CN103012491B - Method for synthesizing ruthenium complex through one-pot method - Google Patents
Method for synthesizing ruthenium complex through one-pot method Download PDFInfo
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- CN103012491B CN103012491B CN201210580432.5A CN201210580432A CN103012491B CN 103012491 B CN103012491 B CN 103012491B CN 201210580432 A CN201210580432 A CN 201210580432A CN 103012491 B CN103012491 B CN 103012491B
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Abstract
The invention discloses a method for synthesizing a ruthenium complex through a one-pot method, which comprises the following steps: A) reacting dichloro(p-cymene) ruthenium dimer and 4,4'-dinonyl-2,2'-bipyridine in polar organic solvent while heating, thus obtaining a (4,4'-dinonyl-2,2'-bipyridine)-chloro(p-cymene) ruthenium generation solution; B) adding 2,2'-bipyridine-4,4'-dicarboxylic acid into the generation solution obtained in the step A), and reacting while heating, thus obtaining a cis-dichloro-(4,4'-dinonyl-2,2'-bipyridine)-(2,2'-bipyridine-4,4'-dicarboxylic acid) ruthenium (II) complex generation solution; and C) adding isothiocyanate into the generation solution obtained in the step B), and reacting while heating, thus generating a cis-di(isothiocyano)-(4,4'-dinonyl-2,2'-bipyridine)-(2,2'-bipyridine-4,4'-dicarboxylic acid) ruthenium (II) complex. According to the method for synthesizing a ruthenium complex through a one-pot method, Ru(dnbpy)(dcbpy)(NCS)2 can be obtained with the advantages of high purity, high yield and low cost; the purity of the target product can be increased by 28%; and when the product is used for a dye-sensitized solar cell, the photoelectric conversion efficiency can be obviously increased by 50%.
Description
Technical field
The invention belongs to organic synthesis field, particularly relate to a kind of synthetic method of the ruthenium complex for dye-sensitized solar cell.
Background technology
The instead energy of fossil oil, the solar cell that make use of sunlight receives publicity, and people have carried out various research to it.Solar cell is a kind of is the photoelectric conversion device of electric energy by transform light energy, due to using sunlight as the energy, so minimum on the impact of global environment, can be popularized widely.
Apply by the dye-sensitized solar cell of the photoresponse electronics movement of dye sensitization (hereinafter referred to as DSSC(Dye-Sensitized Solar Cell)), instead the solar cell of future generation of silicon (Si) class solar cell etc. receives publicity in recent years, and is extensively studied.As sensitizing dye, use the material that effectively can absorb the light near visible ray, such as ruthenium (Ru) complex compound etc.
As dye-sensitized solar cell, owing to having higher photoelectric transformation efficiency, do not need the manufacturing installation of the large costs such as vacuum unit, and the cheap semiconductor materials such as titanium oxide can be used to manufacture simply with high productivity, so potentiality become the solar cell of a new generation.
A lot of institute is studied just energetically now, containing 4,4 '-dinonyl-2,2 '-bipyridine ligand (hereinafter referred to as " dnbpy " or " L1 ") and 2,2 '-dipyridyl-4,4 '-dicarboxylic acid (is also referred to as 4,4 '-dicarboxyl-2,2 '-dipyridyl, hereinafter referred to as " dcbpy " or " L2 ") the nanocrystalline titanium dioxide of ruthenium (II) complex compound sensitization.
The mesoporous type porous silica titanium film having adsorbed sensitizing dye is the key component of the novel solar battery of the photoelectric transformation efficiency guaranteeing to have 10% to 11%.In addition, ruthenium complex as sensitizing agent use in, solar cell shows satisfactory stability, and its actual be applied to into may.
At present, in dye sensitization solar battery, referred to as cis-two (isothiocyano)-(4 of Z907,4 '-dinonyl-2,2 '-dipyridyl)-(2,2 '-dipyridyl-4,4 '-dicarboxylic acid) close ruthenium (II) complex compound (hreinafter referred to as " Ru (dnbpy) (dcbpy) (NCS)
2" or " RuL1L2 (NCS)
2") be widely studied and use.There are very high requirement in the efficiency of dye sensitization solar battery and life-span for the purity of dyestuff, but the product purity using current synthetic method to obtain is low, needs to purify further, complex steps, inefficiency, cost intensive, limits their application in dye sensitization solar battery.
Synthesis about ruthenium complex dye has reported in literature, as non-patent literature 1 (Peng Wanget al, " A stable quasi-soid-state dye-sensitized solar cell with an amphiphilicruthenium sensitizer and polymer gel electrolyte " Nature materials, 2003,402 ~ 407) describe in Ru (dnbpy) (dcbpy) (NCS)
2synthetic method, comprising, by [RuCl
2(p-cymene)]
2with part dnbpy, stirring under nitrogen protection, 60 DEG C of reactions 4 hours; Part dcbpy is added in obtained solution, then back flow reaction 4 hours.Excessive NH is added in the most backward reaction solution
4nCS, back flow reaction 4 hours.
In addition at non-patent literature 2 (Md.K.Nazeeruddin et al, " Stepwise assembly ofamphiohilic ruthenium sensitizers and their applications in dye-sensitized solarcell " Coordination chemistriy Reviews, 2004,248,1317-1328) in describe [RuCl
2(p-cymene)]
2with part dnbpy, DMF at 55 ~ 65 DEG C, stirring under nitrogen protection, reacting 4 hours; After end, in the solution obtained, add dcbpy, react 4 hours at 155 ~ 165 DEG C.Finally add excessive NH
4nCS, back flow reaction 5 hours again at 140 ~ 150 DEG C.
The patent documentation 1(U.S. the 5th, 463, No. 057 patent) describe the synthetic method of analogous products in specification sheets embodiment 3,4.The first step synthesis RuCl
2(L) (DMSO), L is part, and DMSO is dimethyl sulfoxide (DMSO).By RuCl
2(DMSO) and 4,4 '-dimethyl-2,2 '-dipyridyl refluxes 1 hour in chloroform.Solvent is removed with Rotary Evaporators after solution cooling.The dissolution of solid obtained in acetone, filters.In filtrate, add ether, occur yellow mercury oxide.Filter, with washed with diethylether, vacuum-drying.Second step synthesis RuLL
2cl
2, wherein L is 4,4 '-dimethyl-2,2 '-dipyridyl, L
2be 4,4 '-dicarboxyl-2,2 '-dipyridyl.By RuCl
2l (DMSO)
2with 4,4 '-dicarboxyl-2,2 '-dipyridyl refluxes 3 ~ 4 hours in DMF.After reaction mixture filters, filtrate evaporate to dryness.The solution of solid acetone/diethyl ether=1/1 obtained, ether washs respectively, vacuum-drying.3rd step synthesis RuLL
2(SCN)
2, wherein L is 4,4 '-dimethyl-2,2 '-dipyridyl, L
2be 4,4 '-dicarboxyl-2,2 '-dipyridyl.RuLL
2cl
2with Sodium Thiocyanate 99 in the mixing solutions of DMF and water, reflux 6 hours under nitrogen protection.Be cooled to room temperature, filter, the HClO of the solid pH=3 obtained
4the aqueous solution, acetone-diethyl ether mixed solution, washed with diethylether, obtains product after drying.Method in this patent is to the RuCl as intermediate product
2(L) (DMSO) and RuLL
2cl
2carry out being separated, purifying, so need long time to obtaining final product.In addition, the isolation andpurification of intermediate product be result in the reduction of target product yield.
In the technology recorded in above-mentioned patent documentation and non-patent literature 1,2, the product purity obtained is lower, need could apply on the solar cell with the Methods For Purification of column chromatography further, and it is low by the method for Sephadex Lh-20 column chromatography not only efficiency of purifying, output is little, and with high costs, be unsuitable for production application.
Summary of the invention
The object of the invention is in the synthetic method in order to solve ruthenium in prior art (II) complex compound, the product purity obtained is low, need the technical problem using column chromatography to purify further, there is provided one can be in enormous quantities, high yield, high purity, without the need to cis-two (isothiocyano)-(4 of purifying, 4 '-dinonyl-2,2 '-dipyridyl)-(2,2 '-dipyridyl-4,4 '-dicarboxylic acid) close ruthenium (II) complex compound Ru (dnbpy) (dcbpy) (NCS)
2synthetic method.
The present invention adopts one pot process ruthenium complex, and the method comprises the steps:
Steps A), by Paracymene ruthenous chloride dimer ([RuCl
2(p-cymene)]
2) and 4,4 '-dinonyl-2,2 '-dipyridyl (dnbpy) reacting by heating in polar organic solvent, obtains (4,4 '-dinonyl-2,2 '-dipyridyl)-Paracymene ruthenium chloride (Ru (p-cymene) (dnbpy) Cl) generates liquid; Wherein, temperature of reaction is 30 DEG C ~ 50 DEG C, and the reaction times is 3 ~ 7 hours;
Step B), to steps A) obtain (4,4 '-dinonyl-2,2 '-dipyridyl)-Paracymene ruthenium chloride generates in liquid, add 2,2 '-dipyridyl-4,4 '-dicarboxylic acid (dcbpy), reacting by heating, obtain cis-two chloro-(4,4 '-dinonyl-2,2 '-dipyridyl)-(2,2 '-dipyridyl-4,4 '-dicarboxylic acid) close ruthenium (II) complex compound (Ru (dnbpy) (dcbpy) Cl
2) generate liquid; And
Step C), to step B) obtain cis-two chloro-(4,4 '-dinonyl-2,2 '-dipyridyl)-(2,2 '-dipyridyl-4,4 '-dicarboxylic acid) ruthenium complex generates in liquid, add isothiocyanate, reacting by heating, generate cis-two (isothiocyanos)-(4,4 '-dinonyl-2,2 '-dipyridyl)-(2,2 '-dipyridyl-4,4 '-dicarboxylic acid) close ruthenium (II) complex compound (Ru (dnbpy) (dcbpy) (NCS)
2).
By optimization step A) the reaction conditions such as temperature of reaction and reaction times, if temperature of reaction is 30 DEG C ~ 50 DEG C, preferably temperature of reaction is 40 DEG C ~ 50 DEG C, the reaction times is 3 ~ 7 hours, the synthesis of intermediate product Ru (p-cymene) (dnbpy) Cl can be made to carry out fully, reduce the growing amount of the by products such as isomer significantly.Compared with the situation being 55 DEG C to 65 DEG C with the first step temperature of reaction, can make target product Ru (dnbpy) (dcbpy) (NCS)
2purity improve about more than 28%, battery efficiency improve 50%.If the first step temperature of reaction is more than 55 DEG C, or the by product of time more than 7 hours then beyond target product generates significantly as precipitate, this by product makes solar battery efficiency significantly reduce, so be more preferably steps A) temperature of reaction be no more than this by product start separate out temperature 55 DEG C, the time is no more than 7 hours.Thus, cis-two (isothiocyano)-(4 of target product can be obtained with high purity, high yield, low cost, 4 '-dinonyl-2,2 '-dipyridyl)-(2,2 '-dipyridyl-4,4 '-dicarboxylic acid) close ruthenium (II) complex compound (Ru (dnbpy) (dcbpy) (NCS)
2).
In the present invention, term " one kettle way " refers to steps A), step B) the generation liquid that obtains does not carry out being separated, purification processes, the generation liquid obtained is directly used in next step, make steps A), step B), step C) in same reaction vessel, carry out One-step Synthesis, be called for short one kettle way (one-potsynthesis).Due in one kettle way, misalign a product { (4,4 '-dinonyl-2,2 '-dipyridyl)-Paracymene ruthenium chloride, cis-two chloro-(4,4 '-dinonyl-2,2 '-dipyridyl)-(2,2 '-dipyridyl-4,4 '-dicarboxylic acid) close ruthenium (II) complex compound } carry out being separated, purifying, so can be synthesized target product Ru (dnbpy) (dcbpy) (NCS) by simple operation
2.Save be separated, time required for purification intermediate product, avoid the reduction of the separation due to intermediate product, the yield caused of purifying.Steps A for one kettle way), step B by optimizing the reaction conditions such as temperature of reaction and reaction times, overall generated time can be shortened.
Be preferably, steps A) (4,4 '-dinonyl-2,2 '-dipyridyl)-Paracymene ruthenium chloride of obtaining generates liquid and is cooled to room temperature, then carry out step B).By such formation, the growing amount of the by products such as isomer can be reduced, obtain highly purified target product Ru (dnbpy) (dcbpy) (NCS)
2.
Wherein, described polar organic solvent is dimethyl formamide, obtains target product Ru (dnbpy) (dcbpy) (NCS) by using general organic solvent
2.
Wherein, described isothiocyanate is isothiocyanic acid ammonium, sodium isothiocyanate and/or isothiocyanic acid potassium.
Wherein, step B) and step C) reaction times and temperature all can refer to prior art, as: step B) react 3 ~ 7 hours at 150 ~ 165 DEG C, preferably 150 DEG C of reactions 4 hours.Step C) react 3 ~ 7 hours at 140 ~ 155 DEG C, preferably 150 DEG C are reacted 4 hours.
Positive progressive effect of the present invention is: the method for one pot process ruthenium complex of the present invention, can high purity, high yield, obtain Ru (dnbpy) (dcbpy) (NCS) at low cost
2, make the purity of target product improve 28%, be applied on dye sensitization solar battery, make photoelectric transformation efficiency significantly improve 50%.
Accompanying drawing explanation
Fig. 1 is the HPLC spectrogram of the Z907-1 that embodiment 1 is synthesized; Purity 67.1%, the peak of 15 minutes is target product Ru (dnbpy) (dcbpy) (NCS)
2, other peak is impurity peaks;
Fig. 2 is the HPLC spectrogram of the Z907-2 of the 2-in-1 one-tenth of embodiment; Purity 72.5%, the peak of 15 minutes is target product Ru (dnbpy) (dcbpy) (NCS)
2, other peak is impurity peaks;
Fig. 3 is the HPLC spectrogram of the Z907-0 that comparative examples 1 is synthesized; Purity 56.7%, the peak of 15 minutes is target product Ru (dnbpy) (dcbpy) (NCS) 2, and other peak is impurity peaks;
Fig. 4 comparative examples (Z907-0), embodiment 1(Z907-1) and embodiment 2(Z907-2) I-V graphic representation; And
Fig. 5 comparative examples (Z907-0), embodiment 1(Z907-1) and embodiment 2(Z907-2) IPCE spectrogram.
Embodiment
Cis-two (isothiocyano)-(4 of the present invention, 4 '-dinonyl-2,2 '-dipyridyl)-(2,2 '-dipyridyl-4,4 '-dicarboxylic acid) close ruthenium (II) complex compound (Ru (dnbpy) (dcbpy) (NCS)
2) synthesis flow as follows:
Embodiment 1Ru (dnbpy) (dcbpy) (NCS)
2(Z907-1) synthesis
Steps A) synthesis of Ru (p-cymene) (dnbpy) Cl
Paracymene ruthenous chloride dimer (0.8g, 1.28mmol) that will be dissolved in DMF (150mL) solvent adds three-necked round bottom flask, three-necked round bottom flask aluminium foil is wrapped up, in lucifuge and Ar gas atmosphere, by solution stirring after 15 minutes, in solution, add 4,4 '-dinonyl-2,2 '-dipyridyl (1.06g, 2.56mmol), in lucifuge and Ar gas atmosphere, by solvothermal to 40 DEG C, react 4 hours.Be cooled to room temperature afterwards.
Step B) Ru (dnbpy) (dcbpy) Cl
2synthesis
In steps A) add 4,4 '-dicarboxyl-2,2 '-dipyridyl (0.8g, 2.56mmol) in reacted three-necked round bottom flask, at 150 DEG C, react 4 hours again.
Step C) Ru (dnbpy) (dcbpy) (NCS)
2synthesis
Again in step B) add NH in reacted flask
4nCS (8g, 0.14mol), reacts 4 hours again at 150 DEG C.After being cooled to room temperature, with Rotary Evaporators DMF evaporate to dryness, in remaining liq, add 0.5M NaOH solution (15mL), obtain dark red liquid.Solution adds 0.5M HNO after filtering
3, there is red precipitate in (about 8mL) acidifying.Put into refrigerator and cooled but to spend the night, after returning back to room temperature, filter, 0.1M HNO used respectively by the solid obtained
3the aqueous solution and ether: the liquid scrubbing of sherwood oil=1:1.Crude product is dissolved in the 0.2M NaOH aqueous solution (15mL), then adds 0.5M HNO
3, there is red precipitate in acidifying.Put into refrigerator and cooled but to spend the night, after returning back to room temperature, filter, 0.1M HNO used respectively by the solid obtained
3the aqueous solution and ether: the liquid scrubbing of sherwood oil=1:1, dry.Obtain target product 2.04g, productive rate 91.7%, purity 67.1%.HPLC spectrogram as shown in Figure 1.
Embodiment 2Ru (dnbpy) (dcbpy) (NCS)
2(Z907-2) synthesis
Steps A) synthesis of Ru (p-cymene) (dnbpy) Cl
Paracymene ruthenous chloride dimer (0.8g, 1.28mmol) that will be dissolved in DMF (150mL) solvent adds three-necked round bottom flask, three-necked round bottom flask aluminium foil is wrapped up, in lucifuge and Ar gas atmosphere, by solution stirring after 15 minutes, in solution, add 4,4 '-dinonyl-2,2 '-dipyridyl (1.06g, 2.56mmol), in lucifuge and Ar gas atmosphere, by solvothermal to 40 DEG C, react 6 hours.Be cooled to room temperature afterwards.
Step B) Ru (dnbpy) (dcbpy) Cl
2synthesis
In steps A) add 4,4 '-dicarboxyl-2,2 '-dipyridyl (0.8g, 2.56mmol) in reacted flask, at 150 DEG C, react 4 hours again.
Step C) Ru (dnbpy) (dcbpy) (NCS)
2synthesis
Again in step B) add NH in reacted flask
4nCS (8g, 0.14mol), reacts 4 hours again at 150 DEG C.After being cooled to room temperature, with Rotary Evaporators DMF evaporate to dryness, in remaining liq, add 0.5M NaOH solution (15mL), obtain dark red liquid.Solution adds 0.5M HNO after filtering
3, there is red precipitate in (about 8mL) acidifying.Put into refrigerator and cooled but to spend the night, after returning back to room temperature, filter, 0.1M HNO used respectively by the solid obtained
3the aqueous solution and ether: the liquid scrubbing of sherwood oil=1:1.Crude product is dissolved in the 0.2M NaOH aqueous solution (15mL), then adds 0.5M HNO
3, there is red precipitate in acidifying.Put into refrigerator and cooled but to spend the night, after returning back to room temperature, filter, 0.1M HNO used respectively by the solid obtained
3the aqueous solution and ether: the liquid scrubbing of sherwood oil=1:1, dry.Obtain product 2.06g, productive rate 92.5%, purity 72.5%.HPLC spectrogram as shown in Figure 2.
Embodiment 3Ru (dnbpy) (dcbpy) (NCS)
2(Z907-3) synthesis
Steps A) synthesis of Ru (p-cymene) (dnbpy) Cl
Paracymene ruthenous chloride dimer (0.8g, 1.28mmol) that will be dissolved in DMF (150mL) solvent adds three-necked round bottom flask, three-necked round bottom flask aluminium foil is wrapped up, in lucifuge and Ar gas atmosphere, by solution stirring after 15 minutes, in solution, add 4,4 '-dinonyl-2,2 '-dipyridyl (1.06g, 2.56mmol), in lucifuge and Ar gas atmosphere, by solvothermal to 30 DEG C, react 4 hours.Be cooled to room temperature afterwards.
Step B) Ru (dnbpy) (dcbpy) Cl
2synthesis
In steps A) add 4,4 '-dicarboxyl-2,2 '-dipyridyl (0.8g, 2.56mmol) in reacted flask, at 150 DEG C, react 4 hours again.
Step C) Ru (dnbpy) (dcbpy) (NCS)
2synthesis
Again in step B) add NH in reacted flask
4nCS (8g, 0.14mol), reacts 4 hours again at 150 DEG C.After being cooled to room temperature, with Rotary Evaporators DMF evaporate to dryness, in remaining liq, add 0.5M NaOH solution (15mL), obtain dark red liquid.Solution adds 0.5M HNO after filtering
3, there is red precipitate in (about 8mL) acidifying.Put into refrigerator and cooled but to spend the night, after returning back to room temperature, filter, 0.1M HNO used respectively by the solid obtained
3the aqueous solution and ether: the liquid scrubbing of sherwood oil=1:1.Crude product is dissolved in the 0.2M NaOH aqueous solution (15mL), then adds 0.5M HNO
3, there is red precipitate in acidifying.Put into refrigerator and cooled but to spend the night, after returning back to room temperature, filter, 0.1M HNO used respectively by the solid obtained
3the aqueous solution and ether: the liquid scrubbing of sherwood oil=1:1, dry.Obtain product 2.06g, productive rate 91.2%, purity 63.4%.
Embodiment 4Ru (dnbpy) (dcbpy) (NCS)
2(Z907-4) synthesis
Steps A) synthesis of Ru (p-cymene) (dnbpy) Cl
Paracymene ruthenous chloride dimer (0.8g, 1.28mmol) that will be dissolved in DMF (150mL) solvent adds three-necked round bottom flask, three-necked round bottom flask aluminium foil is wrapped up, in lucifuge and Ar gas atmosphere, by solution stirring after 15 minutes, in solution, add 4,4 '-dinonyl-2,2 '-dipyridyl (1.06g, 2.56mmol), in lucifuge and Ar gas atmosphere, by solvothermal to 50 DEG C, react 4 hours.Be cooled to room temperature afterwards.
Step B) Ru (dnbpy) (dcbpy) Cl
2synthesis
In steps A) add 4,4 '-dicarboxyl-2,2 '-dipyridyl (0.8g, 2.56mmol) in reacted flask, at 150 DEG C, react 4 hours again.
Step C) Ru (dnbpy) (dcbpy) (NCS)
2synthesis
Again in step B) add NH in reacted flask
4nCS (8g, 0.14mol), reacts 4 hours again at 150 DEG C.After being cooled to room temperature, with Rotary Evaporators DMF evaporate to dryness, in remaining liq, add 0.5M NaOH solution (15mL), obtain dark red liquid.Solution adds 0.5M HNO after filtering
3, there is red precipitate in (about 8mL) acidifying.Put into refrigerator and cooled but to spend the night, after returning back to room temperature, filter, 0.1M HNO used respectively by the solid obtained
3the aqueous solution and ether: the liquid scrubbing of sherwood oil=1:1.Crude product is dissolved in the 0.2M NaOH aqueous solution (15mL), then adds 0.5M HNO
3, there is red precipitate in acidifying.Put into refrigerator and cooled but to spend the night, after returning back to room temperature, filter, 0.1M HNO used respectively by the solid obtained
3the aqueous solution and ether: the liquid scrubbing of sherwood oil=1:1, dry.Obtain product 2.06g, productive rate 91.5%, purity 66.3%.
Embodiment 5Ru (dnbpy) (dcbpy) (NCS)
2(Z907-5) synthesis
Steps A) synthesis of Ru (p-cymene) (dnbpy) Cl
Paracymene ruthenous chloride dimer (0.8g, 1.28mmol) that will be dissolved in DMF (150mL) solvent adds three-necked round bottom flask, three-necked round bottom flask aluminium foil is wrapped up, in lucifuge and Ar gas atmosphere, by solution stirring after 15 minutes, in solution, add 4,4 '-dinonyl-2,2 '-dipyridyl (1.06g, 2.56mmol), in lucifuge and Ar gas atmosphere, by solvothermal to 40 DEG C, react 3 hours.Be cooled to room temperature afterwards.
Step B) Ru (dnbpy) (dcbpy) Cl
2synthesis
In steps A) add 4,4 '-dicarboxyl-2,2 '-dipyridyl (0.8g, 2.56mmol) in reacted flask, at 150 DEG C, react 4 hours again.
Step C) Ru (dnbpy) (dcbpy) (NCS)
2synthesis
Again in step B) add NH in reacted flask
4nCS (8g, 0.14mol), reacts 4 hours again at 150 DEG C.After being cooled to room temperature, with Rotary Evaporators DMF evaporate to dryness, in remaining liq, add 0.5M NaOH solution (15mL), obtain dark red liquid.Solution adds 0.5M HNO after filtering
3, there is red precipitate in (about 8mL) acidifying.Put into refrigerator and cooled but to spend the night, after returning back to room temperature, filter, 0.1M HNO used respectively by the solid obtained
3the aqueous solution and ether: the liquid scrubbing of sherwood oil=1:1.Crude product is dissolved in the 0.2M NaOH aqueous solution (15mL), then adds 0.5M HNO
3, there is red precipitate in acidifying.Put into refrigerator and cooled but to spend the night, after returning back to room temperature, filter, 0.1M HNO used respectively by the solid obtained
3the aqueous solution and ether: the liquid scrubbing of sherwood oil=1:1, dry.Obtain product 2.06g, productive rate 91.1%, purity 62.1%.
Comparative examples 1 is by non-patent literature 1, method synthesis Ru (dnbpy) (dcbpy) (NCS) that non-patent literature 2 is identical
2(Z907-0).
Steps A) synthesis of Ru (p-cymene) (dnbpy) Cl
Paracymene ruthenous chloride dimer (0.8g, 1.28mmol) that will be dissolved in DMF (150mL) solvent adds three-necked round bottom flask, three-necked round bottom flask aluminium foil is wrapped up, in lucifuge and Ar gas atmosphere, by solution stirring after 15 minutes, in solution, add 4,4 '-dinonyl-2,2 '-dipyridyl (1.06g, 2.56mmol), in lucifuge and Ar gas atmosphere, by solvothermal to 60 DEG C, react 4 hours.
Step B) Ru (dnbpy) (dcbpy) Cl
2synthesis
In steps A) add 4,4 '-dicarboxyl-2,2 '-dipyridyl (0.8g, 2.56mmol) in reacted flask, at 150 DEG C, react 4 hours again.
Step C) Ru (dnbpy) (dcbpy) (NCS)
2synthesis
In step B) add NH in reacted flask
4nCS (8g, 0.14mol), reacts 4 hours again at 150 DEG C.After being cooled to room temperature, with Rotary Evaporators DMF evaporate to dryness, in remaining liq, add water (50mL), occur red precipitate.Filter, the liquid scrubbing of water and ether used respectively by the solid obtained.As a result, obtain solid Ru (dnbpy) (dcbpy) (NCS)
22.03g, yield is 91%, purity 56.7%.HPLC spectrogram as shown in Figure 3.
Table 1 comparative examples, embodiment 1,3 and 4 synthesis Ru (dnbpy) (dcbpy) (NCS)
2(Z907-1, Z907-3, Z907-4) compares
Result shows: as can be seen from Table 1, Ru (dnbpy) (dcbpy) (NCS)
2the purity of Z907 brings up to 66.3% from 56.7%.
Table 2 embodiment 1, embodiment 2 and embodiment 5 are synthesized Ru (dnbpy) (dcbpy) (NCS)
2(Z907-1, Z907-2, Z907-5) compares
Result shows: as can be seen from Table 2, Ru (dnbpy) (dcbpy) (NCS)
2the purity of Z907 brings up to 72.5% from 62.1%.
Ru (dnbpy) (dcbpy) (NCS) of effect example test comparison embodiment 1, embodiment 1, the 2-in-1 one-tenth of embodiment
2(Z907-0, Z907-1, Z907-2) dyestuffs purity is on the impact of the efficiency of solar cell.
1. the making of dye solution
Z907-0, Z907-1, Z907-2 are dissolved in acetonitrile respectively: in the solvent of the trimethyl carbinol=1:1, are made into the dye solution of 0.4M.
2.TiO
2the making of electrode
The commercially available TiO that particle diameter is 20nm
2slurry silk screen brush method is coated on FTO conductive glass surface, is placed in retort furnace and sinters 2 hours at 500 DEG C, obtain the TiO of 20 μm
2film.TiO
2electrode soaks 2 days in dye solution.
3. battery makes
TiO
2electrode and commercially available Pt electrode hot melt adhesive engage, and inject electrolytic solution.
4. test by the standard light source of AM1.5, result is as shown in table 3, Fig. 4 and Fig. 5.
Ru (dnbpy) (dcbpy) (NCS) that table 3 comparative examples, embodiment 1 and embodiment 2 obtain
2(Z907-0, Z907-1, Z907-2) carries out solar cell characterization result
Result shows: as can be seen from table 3, Fig. 4 and Fig. 5, Ru (dnbpy) (dcbpy) (NCS)
2the purity of Z907 brings up to 72.5% from 56.7%.The photoelectric transformation efficiency of battery brings up to 4.5% from 3%, and the photoelectric transformation efficiency under all-wave is long also significantly strengthens.Therefore, at target product Ru (dnbpy) (dcbpy) (NCS)
2the purity of Z907 improves on the basis of 28%, and photoelectric transformation efficiency significantly improves 50%.
Claims (8)
1. utilize a method for one pot process ruthenium complex, comprising:
Steps A), by Paracymene ruthenous chloride dimer and 4,4 '-dinonyl-2,2 '-dipyridyl reacting by heating in polar organic solvent, obtains (4,4 '-dinonyl-2,2 '-dipyridyl)-Paracymene ruthenium chloride and generates liquid; Wherein, temperature of reaction is 30 DEG C ~ 50 DEG C, and the reaction times is 3 ~ 7 hours, and wherein, described polar organic solvent is dimethyl formamide;
Step B), to steps A) obtain (4,4 '-dinonyl-2,2 '-dipyridyl)-Paracymene ruthenium chloride generates in liquid, add 2,2 '-dipyridyl-4,4 '-dicarboxylic acid, reacting by heating, obtain cis-two chloro-(4,4 '-dinonyl-2,2 '-dipyridyl)-(2,2 '-dipyridyl-4,4 '-dicarboxylic acid) close ruthenium (II) complex compound generation liquid; And
Step C), to step B) obtain cis-two chloro-(4,4 '-dinonyl-2,2 '-dipyridyl)-(2,2 '-dipyridyl-4,4 '-dicarboxylic acid) ruthenium complex generates in liquid, adds isothiocyanate, reacting by heating, generate cis-two (isothiocyanos)-(4,4 '-dinonyl-2,2 '-dipyridyl)-(2,2 '-dipyridyl-4,4 '-dicarboxylic acid) close ruthenium (II) complex compound.
2. method according to claim 1, is characterized in that, steps A) temperature of reaction be 40 DEG C ~ 50 DEG C.
3. method according to claim 1, is characterized in that, steps A) (4,4 '-dinonyl-2,2 '-dipyridyl)-Paracymene ruthenium chloride of obtaining generates liquid and is cooled to room temperature, then carry out step B).
4. method according to claim 1, is characterized in that, described isothiocyanate is isothiocyanic acid ammonium, sodium isothiocyanate and/or isothiocyanic acid potassium.
5. method according to claim 1, is characterized in that, step B) react 3 ~ 7 hours at 150 ~ 165 DEG C.
6. method according to claim 5, is characterized in that, step B) 150 DEG C of reactions 4 hours.
7. method according to claim 1, is characterized in that, step C) react 3 ~ 7 hours at 140 ~ 155 DEG C.
8. method according to claim 7, is characterized in that, step C) 150 DEG C of reactions 4 hours.
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