CN103145761B - Utilize the method for recrystallization method purification Ruthenium complex crude product - Google Patents

Utilize the method for recrystallization method purification Ruthenium complex crude product Download PDF

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CN103145761B
CN103145761B CN201210580732.3A CN201210580732A CN103145761B CN 103145761 B CN103145761 B CN 103145761B CN 201210580732 A CN201210580732 A CN 201210580732A CN 103145761 B CN103145761 B CN 103145761B
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ruthenium complex
solvent
formula
crude product
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CN103145761A (en
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詹文海
杨松旺
李勇明
刘岩
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Jiangsu Institute Of Advanced Inorganic Materials
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Shanghai Institute of Ceramics of CAS
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    • Y02E10/542—Dye sensitized solar cells

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Abstract

The invention discloses a kind of method utilizing recrystallization method purification Ruthenium complex crude product, it comprises the steps: steps A) dipyridyl Ruthenium complex crude product is dissolved in mixed solvent under stirring heating, form saturated solution, filtered while hot removes insoluble impurities; Wherein, described mixed solvent comprises high-dissolvability solvent and low solubility solvent; Step B) slowly cool to room temperature, then freezing crystallize out gradually; And step C) filter, drying obtains ruthenium complex product.Of the present invention method is simple, is applicable to scale operation, and output is high, and cost is low, the feature such as short consuming time, the product purity after purification is high, quality better, can significantly improve the photoelectric transformation efficiency of dye sensitization solar battery, enhance device stability, has broad application prospects.

Description

Utilize the method for recrystallization method purification Ruthenium complex crude product
Technical field
The present invention relates to a kind of method of Ruthenium complex crude product of purifying.
Background technology
Because oil crisis grows in intensity, sun power is more and more subject to the extensive attention of countries in the world as one of renewable energy source.1991, Lausanne, SUI engineering college with O ' Regan publishes an article on world-renowned periodical Nature, reports a kind of novel solar battery, take nano-crystalline titanium dioxide as opto-electronic conversion semi-conductor, dyestuff is photosensitizer, and battery efficiency is record-breaking reaches 7.1% ~ 7.9%.2011, deng people with based on Co(II/III) redox couple of four (dipyridyls) is for electrolytic solution, and with porphyrin as sensitizing agent, photoelectric transformation efficiency reaches 12.3%, is current reported maximum.Dye sensitization solar battery, as solar photo-electric conversion device of new generation, has all started research boom in the world, actively prepares to gain the initiative.
In dye sensitization solar battery, titanium dioxide semiconductor film has the characteristic of opto-electronic conversion as working electrode, but due to the restriction of self character, the visible ray in solar spectrum and near infrared light cannot be utilized, so in the making processes of working electrode, require titanium dioxide electrodes to soak in the dye solution of 0.1 ~ 0.3M, absorption sensitizing agent, to widen the light abstraction width of solar cell.
Dyestuff is as the key components of dye sensitization solar battery, and the feasibility for the photoelectric transformation efficiency of solar cell, life-span, cost and scale operation has vital impact.Bipyridyl ruthenium complex compound is the sensitizing agent being applied to dye sensitization solar battery the earliest, and Stability Analysis of Structures, efficiency is high, the feasibility with practical application, and as the star molecule of opto-electronic conversion, research enthusiasm does not go downhill permanently.Bipyridyl ruthenium (Ru) complex compound such as shown in formula I is exactly the one in dyestuff.
Wherein, X 1for formula (2) ~ (19) one of them and X 2for hydrogen, or X 1with X 2be all formula (2) ~ (19) one of them;
Wherein, R 1~ R 40be independently H, C th 2t+1(t=1 ~ 15), OC vh 2v+1(v=1 ~ 15), SC wh 2w+1(w=1 ~ 15) or be expression (36) ~ (37) one of them, and n is 0 ~ 2, m is 1 ~ 4, wherein, Y 1for sulphur (S), methene (CH 2), (R is H or C to ammonium (N-R) xh 2x+1(x=1 ~ 15) one of them), oxygen (O) or selenium (Se) one of them;
Y in its Chinese style (2) ~ (19) 2can be independently formula (20) ~ (37) one of them;
Wherein, i=1 ~ 15 in formula (21), and wherein, j=1 ~ 15 in formula (22), and k=1 ~ 15 in (23), wherein R 41~ R 45, R 48~ R 58be independently H, C ah 2A+1(A=1 ~ 15), OC bh 2B+1(B=1 ~ 15), SC dh 2D+1(D=1 ~ 15) or be expression (36) ~ (37); Wherein, R 46~ R 47, be independently H, C eh 2E+1(E=1 ~ 6) or OC fh 2F+1(F=1 ~ 6) or SC gh 2G+1(G=1 ~ 15), its Chinese style (36) and the R in formula (37) 59with R 60be independently H or C jh 2J+1(J=1 ~ 15) and r is 0 ~ 6, and formula (24), formula (26), formula (27), formula (28) and C in formula (29) qh 2qq=1 ~ 3;
Wherein Z 1for formula (38) ~ (44) one of them.Wherein Z 2for hydrogen or formula (38) ~ (44) one of them or be Z 1with Z 2for identical group;
Wherein, R 61with R 62be independently H, C ih 2I+1(I=1 ~ 15), OC jh 2J+1(J=1 ~ 15) or SC kh 2K+1(K=1 ~ 15) one of them; Wherein A 1represent hydrogen, lithium, sodium, potassium, quarternary ammonium salt (such as formula (45) Suo Shi) or other positively charged ion or group;
Wherein, R 63~ R 66be independently H or C yh 2y+1(y=1 ~ 15).
It is important to note that as the X in formula (1) 2for H, Z 1with Z 2be all formula (38), X 1for formula (2) ~ (5) one of them, and n=0, Y in formula (2) ~ (5) 1during for sulphur (S), then the Y in formula (2) ~ (5) 2be not formula (20), formula (21) or formula (22).
In addition, as the Z in formula (1) 1with Z 2be all formula (38) and X 1with X 2be all formula (2) ~ (5) one of them, and n=0, Y in formula (2) ~ (5) 1during for sulphur (S), then the Y in formula (2) ~ (5) 2be not formula (20), formula (21) or formula (22).
Particularly, the structure of bipyridyl ruthenium Complex dyes as shown in following formula (61) ~ (76), Z 1with Z 2be all formula (38) or formula (40).
Wherein, the R in formula (61) 67, R 68, R 69with R 70be independently H, C eh 2E+1(E=1 ~ 6), OC fh 2F+1(F=1 ~ 6), SC gh 2G+1(G=1 ~ 15) or be formula (36) ~ (37) one of them; R in formula (62) 71, R 72, R 73with R 74be independently H, C ah 2A+1(A=1 ~ 15), OC bh 2B+1(B=1 ~ 15) or SC dh 2D+1(D=1 ~ 15) or be formula (36) ~ (37) one of them; R in formula (63) 75with R 76be independently H, C th 2t+1(t=1 ~ 15), OC vh 2v+1(v=1 ~ 15) or SC wh 2w+1(w=1 ~ 15) or be formula (36) ~ (37) one of them; R in formula (64) ~ (66) 77, R 78, R 79, R 80, R 81with R 82be independently SC gh 2G+1(G=1 ~ 15) or be formula (36) ~ (37) one of them; R in formula (67) 83, R 84, R 85with R 86be independently H, C ah 2A+1(A=1 ~ 15), OC bh 2B+1(B=1 ~ 15), SC dh 2D+1(D=1 ~ 15) or be formula (36) ~ (37) one of them; R in formula (75) ~ (76) 87, R 88, R 89with R 90be independently H or C jh 2J+1(J=1 ~ 15) one of them.
A in formula (61) ~ (76) 1be independently hydrogen, lithium, sodium, potassium, quarternary ammonium salt (such as formula (45) Suo Shi).
Wherein, R 63, R 64, R 65with R 66be independently H or C yh 2y+1(y=1 ~ 20).
The bipyridyl ruthenium Complex dyes synthesized in the existing document of part is not purified further, but be directly used as the sensitizing agent of solar cell, as non-patent literature 1, non-patent literature 2, non-patent literature 3, patent documentation 1, patent documentation 2, patent documentation 3.But be through experimental verification, the thick product of dyestuff, due to containing unreacted raw material, by product and some other isomer, makes power conversion efficiency (pce) low, poor stability.But highly purified bipyridyl ruthenium Complex dyes is expensive, occupies very large share in the production cost of whole solar module, constrains the application of dye sensitization solar battery.And cost of purifying in the making processes of dyestuff occupies the over half of cost.Bipyridyl ruthenium Complex dyes has the feature that crystal property is poor, polarity is large, and these all cause the difficulty of purification.Having no idea to be purified by common silicagel column, is generally that the chromatography column being filler by SephadexLH-20 is separated, as non-patent literature 4, non-patent literature 5, patent documentation 4 in document.This filler is expensive, and material is very easily deteriorated, and after repeatedly using, refining effect is difficult to ensure.The a large amount of high-purity solvent consumed in purification process make cost remain high further.On the other hand, although material cost is high, the product production that column chromatography provides but still cannot meet the demands.
Although patent documentation 5 provides the method for the light-sensitive coloring agents such as a kind of preparative high-performance liquid chromatographic purification Z907 in addition, thus the light-sensitive coloring agent such as Z907 of high purity, high-quality can be obtained.The structural formula of Z907 as the formula (1),
Wherein, Z 1with Z 2be all-COOH, and X 1with X 2be all-C 9h 19.
But preparative high-performance liquid chromatographic is larger than SephadexLH-20 chromatography column limitation, requirement as envrionment conditions is harsher, the maintenance cost etc. of instrument, and preparation scale performance liquid chromatographic column and a large amount of highly purified high performance liquid phase level reagent consumed in purifying make cost higher.Preparation scale performance liquid chromatographic column diameter is no more than 5 centimetres simultaneously, and each sample size is no more than 20 milliliters, and the product obtained after primary purification is more less than SephadexLH-20 chromatography column.
This just causes difficulty to large-scale production, and along with the raising of output, the space that equipment cost, material cost and human cost significantly do not decline.
Non-patent literature 1:P.Liskaetal, " cis-Diaquabis (2; 2'-bipyridyl-4; 4 '-dicarboxylate)-ruthenium (II) SensitizesWideBandGapOxideSemiconductorsVeryEfficientlyo veraBroadSpectralRangeintheVisible ", J.Am.Chem.Soc.1988,110,3686 ~ 3687 (p3686);
Non-patent literature 2:M.K.Nazeeruddinetal, " ConversionofLighttoElectricitybycis-X 2bis (2,2 '-bipyridyl-4,4 '-dicarboxylate) ruthenium (II) Charge-TransferSensitizers (X=Cl-, Br-, I-, CN-, andSCN-) onNanocrystallineTiO 2electrodes ", J.Am.Chem.Soc.1993,115,6382 ~ 6390 (p6383:Materials);
Non-patent literature 3:Md.K.Nazeeruddinetal, " Acid-BaseEquilibriaof (2; 2'-bipyridyl-4; 4'-dicarboxylicacid) ruthenium (II) ComplexesandtheEffectofProtonationonCharge-TransferSensi tizationofNanocrystallineTitania ", Inorg.Chem.1999,38,6298 ~ 6305 (p6299:Synthesisofcomplexs1, and2, p6303:HPLCofcomplex2)
Non-patent literature 4:M.K.Nazeeruddinetal, " Engineeringofefficientpanchromaticsensitizersfornanocrys tallineTiO 2-basedsolarcells ", J.Am.Chem.2001,123,1613-1624 (p483:Synthesis)
Non-patent literature 5:PengWangetal, " Astablequasi-solid-statedye-sensitizedsolarcellwithanamp hiphilicrutheniumsensitizerandpolymergelelectrolyte " Naturematerials, 2003,402 ~ 407 (p406:Methods)
Patent documentation 1: United States Patent (USP) No. 5463057 specification sheets (embodiment 1, embodiment 2);
Patent documentation 2: Unexamined Patent 11-279188 publication (paragraph 0004 to 0005);
Patent documentation 3: JP 2001-139587 publication (paragraph 0004 to 0005);
Patent documentation 4: US Patent No. 2007/0265443A1
Patent documentation 5: US Patent No. 2010/0275391A1
Summary of the invention
The present invention is exactly for the problems referred to above, provides a kind of new method of purification to improve the purity of bipyridyl ruthenium Complex dyes, make it to reach and exceed column chromatography purify after dyestuff apply on the solar cell after photoelectric transformation efficiency.Increase substantially production efficiency simultaneously, improve output, reduce material cost, equipment cost and human cost.
The present invention utilizes recrystallization method purification Ruthenium complex crude product, and the method comprises the steps:
Steps A) dipyridyl Ruthenium complex crude product is dissolved in mixed solvent under stirring heating, form saturated solution, filtered while hot removes insoluble impurities; Wherein, described mixed solvent comprises high-dissolvability solvent and low solubility solvent;
Step B) slowly cool to room temperature, then freezing crystallize out gradually; And
Step C) filter, drying obtains ruthenium complex product.
Steps A) by after dipyridyl Ruthenium complex crude product is mixed with appropriate mixed solvent, dissolve completely after being heated to proper temperature, form saturated solution, bipyridyl ruthenium complex compound can be made under cold condition subsequently to separate out solid gradually by self-assembly behavior.
Wherein, steps A) in, described high-dissolvability solvent is the solvent solubleness of ruthenium complex being greater than to 1g/mL, comprise tetrahydrofuran (THF), N, N '-dimethyl methane amide, N, N '-diethylformamide, N, N '-dipropyl formamide, tetramethyl ammonium hydroxide solution, tetraethyl ammonium hydroxide solution, TBAH solution, acetone and/or butanone, be preferably tetrahydrofuran (THF), N, N '-dimethyl methane amide, N, N '-diethylformamide, acetone and/or butanone; Described low solubility solvent is the solvent solubleness of ruthenium complex being less than to 0.1g/mL, comprise ethyl acetate, sherwood oil, ether, methyl-phenoxide, phenyl ethyl ether, chloroform, methylene dichloride, acetonitrile, ethanol, methyl alcohol, formaldehyde, formic acid, acetic acid, benzene, toluene, phenylformic acid, normal hexane, hexanaphthene, chlorobenzene, iodobenzene and/or water, be preferably chloroform, acetonitrile, ethanol, methyl alcohol and/or water.
Preferably, steps A) in, every gram of dipyridyl Ruthenium complex crude product is dissolved in the mixed solvent comprising 5 ~ 20mL high-dissolvability solvent and 10 ~ 200mL low solubility solvent.Consumption like this can guarantee that dipyridyl Ruthenium complex crude product is dissolved completely under Elevated Temperature Conditions, be unlikely to again to cause because the solvability of solvent is too strong not have solid to separate out or output too low; And can guarantee that the bipyridyl ruthenium complex product after purifying has quite high quality.
Steps A) in, be preferably heated to 30 ~ 150 DEG C, be more preferably heated to 50 ~ 80 DEG C, preferably keep 0.5 ~ 3 hour, more preferably keep 0.5 ~ 1 hour.Operation like this, can guarantee that bipyridyl ruthenium complex molecules is dissolved completely.
Steps A) in stirring can use mechanical stirring or magnetic agitation mixing.
Steps A) in, the temperature that filtered while hot articles for use used are preheated to the temperature ~ saturated solution of saturated solution as funnel, filter paper, filter membrane, filter flask etc. adds 10 DEG C, and the envrionment temperature of filtered while hot is the temperature of saturated solution.Operation like this can guarantee that bipyridyl ruthenium complex compound can not separate out solid because temperature reduces suddenly in the process of filtering, thus avoids unnecessary loss.
Step B) in, slowly cool to room temperature with the speed of 5 DEG C per hour, saturated solution can be avoided to separate out a large amount of solid at short notice because temperature reduces suddenly, and impurity also precipitates simultaneously, and bipyridyl ruthenium complex compound cannot form excellent crystal formation.
Step B) in, at-40 ~ 0 DEG C after cooling, preferably at-40 ~-10 DEG C, freezing 2 ~ 72 hours, preferably freezing 24 ~ 48 hours, crystallize out gradually.Operation like this can guarantee the complete crystalline deposit of high purity product, and makes follow-up filtration procedure become more simple to operation.
Step C) in, the membrane filtration of filtration filter paper or 1 ~ 10 μm.
Step C) in, described drying is preferably dry 12h ~ 48h, preferred dry 24h ~ 48h at 40 DEG C ~ 60 DEG C at 30 DEG C ~ 70 DEG C, or described drying is vacuum-drying.
According to the present invention, in the purification process of bipyridyl ruthenium complex compound, utilize saturated solution self-assembly behavior at low temperatures, recrystallization crystallize out, obtain highly purified bipyridyl ruthenium complex product.Do not use expensive SephadexLH-20 filler chromatography column or preparative liquid chromatography and a large amount of highly purified organic solvents, only need the most basic heating, cooling, filter and drying plant, consume a small amount of common solvent, cost is low, equipment is simple, easy and simple to handle, output is high, purity is high, excellent device performance, there is the feasibility of amplifying further and producing.
Accompanying drawing explanation
Fig. 1 is DMF consumption for the impact of output and purity;
Fig. 2 is the high performance liquid chromatography spectrogram of the bipyridyl ruthenium complex product that embodiment 1 obtains;
Fig. 3 is acetonitrile content for the impact of output and purity;
Fig. 4 is solvent temperature for the impact of output and purity; And
Fig. 5 is freezing temp for the impact of output and purity.
Embodiment
In the following example 1 ~ 28 and comparing embodiment, the bipyridyl ruthenium complex compound adopted is cis-two (isothiocyano)-(2, 2 '-dipyridyl-4, 4 '-dicarboxylic acid)-(4, 4 '-two (5-(5-octyl thiophene-2-base) thiophene-2-base)-second bipyridine) close ruthenium (II) complex compound (cis-di (thiocyanato) bis-(2, 2 '-bipyridyl-4, 4 '-dicarboxylate) (4, 4 '-bis (5-(5-octyl-thiophen-2-yl) thiophen-2-yl)-2, 2 '-bipiridine) ruthenium (II)), its code name is CYC-B1 or Z991, also can be expressed as Ru (dcbpy) (abtpy) (NCS) 2, its structural formula is such as formula shown in (71).
Wherein, A 1for H.Z991 is synthesized by the method for document (Angew.Chem.Ed.2006,45,5822-5825).
Comparing embodiment
According to non-patent literature 4 and non-patent literature 5, be filler with SephadexLH-20, methyl alcohol, water is that eluent carries out column chromatography purification, obtains the Z991 solid that purity is 96%.
The difference of embodiment 1 ~ 7 high-dissolvability solvent load
Cis-two (isothiocyano)-(2 of 1g, 2 '-dipyridyl-4,4 '-dicarboxylic acid)-(4,4 '-two (5-(5-octyl thiophene-2-base) thiophene-2-base)-second bipyridine) close ruthenium (II) complex compound (code name is CYC-B1 or Z991), N, after the mixing of dinethylformamide, 100mL acetonitrile, at 60 DEG C, mix 0.5 hour by magnetic agitation, terminate rear filtered while hot.Filter the funnel that uses, the pre-treatment 0.5 hour in 70 DEG C of baking ovens of filter flask and filter paper.After collecting filtrate, be placed in 60 DEG C of baking ovens, with the speed slow cooling of reduction per hour 5 DEG C to room temperature 25 DEG C.Then, place 24 hours in-30 DEG C of refrigerators.Take out after terminating, with the membrane filtration of 10 μm, collect the Z991 solid obtained, in the baking oven of 50 DEG C, drying 24 hours, obtains Z991 product.In every embodiment, the concrete consumption of high-dissolvability solvent and output and purity are as shown in table 1 and Fig. 1.
The relation of the consumption of table 1 high-dissolvability solvent and the Z991 product production purity of acquisition
The HPLC of the Z991 product that embodiment 1 obtains analyzes as shown in Figure 2
1HNMR(500MHz,d6-DMSO)δppm:9.30(d,1H),9.20(d,1H),9.11(s,1H),9.05(s,1H),8.95(s,1H),8,89(s,1H),8.22(t,2H),8.15(d,2H),7.99(d,1H),7.78(d,1H),7.57(d,1H),7.50(d,1H),7.40(d,1H),7.36(m,3H),7.23(d,1H),6.90(d,1H),6.82(d,1H),2.84(t,3H),2.78(t,3H),1.67(m,4H),1.3(m,20H),0.85(m,6H)。
The consumption of embodiment 8 ~ 14 low solubility solvent is different
Cis-two (isothiocyano)-(2 of 1g, 2 '-dipyridyl-4,4 '-dicarboxylic acid)-(4,4 '-two (5-(5-octyl thiophene-2-base) thiophene-2-base)-second bipyridine) close ruthenium (II) complex compound (code name is CYC-B1 or Z991), 20mLN, after the mixing of dinethylformamide, acetonitrile, at 60 DEG C, mix 0.5 hour by magnetic agitation, terminate rear filtered while hot.Filter the funnel that uses, the pre-treatment 0.5 hour in 70 DEG C of baking ovens of filter flask and filter paper.After collecting filtrate, be placed in 60 DEG C of baking ovens, with the speed slow cooling of reduction per hour 5 DEG C to room temperature 25 DEG C.Then, place 24 hours in-30 DEG C of refrigerators.Take out after terminating, with the membrane filtration of 10 μm, collect the dye solids obtained, in the baking oven of 50 DEG C, drying 24 hours, obtains Z991 product.In every embodiment, the concrete consumption of low solubility solvent and output and purity are as shown in Table 2 and Figure 3.
The consumption of table 2 low solubility solvent and Z991 product production, the purity concerns of acquisition
The difference of embodiment 15 ~ 20 solvent temperature
Cis-two (isothiocyano)-(2 of 1g, 2 '-dipyridyl-4,4 '-dicarboxylic acid)-(4,4 '-two (5-(5-octyl thiophene-2-base) thiophene-2-base)-second bipyridine) close ruthenium (II) complex compound (code name is CYC-B1 or Z991), 20mLN, after the mixing of dinethylformamide, 120mL acetonitrile, under solvent temperature, mix 0.5 hour by magnetic agitation, terminate rear filtered while hot.Filter the funnel that uses, the pre-treatment 0.5 hour in 70 DEG C of baking ovens of filter flask and filter paper.After collecting filtrate, be placed in 60 DEG C of baking ovens, with the speed slow cooling of reduction per hour 5 DEG C to room temperature 25 DEG C.Then, place 24 hours in-30 DEG C of refrigerators.Take out after terminating, with the membrane filtration of 10 μm, collect the dye solids obtained, in the baking oven of 50 DEG C, drying 24 hours, obtains Z991 product.In every embodiment, solvent temperature and output and purity are as shown in table 3 and fig. 4.
The Z991 product production of table 3 solvent temperature and acquisition, purity concerns
The difference of embodiment 21 ~ 25 freezing temp
Cis-two (isothiocyano)-(2 of 1g, 2 '-dipyridyl-4,4 '-dicarboxylic acid)-(4,4 '-two (5-(5-octyl thiophene-2-base) thiophene-2-base)-second bipyridine) close ruthenium (II) complex compound (code name is CYC-B1 or Z991), 10mLN, after the mixing of dinethylformamide, 100mL acetonitrile, at 60 DEG C, mix 0.5 hour by magnetic agitation, terminate rear filtered while hot.Filter the funnel that uses, the pre-treatment 0.5 hour in 70 DEG C of baking ovens of filter flask and filter paper.After collecting filtrate, be placed in 60 DEG C of baking ovens, with the speed slow cooling of reduction per hour 5 DEG C to room temperature 25 DEG C.Then, place 24 hours in the refrigerator reaching freezing temp.Take out after terminating, with the membrane filtration of 10 μm, collect the dye solids obtained, in the baking oven of 50 DEG C, drying 24 hours, obtains Z991 product.In every embodiment, freezing temp and output and purity are as shown in table 4 and fig. 5.
The Z991 product production of table 4 freezing temp and acquisition, purity concerns
Directly lower the temperature in refrigerator after embodiment 26 filtered while hot
Cis-two (isothiocyano)-(2 of 1g, 2 '-dipyridyl-4,4 '-dicarboxylic acid)-(4,4 '-two (5-(5-octyl thiophene-2-base) thiophene-2-base)-second bipyridine) close ruthenium (II) complex compound (code name is CYC-B1 or Z991), 10mLN, after the mixing of dinethylformamide, 100mL acetonitrile, at 60 DEG C, mix 0.5 hour by magnetic agitation, terminate rear filtered while hot.Filter the funnel that uses, the pre-treatment 0.5 hour in 70 DEG C of baking ovens of filter flask and filter paper.After collecting filtrate, directly place 24 hours in-30 DEG C of refrigerators.Take out after terminating, with the membrane filtration of 10 μm, collect the dye solids obtained, in the baking oven of 50 DEG C, drying 24 hours, obtains 0.9g solid, purity 93.6%.
Embodiment 27 drying temperature 60 DEG C
Cis-two (isothiocyano)-(2 of 1g, 2 '-dipyridyl-4,4 '-dicarboxylic acid)-(4,4 '-two (5-(5-octyl thiophene-2-base) thiophene-2-base)-second bipyridine) close ruthenium (II) complex compound (code name is CYC-B1 or Z991), 10mLN, after the mixing of dinethylformamide, 100mL acetonitrile, at 60 DEG C, mix 0.5 hour by magnetic agitation, terminate rear filtered while hot.Filter the funnel that uses, the pre-treatment 0.5 hour in 70 DEG C of baking ovens of filter flask and filter paper.After collecting filtrate, be placed in 60 DEG C of baking ovens, with the speed slow cooling of reduction per hour 5 DEG C to room temperature 25 DEG C.Then, place 24 hours in-30 DEG C of refrigerators.Take out after terminating, with the membrane filtration of 10 μm, collect the dye solids obtained, in the baking oven of 60 DEG C, drying 24 hours, obtains 0.89g solid, purity 95.6%.
Embodiment 28 drying temperature 70 DEG C
Step with embodiment 26, unlike: in the baking oven of 70 DEG C dry 24 hours, obtain 0.89g solid, purity 94.3%.
Embodiment 29N719 dyestuff
code name is N3 or N719
Cis-two (isothiocyano)-two (2 of 1g, 2 '-dipyridyl-4,4 '-dicarboxylic acid) close ruthenium (II) complex compound (code name is N3 or N719), 10mLN, after the mixing of dinethylformamide, 100mL water, at 80 DEG C, mix 0.5 hour by magnetic agitation, terminate rear filtered while hot.Filter the funnel that uses, the pre-treatment 0.5 hour in 80 DEG C of baking ovens of filter flask and filter paper.After collecting filtrate, be placed in 80 DEG C of baking ovens, with the speed slow cooling of reduction per hour 5 DEG C to room temperature 25 DEG C.Then, place 48 hours in-30 DEG C of refrigerators.Take out after terminating, with the membrane filtration of 10 μm, collect the dye solids obtained, in the baking oven of 50 DEG C, drying 24 hours, obtains 0.92g solid, purity 97%.
1HNMR(500MHz,d6-DMSO)δppm:9.52(d,1H),8.92(d,1H),8.75(d,1H),8.19(d,1H),7.80(d,1H),7.49(d,1H).
Embodiment 30Z907 dyestuff
Cis-two (isothiocyano)-(4 of 1g, 4 '-dinonyl-2,2 '-dipyridyl)-(2,2 '-dipyridyl-4,4 '-dicarboxylic acid) ruthenium complex (II) (code name is Z907), 2mL acetone, 50mL acetonitrile mixing after, at 70 DEG C, mix 0.5 hour by magnetic agitation, terminate rear filtered while hot.Filter the funnel that uses, the pre-treatment 0.5 hour in 70 DEG C of baking ovens of filter flask and filter paper.After collecting filtrate, be placed in 70 DEG C of baking ovens, with the speed slow cooling of reduction per hour 5 DEG C to room temperature 25 DEG C.Then, place 24 hours in-30 DEG C of refrigerators.Take out after terminating, with the membrane filtration of 10 μm, collect the dye solids obtained, in the baking oven of 50 DEG C, drying 24 hours, obtains 0.93g solid, purity 96.5%.
1HNMR(500MHz,CD 3OD)δppm:9.72(d,1H),9.28(d,1H),9.08(s,1H),8.92(s,1H),8.55(s,1H),8.42(s,1H),8.28(d,1H),7.88(d,1H),7.70(t,2H),7.40(d,1H),7.05(d,1H),2.95(t,2H),2.75(t,2H),1.95(m,2H),1.40(m,26H),0.90(t,6H).
Embodiment 31K19 dyestuff
Cis-two (isothiocyano)-(4 of 1g, 4 '-two (4-hexyloxystyryl)-2,2 '-dipyridyl)-(2,2 '-dipyridyl-4,4 '-dicarboxylic acid) ruthenium complex (II) (code name is K19), 5mLN, dinethylformamide, 100mL ethanol mixing after, at 60 DEG C, mix 0.5 hour by magnetic agitation, terminate rear filtered while hot.Filter the funnel that uses, the pre-treatment 0.5 hour in 70 DEG C of baking ovens of filter flask and filter paper.After collecting filtrate, be placed in 60 DEG C of baking ovens, with the speed slow cooling of reduction per hour 5 DEG C to room temperature 25 DEG C.Then, place 24 hours in-30 DEG C of refrigerators.Take out after terminating, with the membrane filtration of 10 μm, collect the dye solids obtained, in the baking oven of 50 DEG C, drying 24 hours, obtains 0.87g solid, purity 97.3%.
1HNMR(500MHz,CD 3OD)δppm:9.4(d,1H),9.2(d,1H),8.9(s,1H),8.8(s,1H),8.3(s,1H),8.15(s,1H),8.0(d,1H),7.80(d,1H),7.7～6.9(m,16H),4.1～0.8(44H).
Embodiment 32Z910 dyestuff
Cis-two (isothiocyano)-(4 of 1g, 4 '-two (4-methoxyl-styrene)-2,2 '-dipyridyl)-(2,2 '-dipyridyl-4,4 '-dicarboxylic acid) ruthenium complex (II) (code name is Z910), 10mL acetone, 100mL ethanol mixing after, at 65 DEG C, mix 0.5 hour by magnetic agitation, terminate rear filtered while hot.Filter the funnel that uses, the pre-treatment 0.5 hour in 70 DEG C of baking ovens of filter flask and filter paper.After collecting filtrate, be placed in 65 DEG C of baking ovens, with the speed slow cooling of reduction per hour 5 DEG C to room temperature 25 DEG C.Then, place 24 hours in-30 DEG C of refrigerators.Take out after terminating, with the membrane filtration of 10 μm, collect the dye solids obtained, in the baking oven of 50 DEG C, drying 24 hours, obtains 0.92g solid, purity 95.9%.
1HNMR(500MHz,CD 3OD)δppm:9.4(d,1H),9.2(d,1H),8.9(s,1H),8.8(s,1H),8.3(s,1H),8.15(s,1H),7.9(d,1H),7.80(d,1H),7.2(m,16H),4.1(s,3H),4.0(s,3H).
Embodiment 33K77 dyestuff
Cis-two (isothiocyano)-(4 of 1g, 4 '-two (4-t-butoxystyrene base)-2,2 '-dipyridyl)-(2,2 '-dipyridyl-4,4 '-dicarboxylic acid) ruthenium complex (II) (code name is K77), after 10mLN, N-diethylformamide, 100mL methanol mixed, at 70 DEG C, mix 0.5 hour by magnetic agitation, terminate rear filtered while hot.Filter the funnel that uses, the pre-treatment 0.5 hour in 70 DEG C of baking ovens of filter flask and filter paper.After collecting filtrate, be placed in 70 DEG C of baking ovens, with the speed slow cooling of reduction per hour 5 DEG C to room temperature 25 DEG C.Then, place 24 hours in-30 DEG C of refrigerators.Take out after terminating, with the membrane filtration of 10 μm, collect the dye solids obtained, in the baking oven of 50 DEG C, drying 24 hours, obtains 0.85g solid, purity 96.7%.
1HNMR(500MHz,CD 3OD)δppm:9.45(d,1H),9.25(d,1H),8.95(s,1H),8.8(s,1H),8.35(s,1H),8.2(s,1H),8.0(d,1H),7.0(m,17H),3.0(m,54H).
Embodiment 34C106 dyestuff
Cis-two (isothiocyano)-(4 of 1g, 4 '-two (5-hexyl sulfo-thiophene-2-base)-2,2 '-dipyridyl)-(2,2 '-dipyridyl-4,4 '-dicarboxylic acid) ruthenium complex (II) (code name is C106), 20mLN, N-diethylformamide, 30mL toluene mixing after, at 80 DEG C, mix 0.5 hour by magnetic agitation, terminate rear filtered while hot.Filter the funnel that uses, the pre-treatment 0.5 hour in 80 DEG C of baking ovens of filter flask and filter paper.After collecting filtrate, be placed in 80 DEG C of baking ovens, with the speed slow cooling of reduction per hour 5 DEG C to room temperature 25 DEG C.Then, place 24 hours in-20 DEG C of refrigerators.Take out after terminating, with the membrane filtration of 10 μm, collect the dye solids obtained, in the baking oven of 50 DEG C, drying 24 hours, obtains 0.78g solid, purity 94.6%.
1HNMR(500MHz,d6-DMSO)δppm:9.69(d,1H),9.23(d,1H),9.08(s,1H),8.90(s,1H),8.49(s,1H),8.40(d,1H),8.33(s,1H),8.15(d,1H),7.97(d,1H),7.71(d,1H),7.60(d,1H),7.57(d,1H),7.43(d,1H),7.33(d,1H),7.29(d,1H),6.96(d,1H),3.17(t,2H),3.08(t,2H),1.90(m,2H),1.73-1.81(m,2H),1.60(m,4H),1.42(m,8H),1.01(t,3H),0.96(t,3H).
Embodiment 35C101 dyestuff
Cis-two (isothiocyano)-(4 of 1g, 4 '-two (5-hexyl thiophene-2-base)-2,2 '-dipyridyl)-(2,2 '-dipyridyl-4,4 '-dicarboxylic acid) ruthenium complex (II) (code name is C101), 20mL acetone, 80mL ethyl acetate mixing after, at 60 DEG C, mix 0.5 hour by magnetic agitation, terminate rear filtered while hot.Filter the funnel that uses, the pre-treatment 0.5 hour in 70 DEG C of baking ovens of filter flask and filter paper.After collecting filtrate, be placed in 60 DEG C of baking ovens, with the speed slow cooling of reduction per hour 5 DEG C to room temperature 25 DEG C.Then, place 24 hours in-30 DEG C of refrigerators.Take out after terminating, with the membrane filtration of 10 μm, collect the dye solids obtained, in the baking oven of 50 DEG C, drying 24 hours, obtains 0.84g solid, purity 96.5%.
1HNMR(500MHz,d6-DMSO)δppm:9.65(d,1H),9.10(d,1H),9.00(s,1H),8.85(s,1H),8.40(s,1H),8.35(d,1H),8.25(s,1H),8.10(d,1H),7.95(d,1H),7.65(d,1H),7.55(d,1H),7.45(d,1H),7.10(m,3H),6.85(d,1H),3.05(t,2H),2.95(t,2H),1.80(m,4H),1.50(m,12H),1.00(m,6H).
Embodiment 36TG6 dyestuff
Cis-two (isothiocyano)-(4 of 1g, 4 '-two (the just own sulfenyl styryl of 4-)-2,2 '-dipyridyl)-(2,2 '-dipyridyl-4,4 '-dicarboxylic acid) ruthenium complex (II) (code name is TG6), 5mL acetone, 90mL ethanol mixing after, at 60 DEG C, mix 0.5 hour by magnetic agitation, terminate rear filtered while hot.Filter the funnel that uses, the pre-treatment 0.5 hour in 70 DEG C of baking ovens of filter flask and filter paper.After collecting filtrate, be placed in 60 DEG C of baking ovens, with the speed slow cooling of reduction per hour 5 DEG C to room temperature 25 DEG C.Then, place 24 hours in-30 DEG C of refrigerators.Take out after terminating, with the membrane filtration of 10 μm, collect the dye solids obtained, in the baking oven of 50 DEG C, drying 24 hours, obtains 0.76g solid, purity 97.3%.
1HNMR(500MHz,d6-DMSO)δppm:9.36(d,1H),9.05(d,1H),8.96(s,1H),8.8(s,1H),8.67(s,1H),8.50(s,1H),8.13(s,1H),7.81(d,1H),7.30(m,16H),3.10(m,12H),1.60(m,8H),1.35(m,16H),0.93(t,6H),0.85(m,12H).
The sign of effect example dye sensitization solar battery
1) dye sensitization solar battery is prepared
The dyestuff chosen after purifying in comparing embodiment and section Example is dissolved in acetonitrile: in the mixed solvent of the trimethyl carbinol=1:1, be made into the dye solution of 0.4M.
The commercially available TiO that particle diameter is 20nm 2slurry silk screen brush method is coated on the stannic oxide of FTO(Fluorin doped) conductive glass surface, be placed in retort furnace and sinter 2 hours at 500 DEG C, obtain the TiO of 18-20 μm 2film.TiO 2after electrode soaks 48 hours in dye solution, with dry after solvent washing.
Stannic oxide at FTO(Fluorin doped) surface drilling (diameter is 0.5mm) of conductive glass.Then H 2ptCl 6(2mg platinum/1mL methanol solution) is sprayed on the surface of FTO conductive glass, sinters 0.5 hour, obtain electrode at 410 DEG C.
Inserting thickness is the hot melt adhesive polymer layer of 60 μm between two electrodes, and whole device is bonded firmly at 120 DEG C to 140 DEG C.
0.06MI 2, 0.3MLiI, 0.5M tert .-butylpyridine, be dissolved in acetonitrile and make electrolytic solution, by injecting between two electrodes the aperture on electrode.After confirming that space is all filled up, aperture hot melt adhesive is sealed.
2) current-voltage curve of dye sensitization solar battery, short-circuit current (Jsc), open circuit voltage (Voc), packing factor (FF), photoelectric transformation efficiency (η) is tested under the standard light source of AM1.5.Result is as shown in table 5.
Table 5 dye sensitization solar battery photovoltaic performance compares
Test result shows, the dyestuff of purifying by the method for purification after the optimization in the present invention no matter short-circuit current (Jsc), open circuit voltage (Voc), packing factor (FF), or photoelectric transformation efficiency (η) all improves to some extent.Compare with traditional column chromatography method of purification, the present invention utilizes the recrystallization method dyestuff obtained of purifying that the photoelectric transformation efficiency of battery is brought up to 8.53% from 7.92%, and the efficiency of battery can be made to improve 7.7%.

Claims (8)

1. utilize a method for recrystallization method purification Ruthenium complex crude product, it comprises the steps:
Steps A) dipyridyl Ruthenium complex crude product is dissolved in mixed solvent being heated with stirring at 30 ~ 150 DEG C, form saturated solution, filtered while hot removes insoluble impurities; Wherein, described mixed solvent comprises high-dissolvability solvent and low solubility solvent; Described high-dissolvability solvent is tetrahydrofuran (THF), N, N '-dimethyl methane amide, N, N '-diethylformamide, N, N '-dipropyl formamide, tetramethyl ammonium hydroxide solution, tetraethyl ammonium hydroxide solution, TBAH solution, acetone and/or butanone; Described low solubility solvent is ethyl acetate, sherwood oil, ether, methyl-phenoxide, phenyl ethyl ether, chloroform, methylene dichloride, acetonitrile, ethanol, methyl alcohol, formaldehyde, formic acid, acetic acid, benzene, toluene, phenylformic acid, normal hexane, hexanaphthene, chlorobenzene, iodobenzene and/or water; Every gram of dipyridyl Ruthenium complex crude product is dissolved in the mixed solvent comprising 5 ~ 20mL high-dissolvability solvent and 10 ~ 200mL low solubility solvent;
Step B) slowly cool to room temperature, then at-40 ~ 0 DEG C of freezing crystallize out gradually; And
Step C) filter, drying obtains ruthenium complex product;
Wherein, the structural formula of described bipyridyl ruthenium complex compound such as formula shown in (71),
Wherein, A 1for H.
2. method according to claim 1, is characterized in that, steps A) in, be heated to 30 ~ 150 DEG C and keep 0.5 ~ 3 hour.
3. method according to claim 2, is characterized in that, steps A) in, be heated to 50 ~ 80 DEG C and keep 0.5 ~ 1 hour.
4. method according to claim 1, is characterized in that, steps A) in, the temperature that filtered while hot articles for use used are preheated to the temperature ~ saturated solution of saturated solution adds 10 DEG C, and the envrionment temperature of filtered while hot is the temperature of saturated solution.
5. method according to claim 1, is characterized in that, step B) in, freezing 2 ~ 72 hours at-40 ~ 0 DEG C, crystallize out gradually.
6. method according to claim 5, is characterized in that, step B) in, freezing 24 ~ 48 hours at-40 ~-10 DEG C, crystallize out gradually.
7. method according to claim 1, is characterized in that, step C) in, described drying is dry 12h ~ 48h at 30 DEG C ~ 70 DEG C, or described drying is vacuum-drying.
8. method according to claim 7, is characterized in that, step C) in, described drying is dry 24h ~ 48h at 40 DEG C ~ 60 DEG C.
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