL of ice water, regulating the pH value to be neutral by using an NaOH aqueous solution, stirring the mixture for 0.5h, adding 400mL of dichloromethane for extraction, merging organic layers, washing the organic layers with water, adding anhydrous magnesium sulfate for drying, and separating by adopting column chromatography (a silica gel column, eluent is petroleum ether/ethyl acetate=30:1) to obtain a compound 2 (yellow solid, 10.60g, yield 50%); 1H NMR (300 MHz, CDCl) 3 ):δ(ppm)2.33(s,3H),2.36(s,3H),7.02-7.05(m,5H),7.09(d,8H,J＝8.5),7.16(t,4H),7.235(t,2H),7.42(d,2H,J＝9.0),7.50(d,2H,J＝8.5),7.66(d,2H,J＝8.5),9.80(s,1H)；MS(ESI,m/z):[M+]calcd for C 39 H 32 N 2 O,544.7；found,544.6。
Step two, compound 3 (6.97 g,15.00 mmol) and Compound 2 (2.58 g,4.74 mmol) were dissolved in 240mL of dried dimethyl sulfoxide (DMSO) under nitrogen, and cooled to below 0deg.C in an ice bath. Potassium tert-butoxide (1.60 g,14.22 mmol) was dissolved in 20mL of dry Tetrahydrofuran (THF), and slowly added dropwise to the above solution, with the reaction temperature controlled below 5 ℃. After the completion of the dropwise addition, the reaction was stirred at room temperature (25 ℃ C.) for 8 hours. After the reaction was completed, the reaction mixture was poured into 400mL of ice water, stirred for 1 hour, then stirred with methylene chloride,the organic layers were combined and anhydrous magnesium sulfate (MgSO) 4 ) Drying, and distilling under reduced pressure to remove the solvent to obtain a yellow solid crude product containing cis-trans isomers. The crude product was dissolved in 80mL THF, a small amount of iodine was added and the reaction was refluxed for 9h. Adding 15% NaOH solution 75mL, stirring for 1 hr, removing residual iodine, extracting the combined organic layers with dichloromethane, adding anhydrous magnesium sulfate (MgSO 4 ) Drying, distilling under reduced pressure to remove solvent to obtain yellow solid, purifying the crude product by column chromatography (silica gel column, eluent is petroleum ether/dichloromethane=15:1), and separating to obtain compound 4 (yellow solid, 2.71g, yield 88%); 1H NMR (DMSO, 300 MHz): delta (ppm) 2.33 (s, 3H), 2.34 (s, 3H), 6.94 (d, 1H, J=15.0 Hz), 6.99 (s, 1H), 7.01 (M, 1H), 7.08 (M, 2H), 7.13 (d, 6H, J=5.0 Hz), 7.15 (d, 5H, J=10 Hz), 7.24 (d, 2H), 7.37 (d, 4H, J=10 Hz), 7.48 (d, 1H), 7.55 (d, 4H), 7.77 (d, 2H) [ M+H ]]calcd for C 45 H 35 N 3 S,649.3；found,650.4.
Step three, after removing the surface oxide layer of metallic sodium (0.62 g,0.027 mol), it was added to 60mL of t-amyl alcohol, to which was added 0.05g of anhydrous ferrous chloride. After stirring and heating under reflux to give a yellow clear solution, compound 4 (8.45 g,0.013 mol) and compound 5 (3.08 g,0.013 mol) were added and reacted under reflux for 2h. After the reaction was completed, the solution was poured into 300mL of deionized water, and filtered to obtain a crude product. Purification by column chromatography (silica gel column, eluent petroleum ether/dichloromethane=25:1) afforded compound 6 (yellow solid, 4.58g, 42% yield); 1H NMR (DMSO, 300 MHz): delta (ppm) 2.33 (s, 3H), 2.34 (s, 3H), 6.94 (d, 1H, J=15.0 Hz), 6.99 (s, 1H), 7.00 (t, 1H), 7.08 (d, 2H), 7.13 (d, 6H, J=5.0 Hz), 7.15 (d, 4H, J=10 Hz), 7.19 (s, 2H), 7.24 (t, 2H), 7.36 (t, 1H), 7.37 (d, 4H, J=10 Hz), 7.43 (d, 1H), 7.55 (d, 4H), 7.77 (d, 2H), 7.85 (d, 2H), 7.95 (s, 1H) [ M+H ]]calcd for C 54 H 40 N 4 O 2 S 2 ,840.3；found,841.4.
Step four, under the protection of nitrogen, compound 6 (1.88 g,2.24 mmol) is dissolved in 25mL of dry dichloromethane and N, N' -dimethylformamide (DMF, 1.96g,26.88 mmol), the temperature is reduced to below 5 ℃ by ice bath, dry phosphorus oxychloride (3.47 g,22.63 mmol) is slowly added dropwise, the reaction temperature is controlled to be 15 ℃ and stirring is carried outAfter the reaction is completed, pouring the mixture into 400mL of ice water, regulating the pH value to be neutral by using an aqueous solution of NaOH, stirring the mixture for 0.5h, adding 400mL of dichloromethane, extracting and separating the mixture, combining the organic layers, adding anhydrous magnesium sulfate for drying, and separating the mixture by adopting column chromatography (a silica gel column, eluent is petroleum ether/ethyl acetate=20:1) to obtain a compound 7 (orange solid, 1.19g and yield 61%); 1H NMR (DMSO, 300 MHz): delta (ppm) 2.33 (s, 3H), 2.34 (s, 3H), 6.95 (d, 1H, J=15.0 Hz), 6.99 (s, 1H), 7.00 (t, 1H), 7.08 (d, 2H), 7.13 (d, 6H, J=5.0 Hz), 7.15 (d, 4H, J=10 Hz), 7.19 (s, 2H), 7.24 (t, 2H), 7.37 (d, 4H, J=10 Hz), 7.43 (d, 1H), 7.55 (d, 4H), 7.77 (d, 2H), 7.85 (d, 1H), 7.95 (s, 1H), 8.15 (d, 1H), 9.84 (s, 1H) [ M+H ]]calcd for C 55 H 40 N 4 O 3 S 2 ,868.3；found,869.4.
Step five, under nitrogen protection, 50mL four-necked flask was charged with compound 7 (2.00 g,2.30 mmol), cyanoacetic acid (0.59 g,6.90 mmol), 0.20mL piperidine and 25mL acetonitrile, and the mixture was heated under reflux for 8h. After the reaction, performing rotary evaporation to obtain a crude product, and separating by adopting a flash column chromatography (silica gel column, eluent is dichloromethane: ethanol=30:1) to obtain a target dye compound 8 (red solid, 1.74g, yield 81%); 1H NMR (DMSO, 300 MHz): delta (ppm) 2.33 (s, 3H), 2.34 (s, 3H), 6.95 (d, 1H, J=15.0 Hz), 6.99 (s, 1H), 7.00 (t, 1H), 7.08 (d, 2H), 7.13 (d, 6H, J=5.0 Hz), 7.15 (d, 4H, J=10 Hz), 7.19 (s, 2H), 7.24 (t, 2H), 7.37 (d, 4H, J=10 Hz), 7.43 (d, 1H), 7.55 (d, 4H), 7.77 (d, 2H), 7.85 (d, 1H), 8.13 (d, 1H), 8.20 (d, 1H), 8.61 (s, 1H), 12.56 (s, 1H).+M.]calcd for C 58 H 41 N 5 O 4 S 2 ,935.3；found,935.4.
Example 2
Step one, under the protection of nitrogen, dry DMF (5.66 g,77.48 mmol) was added to a 100mL four-necked flask and POCl was slowly added dropwise 3 (5.94 g,38.74 mmol) and the temperature was controlled below 0deg.C. After the completion of the dropwise addition, the ice bath was removed, and the mixture was stirred at room temperature for 1 hour to obtain a Vilsmeier reagent. A solution of compound 1 (20.00 g,38.74 mmol) in 50mL of dichloromethane was added dropwise to the reaction flask. The temperature was controlled at 0℃and the reaction was stirred for 16h. After the reaction is finished, pouring the mixture into 400mL of ice water, regulating the pH value to be neutral by using NaOH aqueous solution, stirring the mixture for 0.5h, and adding 400mL of dichloroMethane extraction, combining organic layers, washing with water, adding anhydrous magnesium sulfate, drying, separating by column chromatography (silica gel column, eluent is petroleum ether/ethyl acetate=30:1) to obtain compound 2 (yellow solid, 5.30g, yield 25%),
step two, compound 3 (2.32 g,5.00 mmol) and Compound 2 (2.72 g,5.00 mmol) were dissolved in 250mL of dry N, N' -dimethylformamide under nitrogen and cooled to below 0deg.C in an ice bath. Potassium tert-butoxide (1.60 g,14.22 mmol) was dissolved in 20mL of dry tetrahydrofuran, and slowly added dropwise to the above solution, with the reaction temperature controlled below 5 ℃. After the completion of the dropwise addition, the reaction was stirred at room temperature (25 ℃ C.) for 10 hours. After the completion of the reaction, the reaction solution was poured into 400mL of ice water and stirred for 1 hour, then dichloromethane was used, the organic layers were combined and dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude yellow solid product containing the cis-trans isomer. The crude product was dissolved in 80mL tetrahydrofuran, a small amount of iodine was added, and the reaction was refluxed for 9h. 75mL of 15% NaOH solution by mass fraction was added and stirred for 1 hour, the remaining iodine was removed, the combined organic layers were extracted with methylene chloride, dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure to give a yellow solid, and the crude product was purified by column chromatography (silica gel column, eluent petroleum ether/methylene chloride=15:1) and isolated to give compound 4 (yellow solid, 2.00g, yield 62%).
Step three, after removing the surface oxide layer of metallic sodium (0.62 g,0.027 mol), it was added to 60mL of t-amyl alcohol, and then 0.05g of anhydrous ferrous chloride was added thereto. After stirring and heating under reflux to give a yellow clear solution, compound 4 (8.44 g,0.013 mol) and compound 5 (6.17 g,0.026 mol) were added and reacted under reflux for 5 hours. After the reaction was completed, the solution was poured into 300mL of deionized water, and filtered to obtain a crude product. Purification by column chromatography (silica gel column, eluent petroleum ether/dichloromethane=25:1) afforded compound 6 (yellow solid, 4.14g, 38% yield).
Step four, under the protection of nitrogen, dissolving the compound 6 (4.20 g,5 mmol) in 25mL of dry 1, 2-dichloroethane and DMF (0.37 g,5 mmol), cooling to below 5 ℃ in an ice bath, and slowly dropwise adding dry POCl 3 (0.77 g,5 mmol) and stirring at 0deg.C for 16hAfter completion, the mixture was poured into 400mL of ice water, the pH was adjusted to neutrality with an aqueous NaOH solution, after stirring for 0.5 hour, 400mL of methylene chloride was added to extract the fractions, and after combining the organic layers, anhydrous magnesium sulfate was added to dry the fractions, and separation was performed by column chromatography (silica gel column, eluent: petroleum ether/ethyl acetate=20:1) to give compound 7 (orange solid, 0.66g, yield 15%).
Step five, under nitrogen protection, 50mL four-necked flask was charged with compound 7 (4.35 g,5.00 mmol), cyanoacetic acid (0.43 g,5.00 mmol), 0.20mL piperidine and 25mL acetonitrile, and the mixture was heated under reflux for 10h. After the reaction, the crude product was distilled off by rotary evaporation, and then separated by flash column chromatography (silica gel column, eluent: dichloromethane: ethanol=15:1) to give the objective dye compound 8 (red solid, 1.20g, yield 26%).
Example 3
Step one, under nitrogen protection, dry DMF (11.33 g,154.96 mmol) was added to a 100mL four-necked flask and POCl was slowly added dropwise 3 (11.88 g,77.48 mmol) and the temperature was controlled below 0deg.C. After the completion of the dropwise addition, the ice bath was removed, and the mixture was stirred at room temperature for 1 hour to obtain a Vilsmeier reagent. A solution of compound 1 (20.00 g,38.74 mmol) in 50mL trichloroethane was added dropwise to the reaction flask. The temperature is controlled at 45 ℃ and the reaction is stirred for 10 hours. After the reaction was completed, the mixture was poured into 400mL of ice water, the pH was adjusted to neutrality with an aqueous NaOH solution, stirred for 0.5h, then 400mL of dichloromethane was added for extraction, the organic layer was washed with water, dried over anhydrous magnesium sulfate, and separated by column chromatography (silica gel column, eluent: petroleum ether/ethyl acetate=30:1) to give compound 2 (yellow solid, 6.32g, yield 30%).
Step two, under nitrogen protection, compound 3 (11.61 g,25.00 mmol) and compound 2 (2.72 g,5.00 mmol) were dissolved in 250mL dry chloroform and cooled to below 0deg.C in an ice bath. Sodium hydride (0.34 g,14.00 mmol) was dissolved in 20mL of dry tetrahydrofuran and slowly added dropwise to the above solution, with the reaction temperature controlled below 5 ℃. After the completion of the dropwise addition, the reaction was stirred at room temperature (25 ℃ C.) for 4 hours. After the completion of the reaction, the reaction mixture was poured into 400mL of ice water and stirred for 1 hour, then dichloromethane was used, the organic layers were combined, dried over anhydrous magnesium sulfate and distilled under reduced pressure to remove the solvent, whereby a crude yellow solid product containing cis-trans isomers was obtained. The crude product was dissolved in 80mL tetrahydrofuran, a small amount of iodine was added, and the reaction was refluxed for 9 hours. 75mL of 15% NaOH solution by mass fraction was added and stirred for 1 hour, the remaining iodine was removed, the combined organic layers were extracted with methylene chloride, dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure to give a yellow solid, and the crude product was purified by column chromatography (silica gel column, eluent petroleum ether/methylene chloride=15:1) and isolated to give compound 4 (yellow solid, 2.22g, yield 68%).
Step three, after removing the surface oxide layer of metallic sodium (0.62 g,0.027 mol), it was added to 60mL of t-amyl alcohol, to which was added 0.05g of anhydrous ferrous chloride. After stirring and heating under reflux to give a yellow clear solution, compound 4 (8.45 g,0.013 mol) and compound 5 (12.34 g,0.052 mol) were added and reacted under reflux for 1h. After the reaction was completed, the solution was poured into 300mL of deionized water, and filtered to obtain a crude product. Purification by column chromatography (silica gel column, eluent petroleum ether/dichloromethane=25:1) afforded compound 6 (yellow solid, 3.49g, 32% yield).
Step four, under the protection of nitrogen, dissolving the compound 6 (4.21 g,5 mmol) in 25mL of dry 1, 2-dichloroethane and DMF (4.39 g,60 mmol), cooling to below 5 ℃ in an ice bath, and slowly dropwise adding dry POCl 3 (9.20 g,60 mmol), stirring at 45deg.C for 8 hr, adding into 400mL ice water after the reaction, adjusting pH to neutrality with NaOH aqueous solution, stirring for 0.5 hr, adding 400mL dichloromethane, extracting, separating, mixing organic layers, adding anhydrous magnesium sulfate, drying, and separating by column chromatography (silica gel column, eluent petroleum ether/ethyl acetate=20:1) to obtain compound 7 (orange solid, 0.82g, yield 19%).
Step five, under nitrogen protection, 50mL four-necked flask was charged with compound 7 (4.35 g,5.00 mmol), cyanoacetic acid (2.13 g,25.00 mmol), 0.20mL piperidine and 25mL acetonitrile, and the mixture was heated under reflux for 10h. After the reaction, the crude product was distilled off by rotary evaporation, and then separated by flash column chromatography (silica gel column, eluent: dichloromethane: ethanol=40:1) to obtain dye compound 8 (red solid, 1.67g, yield 36%).
It is to be noted that, since the products of each step of examples 2 and 3 are the same as those of example 1, the product characterization data of each step of examples 2 and 3 are the same as those of example 1.
The test data for each example are described below:
the ultraviolet absorption spectrum of the organic dye compound 8 prepared in the first and the above examples 1-3 is shown in FIG. 1, and it is seen from the graph that the dye compound has two distinct absorption peaks at 355nm and 536nm, and the molar extinction coefficients are 5.58×10, respectively 4 M -1 cm -1 And 5.41×10 4 M -1 cm -1 From this, it can be seen that the dye has a large absorption wavelength and a high molar extinction coefficient, so that the dye is favorable for fully absorbing and utilizing sunlight in a long-wave range.
Second, as shown in FIG. 2, when the dye is adsorbed on TiO 2 After the film surface, dyes and TiO 2 The complex action of the surface and the accumulation action between the dyes can change the absorption spectrum of the dyes, and red shift and blue shift can occur. Dye molecules in TiO 2 The accumulation of the surface is disadvantageous for the photoelectric conversion performance of the dye.
Third, as shown in FIG. 3, FIG. 3 is TiO 2 SEM electron micrograph of a cut surface of the film revealed that the film had a thickness of about 3. Mu.m.
UV absorbance data of dye in dichloromethane solution, and the dye in TiO 2 The uv absorbance data of the film surface and the difference between the two are summarized in table 1.
Table 1 dye in solution neutralization of TiO 2 Ultraviolet absorbance spectral data on film
As can be seen from Table 1, dye compound 8 was found in TiO as compared to the ultraviolet absorption spectrum in solution 2 The ultraviolet absorption spectrum of the film surface is only blue shifted by 3nm. A similar dye structure is reported in the literature (D.P.Hagberg, T.Marinado, K.I M. Karlsson, qin, G.Boschloo, T.Brinck, A.Hagfeldt, and L.Sun, J.Org.Chem.,2007,72,9550-9556.), since TPB having a double propeller structure is not used as an electron donating group, it can be seen that the dye in this document is present in TiO 2 The ultraviolet absorption spectrum of the surface is blue shifted by 48nm, higher than the dye compound 8 in this embodiment. It can be seen from the comparison that TPB is indeed effective in inhibiting the accumulation between dye molecules as an electron donating group.
Example 4
This example provides the use of the organic dye compound 8 prepared in examples 1 to 3 in the preparation of dye sensitized solar cells, comprising the following specific steps:
preparation of TiO by knife coating 2 The film (particle diameter is 20 nm) is FTO conductive glass with square resistance of 15 omega. TiO (titanium dioxide) 2 The photoanode consists of two films, a 10 μm transparent layer as the bottom layer and a 3 μm scattering layer as the top layer. Calcining at 450 ℃ for 30min, and soaking into the solution (dye bath) of the synthesized dye for 12h when the temperature is reduced to 80 ℃. The dye bath adopts a mixed solution with the volume ratio of ethanol/DMF=4/1 as a solvent, the dye concentration is 0.25mM, and the concentration of the co-adsorbent cholic acid is 10mM. The electrolyte adopts a mixed solution with the volume ratio of 3-methoxypropionitrile/acetonitrile=4/1 as a solvent, and the concentration of the contained components is 1.0M of 1-hexyl-3-methylimidazolium iodide (MHMII), 30mM of lithium iodide (LiI), 30mM of iodine, 0.1M of guanidine thiocyanate (GuNCS) and 0.5M of 4-tert-butylpyridine (TBP). Battery test conditions: standard light intensity (AM 1.5, 100mW cm) -2 ) Provided by solar simulators (Oriel, 91192). The volt-ampere characteristics of the cells were recorded by a potentiostat (Princeton Applied Research, 263A) with a window area of 0.15cm 2 . In this scheme, where the unit M refers to mol/L and mM refers to mmol/L.
Table 2 photovoltaic performance data for dye sensitized solar cells based on dye compound 8 and reference dye N719
The present invention is not limited to the above-mentioned embodiments, but is intended to be limited to the following embodiments, and any modifications, equivalent changes and variations in the above-mentioned embodiments can be made by those skilled in the art without departing from the scope of the present invention.
Claims (6)
1. A pure organic photosensitive dye of a stepped energy transfer structure, characterized in that: has the following structural formula:
2. a preparation method of a pure organic photosensitive dye with a stepped energy transfer structure is characterized by comprising the following steps of:
step one, slowly dropwise adding phosphorus oxychloride into dry N, N' -dimethylformamide under the protection of nitrogen to prepare a Vilsmeier reagent, then dropwise adding a mixed solution of a compound 1 and a reaction solvent into the Vilsmeier reagent, and carrying out a Vilsmeier reaction to obtain a compound 2; the synthetic route is as follows:
step two, under the protection of nitrogen, in the presence of tetrahydrofuran and sodium hydride, the compound 2 and the compound 3 are dissolved in dry dimethyl sulfoxide, and the compound 4 is obtained through a Wittig reaction, wherein the synthetic route is as follows:
step three, adding the compound 4 and the compound 5 into the tertiary amyl alcohol solvent in the presence of the tertiary amyl alcohol solvent and metallic sodium under the catalysis of ferrous chloride, and carrying out reflux reaction to obtain a compound 6, wherein the synthetic route is as follows:
step four, slowly dropwise adding phosphorus oxychloride into dry N, N' -dimethylformamide under the protection of nitrogen to prepare a Vilsmeier reagent, dropwise adding a dichloromethane solution of the compound 6 into the Vilsmeier reagent, and carrying out Vilsmeier reaction to obtain a compound 7, wherein the synthetic route is as follows:
step five, under the protection of nitrogen, mixing the compound 7 with cyanoacetic acid in the presence of acetonitrile, adding a catalyst piperidine into the mixture, and carrying out Knoevenagel condensation reaction to obtain a target dye compound 8, wherein the synthetic route is as follows:
3. the method for preparing the pure organic photosensitive dye with the stepped energy transmission structure according to claim 2, wherein the method comprises the following steps:
step one, slowly dropwise adding phosphorus oxychloride into dry N, N' -dimethylformamide under the protection of nitrogen to prepare a Vilsmeier reagent, then dropwise adding a mixed solution of the compound 1 and a reaction solvent into the Vilsmeier reagent, reacting at a temperature of between 0 and 45 ℃ for 10 to 16 hours to obtain a compound 2; compound 1: phosphorus oxychloride: the molar ratio of N, N' -dimethylformamide is 1: 1-2: 2 to 4;
step two, under the protection of nitrogen, in the presence of tetrahydrofuran and sodium hydride, dissolving the compound 2 and the compound 3 in dry dimethyl sulfoxide, and carrying out a Wittig reaction for 4-10 h to obtain a compound 4, wherein the molar ratio of the compound 2 to the compound 3 is 1:1 to 5;
step three, adding the compound 4 and the compound 5 into a tertiary amyl alcohol solvent under the catalysis of ferrous chloride in the presence of the tertiary amyl alcohol solvent and metallic sodium, and carrying out reflux reaction for 1-5 h to obtain a compound 6, wherein the molar ratio of the compound 4 to the compound 5 is 1:1 to 4;
step four, slowly dropwise adding phosphorus oxychloride into dry N, N' -dimethylformamide under the protection of nitrogen to prepare a Vilsmeier reagent, then dropwise adding the mixed solution of the compound 6 and dichloromethane into the Vilsmeier reagent, reacting at the temperature of 0-45 ℃ for 8-16 hours to obtain the compound 7;
step five, under the protection of nitrogen, mixing the compound 7 with cyanoacetic acid in the presence of acetonitrile, adding a catalyst piperidine into the mixture, and carrying out Knoevenagel condensation reaction for 8-10 h to obtain a target dye compound 8, wherein the molar ratio of the compound 7 to the cyanoacetic acid is 1:1 to 5.
4. A method for preparing a pure organic photosensitive dye of a stepped energy transfer structure according to claim 3, wherein: in the fifth step, the target product compound 8 is subjected to post-treatment through the following steps: and after the reaction is completed, steaming to obtain a crude product, separating by adopting a rapid column chromatography, wherein the eluent is a mixed solution of dichloromethane and ethanol, and obtaining the organic dye.
5. The method for preparing the pure organic photosensitive dye with the stepped energy transmission structure according to claim 4, wherein the method comprises the following steps: the leaching solution is prepared from dichloromethane and ethanol, wherein the dichloromethane: the volume ratio of the ethanol is 15-40: 1.
6. the use of a pure organic photoactive dye of a stepped energy transfer structure according to claim 1 for the preparation of dye sensitized solar cells, wherein: the preparation method comprises the following steps: preparation of TiO by knife coating 2 Film, FTO conductive glass with substrate of sheet resistance 15 omega and TiO 2 The film is composed of an upper layer and a lower layer, and comprises a transparent layer of a bottom layer and a powder of an upper layerFiring the layer, calcining for 30 minutes at 450 ℃, and soaking the layer into a dye bath of the synthesized dye when the temperature is reduced to 80 ℃; the dye bath adopts ethanol: DMF volume ratio was 4:1 as a solvent, wherein the dye concentration is 0.25mM, and the concentration of the co-adsorbent cholic acid is 10mM; the electrolyte adopts 3-methoxy propionitrile: the volume ratio of acetonitrile is 4:1 as a solvent, wherein the concentration of the components is respectively 1.0M 1-hexyl-3-methylimidazole iodized salt, 30mM lithium iodide, 30mM iodine, 0.1M guanidine thiocyanate and 0.5M 4-tert-butylpyridine; the pure organic photosensitizing dye and the reference dye of the stepped energy transmission structure according to claim 1 were used as photosensitizing dyes, respectively, and the batteries were assembled according to the above-mentioned battery preparation steps, and then the photoelectric properties of the batteries were tested according to the same conditions.
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