CN103145760B - Post-processing method of ruthenium complex reaction liquid and obtained ruthenium complex crude products - Google Patents

Post-processing method of ruthenium complex reaction liquid and obtained ruthenium complex crude products Download PDF

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CN103145760B
CN103145760B CN201210580721.5A CN201210580721A CN103145760B CN 103145760 B CN103145760 B CN 103145760B CN 201210580721 A CN201210580721 A CN 201210580721A CN 103145760 B CN103145760 B CN 103145760B
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ruthenium complex
precipitation
reaction solution
solvent
formula
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CN103145760A (en
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张焘
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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Abstract

The invention discloses a post-processing method of ruthenium complex reaction liquid. The method includes the following steps: step A. cooling the ruthenium complex reaction liquid to 10-50 DEG C; step B. adding the solvent which is frozen to -50-0 DEG C and used for precipitation, precipitating out ruthenium complex, and obtaining ruthenium complex precipitation mixed liquor; step C. enabling the ruthenium complex precipitation mixed liquor to be in full precipitation at the temperature of -50-0 DEG C; and step D. unfreezing, filtering, cleaning, drying and obtaining ruthenium complex crude products. According to the post-processing method of ruthenium complex reaction liquid, before the solvent used for precipitation is added, the ruthenium complex reaction liquid does not need to be steamed in a rotary mode to remove the solvent, but precipitation is directly carried out. Therefore, post-processing time is shortened, isomer production is reduced, and ruthenium complex crude products can be obtained with high yield and low cost.

Description

The post-treating method of ruthenium complex reaction solution and the Ruthenium complex crude product of acquisition
Technical field
The present invention relates to a kind of post-treating method of ruthenium complex reaction solution and the Ruthenium complex crude product of acquisition.
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, expects to be popularized widely.
Apply by dye-sensitized solar cell (the Dye-Sensitized Solar Cell of the photoresponse electronics movement of dye sensitization, referred to as DSSC), owing to having higher photoelectric transformation efficiency, do not need the purifying plant of the large costs such as vacuum unit, and the cheap semiconductor materials such as titanium oxide can be used to purify simply with good productivity, so expect the solar cell becoming a new generation.As sensitizing dye, use the material that effectively can absorb the light near visible ray, such as, ruthenium (Ru) complex compound shown in formula I is exactly wherein a kind of.
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).
Work as Z 1with Z 2be all formula (38) and X 1n for formula (2) and in formula (2) is 0, and Y 1for sulphur (S), and X 2for hydrogen or and X 1during for identical group formula (2), wherein Y 2be not formula (20) ~ (22) or formula (31), now, Y in formula (2) 2only can be formula (23) ~ (30) or formula (32) ~ (37) one of them;
Work as Z 1with Z 2be all formula (38) and X 1n for formula (3) and in formula (3) is 0, and Y 1for sulphur (S), and X 2for hydrogen or and X 1during for identical group formula (3), Y 2be not formula (20) ~ (22) or formula (31), now, Y 2only can be formula (23) ~ (30) or formula (32) ~ (37) one of them;
Work as Z 1with Z 2be all formula (38) and X 1n for formula (4) and in formula (4) is 0, and Y 1for sulphur (S), and R in formula (4) 3for hydrogen, and X 2for hydrogen or and X 1during for identical group formula (4), Y 2be not formula (20) ~ (22), now, Y 2only can be formula (23) ~ (37) one of them;
Work as Z 1with Z 2be all formula (38) and X 1n for formula (5) and in formula (5) is 0, and Y 1for sulphur (S), and R in formula (5) 4~ R 7be all hydrogen, and X 2for hydrogen or and X 1during for identical group formula (5), Y 2be not formula (20) ~ (22), now, Y 2only can be formula (23) ~ (37) one of them.
Particularly, ruthenium (Ru) complex structure shown in formula I is such as formula shown in (61) ~ (67):
Wherein, R 67~ R 70be 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), or be expression (36) ~ (37) one of them; Wherein R 71~ R 74be 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) one of them; Wherein, R 75~ R 76be 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; Wherein, R 77~ R 82be independently SC gh 2G+1(G=1 ~ 15) or be expression (36) ~ (37) one of them; Wherein R 83~ 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 expression (36) ~ (37) one of them;
Wherein A 1represent hydrogen, lithium, sodium, potassium, quarternary ammonium salt (such as formula (45) Suo Shi);
Wherein, R 63~ R 66be independently H or C yh 2y+1(y=1 ~ 15).
The first more specific situation is, ruthenium (Ru) complex structure shown in formula I is such as formula shown in (68) ~ (74):
Wherein, A 1represent hydrogen, lithium, sodium, potassium, quarternary ammonium salt (such as formula (45) Suo Shi);
Wherein, R 63~ R 66be independently H or C yh 2y+1(y=1 ~ 15).
The more specific situation of the second is that ruthenium (Ru) complex structure shown in formula I is such as formula shown in (75) ~ (76):
Wherein, R 87~ R 90be independently H or C jh 2J+1(J=1 ~ 15) one of them;
Wherein A 1represent hydrogen, lithium, sodium, potassium, quarternary ammonium salt (such as formula (45) Suo Shi);
Wherein, R 63~ R 66be independently H or C yh 2y+1(y=1 ~ 15).
Ruthenium complex shown in current formula I is Z991, adopt non-patent literature (Chia-Yuan Chen, Shi-Jhang Wu, Chun-Guey Wu, etal, " A Ruthenium Complex with SuperhighLight-Harvesting Capacity for Dye-Sensitized Solar Cells ", Angew.Chem.Int.Ed.2006,45,5822 ~ 5825) one kettle way synthesizes
DMF selected by solvent, and point three-step reaction, the first step is [RuCl 2(p-cymene)] 2with intermediate 1(abtpy) react 4 hours at 70 DEG C; Second step is the first step reaction solution and intermediate 2(dcbpy) react at 130 DEG C and react for 4 hours; 3rd step is second step reaction solution and NH 4sCN obtains target ruthenium complex reaction solution for 4 hours at 110 DEG C or 130 DEG C of reactions.Reacted ruthenium complex (Z991) reaction solution first cools, and then under 65 DEG C ~ 70 DEG C vacuum, rotates evaporative removal solvent, adds water and separates out precipitation, and filtration, washing, drying obtain Ruthenium complex crude product.This post-treating method needs rotary evaporation to remove solvent, require the expenditure of energy and spend the plenty of time, and in crude product, isomer impurities is more.Therefore, the Ruthenium complex crude product of so process is unfavorable for commercial application.
Summary of the invention
The object of the invention is to solve in prior art ruthenium complex after synthesis, reaction solution process be consuming time, power consumption and the higher technical problem of the thick Isomers In Products impurity obtained, a kind of post-treating method of new ruthenium complex reaction solution is provided.
The post-treating method of ruthenium complex reaction solution of the present invention, comprises the steps:
Steps A), ruthenium complex reaction solution is cooled to 10 DEG C ~ 50 DEG C;
Step B), adding the solvent for precipitating being refrigerated to-50 DEG C ~ 0 DEG C, separating out ruthenium complex precipitation, obtain ruthenium complex precipitation mixed solution;
Step C), by step B) ruthenium complex that obtains precipitation mixed solution fully precipitates under being placed in-50 DEG C ~ 0 DEG C temperature; And
Step D), thaw, filter, wash, drying obtains Ruthenium complex crude product.
Preferably, step B), adding the solvent for precipitating being refrigerated to-45 DEG C ~ 0 DEG C, separating out ruthenium complex precipitation, obtain ruthenium complex precipitation mixed solution; Step C), by step B) ruthenium complex that obtains precipitation mixed solution fully precipitates under being placed in-45 DEG C ~ 0 DEG C temperature.
Be preferably, steps A) in, ruthenium complex reaction solution is cooled to room temperature.Operation like this, can reduce the growing amount of the by products such as isomer, obtains the target product Ruthenium complex crude product of higher degree.
Step B) in, described is water, dust technology or dehydrated alcohol for the solvent precipitated, and the described volume for the solvent precipitated is 5 ~ 10 times of the volume of solvent in described ruthenium complex reaction solution, preferably 8 times.By adding the solvent for precipitating of high times amount, precipitation can be made to separate out fully.
Step C) in, under ruthenium complex precipitation mixed solution is placed in-50 DEG C ~ 0 DEG C temperature, preferably at-20 DEG C ~-16 DEG C temperature, more preferably carry out at-18 DEG C of temperature fully precipitating 12 ~ 48 hours, preferably 24 ~ 36 hours.Ruthenium complex precipitation mixed solution, by freezing treatment, can reduce the growing amount of the by products such as isomer.
Step D) in, described in thaw and to carry out at 20 DEG C ~ 40 DEG C, the described washing water washing of 2 ~ 5 times, described drying is dry 24h ~ 48h at 30 DEG C ~ 50 DEG C.
Another object of the present invention is to provide a kind of Ruthenium complex crude product utilizing post-treating method of the present invention to obtain.
Positive progressive effect of the present invention is: based in the aftertreatment of currently known methods, at ruthenium complex reaction solution after overcooling, in order to effectively separate out precipitation, adopts the method for revolving steaming to remove solvent.And ruthenium complex reaction solution of the present invention is after overcooling, need not revolves to boil off to reaction solution and desolventize, but ruthenium complex precipitation separated out by the solvent directly added for precipitating.Method of the present invention has several advantage below:
(1) desolventize process temperature generally up to 65 ~ 75 DEG C owing to revolving to boil off, the generation of the by products such as isomer can be caused, save the growing amount that this process effectively can reduce isomer, thus improve the purity of thick product;
(2) eliminate the use of revolving and steaming instrument, greatly reduce instrument cost;
(3) eliminate and revolve steamed journey, shorten finishing time and be conducive to reducing manufacturing cost.
Thus, the post-treating method of ruthenium complex reaction solution of the present invention, while shortening finishing time, reduces the generation of isomeric by-products.Thus can high yield, obtain Ruthenium complex crude product at low cost.The Ruthenium complex crude product of synthesis like this can be applied to dye sensitization photoelectric converter as dyestuff, typically, can be applied to dye-sensitized solar cell.
Accompanying drawing explanation
Fig. 1 is Ru [(dcbpy) (abtpy) (NCS) of embodiment 1 gained 2] the HPLC color atlas of thick product; Wherein, transverse axis represents dissolution time (min), and the longitudinal axis represents intensity (any scale (scale));
Fig. 2 is Ru [(dcbpy) (abtpy) (NCS) of embodiment 2 gained 2] the HPLC color atlas of thick product; Wherein, transverse axis represents dissolution time (min), and the longitudinal axis represents intensity (any scale (scale));
Fig. 3 is Ru [(dcbpy) (abtpy) (NCS) of embodiment 3 gained 2] the HPLC color atlas of thick product; Wherein, transverse axis represents dissolution time (min), and the longitudinal axis represents intensity (any scale (scale));
Fig. 4 is Ru [(dcbpy) (abtpy) (NCS) of embodiment 4 gained 2] the HPLC color atlas of thick product; Wherein, transverse axis represents dissolution time (min), and the longitudinal axis represents intensity (any scale (scale));
Fig. 5 is Ru [(dcbpy) (abtpy) (NCS) of embodiment 5 gained 2] the HPLC color atlas of thick product; Wherein, transverse axis represents dissolution time (min), and the longitudinal axis represents intensity (any scale (scale));
Fig. 6 is Ru [(dcbpy) (abtpy) (NCS) of embodiment 6 gained 2] the HPLC color atlas of thick product; Wherein, transverse axis represents dissolution time (min), and the longitudinal axis represents intensity (any scale (scale));
Fig. 7 is Ru [(dcbpy) (abtpy) (NCS) of embodiment 7 gained 2] the HPLC color atlas of thick product; Wherein, transverse axis represents dissolution time (min), and the longitudinal axis represents intensity (any scale (scale));
Fig. 8 is Ru [(dcbpy) (abtpy) (NCS) of embodiment 8 gained 2] the HPLC color atlas of thick product; Wherein, transverse axis represents dissolution time (min), and the longitudinal axis represents intensity (any scale (scale));
Fig. 9 is Ru [(dcbpy) (abtpy) (NCS) of embodiment 9 gained 2] the HPLC color atlas of thick product; Wherein, transverse axis represents dissolution time (min), and the longitudinal axis represents intensity (any scale (scale));
Figure 10 is Ru [(dcbpy) (abtpy) (NCS) of embodiment 10 gained 2] the HPLC color atlas of thick product; Wherein, transverse axis represents dissolution time (min), and the longitudinal axis represents intensity (any scale (scale));
Figure 11 is Ru [(dcbpy) (abtpy) (NCS) of comparing embodiment gained 2] the HPLC color atlas of thick product; Wherein, transverse axis represents dissolution time (min), and the longitudinal axis represents intensity (any scale (scale)).
Embodiment
Adopt non-patent literature (Chia-Yuan Chen, Shi-Jhang Wu, Chun-Guey Wu, etal, " A Ruthenium Complex with Superhigh Light-Harvesting Capacity forDye-Sensitized Solar Cells ", Angew.Chem.Int.Ed.2006,45,5822 ~ 5825) one kettle way carries out synthesis ruthenium complex (Z991), for embodiment 1 ~ 7 and comparing embodiment.
Embodiment 1
Steps A) after building-up reactions terminates, under magnetic agitation condition, reaction solution is naturally cooled to room temperature in lucifuge and Ar gas atmosphere.
Step B) deionized water is placed in-18 DEG C of refrigerator and cooled in advance freezes 2h, pour the frozen water higher than solvent volume in reaction solution more than 8 times into steps A) in cooled reaction solution, fully shake up and separate out Ru [(dcbpy) (abtpy) (NCS) 2] precipitation.
Step C) elutriation on the rocks is gone out precipitation after mixed solution be placed in freeze overnight under-18 DEG C of conditions, solid phase is fully precipitated.
Step D) mixed solution is thawed in 25 DEG C after reclaim solid with filter funnel, and fully wash this solid with the deionized water higher than solvent volume in reaction solution 2 times.By this solid dry 24h in 40 DEG C of vacuum driers, obtain Ru [(dcbpy) (abtpy) (NCS) 2] thick product.
Ru [(dcbpy) (abtpy) (NCS) of embodiment 1 gained as can be seen from Figure 1 2] purity of thick product reaches 82.09%, the content of Main By product impurity is 3.15%.
Embodiment 2
Steps A) after building-up reactions terminates, under magnetic agitation condition, reaction solution is naturally cooled to room temperature in lucifuge and Ar gas atmosphere.
Step B) deionized water is placed in-10 DEG C of refrigerator and cooled in advance freezes 2h, pour the water higher than solvent volume in reaction solution 8 times into steps A) be cooled in the reaction solution of room temperature, fully shake up and separate out Ru [(dcbpy) (abtpy) (NCS) 2] precipitation.
Step C) by adding water, the mixed solution after separating out precipitation is placed in freeze overnight under-18 DEG C of conditions, and solid phase is fully precipitated.
Step D) mixed solution is thawed in 25 DEG C after reclaim solid with filter funnel, and fully wash this solid with the deionized water higher than solvent volume in reaction solution 2 times.By this solid dry 24h in 40 DEG C of vacuum driers, obtain Ru [(dcbpy) (abtpy) (NCS) 2] thick product.
As can be seen from Figure 2, Ru [(dcbpy) (abtpy) (NCS) of embodiment 2 gained 2] purity of thick product reaches 80.98%, the content of Main By product impurity is 4.83%.
Embodiment 3
Steps A) after building-up reactions terminates, under magnetic agitation condition, reaction solution is naturally cooled to room temperature in lucifuge and Ar gas atmosphere.
Step B) deionized water is placed in 0 DEG C of refrigerator and cooled in advance freezes 2h, pour the frozen water higher than solvent volume in reaction solution more than 8 times into steps A) in cooled reaction solution, fully shake up and separate out Ru [(dcbpy) (abtpy) (NCS) 2] precipitation.
Step C) elutriation on the rocks is gone out precipitation after mixed solution be placed in freeze overnight under-18 DEG C of conditions, solid phase is fully precipitated.
Step D) mixed solution is thawed in 20 DEG C after reclaim solid with filter funnel, and fully wash this solid with the deionized water higher than solvent volume in reaction solution 2 times.By this solid dry 24h in 40 DEG C of vacuum driers, obtain Ru [(dcbpy) (abtpy) (NCS) 2] thick product.
Ru [(dcbpy) (abtpy) (NCS) of embodiment 3 gained as can be seen from Figure 3 2] purity of thick product reaches 80.01%, the content of Main By product impurity is 5.65%.
Embodiment 4
Steps A) after building-up reactions terminates, under magnetic agitation condition, reaction solution is naturally cooled to 50 DEG C in lucifuge and Ar gas atmosphere.
Step B) deionized water is placed in-18 DEG C of refrigerator and cooled in advance freezes 2h, pour the frozen water higher than solvent volume in reaction solution more than 8 times into steps A) in cooled reaction solution, fully shake up and separate out Ru [(dcbpy) (abtpy) (NCS) 2] precipitation.
Step C) elutriation on the rocks is gone out precipitation after mixed solution be placed in freeze overnight under-18 DEG C of conditions, solid phase is fully precipitated.
Step D) mixed solution is thawed in 40 DEG C after reclaim solid with filter funnel, and fully wash this solid with the deionized water higher than solvent volume in reaction solution 2 times.By this solid dry 24h in 40 DEG C of vacuum driers, obtain Ru [(dcbpy) (abtpy) (NCS) 2] thick product.
Ru [(dcbpy) (abtpy) (NCS) of embodiment 4 gained as can be seen from Figure 4 2] purity of thick product reaches 80.15%, the content of Main By product impurity is 5.45%.
Embodiment 5
Steps A) after building-up reactions terminates, under magnetic agitation condition, reaction solution is naturally cooled to 10 DEG C in lucifuge and Ar gas atmosphere.
Step B) deionized water is placed in-18 DEG C of refrigerator and cooled in advance freezes 2h, pour the frozen water higher than solvent volume in reaction solution more than 8 times into steps A) in cooled reaction solution, fully shake up and separate out Ru [(dcbpy) (abtpy) (NCS) 2] precipitation.
Step C) elutriation on the rocks is gone out precipitation after mixed solution be placed in freeze overnight under-18 DEG C of conditions, solid phase is fully precipitated.
Step D) mixed solution is thawed in 35 DEG C after reclaim solid with filter funnel, and fully wash this solid with the deionized water higher than solvent volume in reaction solution 2 times.By this solid dry 24h in 40 DEG C of vacuum driers, obtain Ru [(dcbpy) (abtpy) (NCS) 2] thick product.
Ru [(dcbpy) (abtpy) (NCS) of embodiment 5 gained as can be seen from Figure 5 2] purity of thick product reaches 81.96%, the content of Main By product impurity is 4.88%.
Embodiment 6
Steps A) after building-up reactions terminates, under magnetic agitation condition, reaction solution is naturally cooled to room temperature in lucifuge and Ar gas atmosphere.
Step B) deionized water is placed in-18 DEG C of refrigerator and cooled in advance freezes 2h, pour the frozen water higher than solvent volume in reaction solution more than 8 times into steps A) in cooled reaction solution, fully shake up and separate out Ru [(dcbpy) (abtpy) (NCS) 2] precipitation.
Step C) elutriation on the rocks is gone out precipitation after mixed solution be placed in freeze overnight under-10 DEG C of conditions, solid phase is fully precipitated.
Step D) mixed solution is thawed in 30 DEG C after reclaim solid with filter funnel, and fully wash this solid with the deionized water higher than solvent volume in reaction solution 2 times.By this solid dry 24h in 40 DEG C of vacuum driers, obtain Ru [(dcbpy) (abtpy) (NCS) 2] thick product.
Ru [(dcbpy) (abtpy) (NCS) of embodiment 6 gained as can be seen from Figure 6 2] purity of thick product reaches 81.65%, the content of Main By product impurity is 4.87%
Embodiment 7
Steps A) after building-up reactions terminates, under magnetic agitation condition, reaction solution is naturally cooled to room temperature in lucifuge and Ar gas atmosphere.
Step B) deionized water is placed in-18 DEG C of refrigerator and cooled in advance freezes 2h, pour the frozen water higher than solvent volume in reaction solution more than 8 times into steps A) in cooled reaction solution, fully shake up and separate out Ru [(dcbpy) (abtpy) (NCS) 2] precipitation.
Step C) elutriation on the rocks is gone out precipitation after mixed solution be placed in freeze overnight under-28 DEG C of conditions, solid phase is fully precipitated.
Step D) mixed solution is thawed in 25 DEG C after reclaim solid with filter funnel, and fully wash this solid with the deionized water higher than solvent volume in reaction solution 2 times.By this solid dry 24h in 40 DEG C of vacuum driers, obtain Ru [(dcbpy) (abtpy) (NCS) 2] thick product.
Ru [(dcbpy) (abtpy) (NCS) of embodiment 7 gained as can be seen from Figure 7 2] purity of thick product reaches 82.03%, the content of Main By product impurity is 3.95%
Embodiment 8
Steps A) after building-up reactions terminates, under magnetic agitation condition, reaction solution is naturally cooled to room temperature in lucifuge and Ar gas atmosphere.
Step B) deionized water is placed in-45 DEG C of refrigerator and cooled in advance freezes 2h, pour the frozen water higher than solvent volume in reaction solution more than 8 times into steps A) in cooled reaction solution, fully shake up and separate out Ru [(dcbpy) (abtpy) (NCS) 2] precipitation.
Step C) elutriation on the rocks is gone out precipitation after mixed solution be placed in freeze overnight under-18 DEG C of conditions, solid phase is fully precipitated.
Step D) mixed solution is thawed in 25 DEG C after reclaim solid with filter funnel, and fully wash this solid with the deionized water higher than solvent volume in reaction solution 2 times.By this solid dry 24h in 40 DEG C of vacuum driers, obtain Ru [(dcbpy) (abtpy) (NCS) 2] thick product.
Ru [(dcbpy) (abtpy) (NCS) of embodiment 8 gained as can be seen from Figure 8 2] purity of thick product reaches 81.88%, the content of Main By product impurity is 3.91%.
Embodiment 9
Steps A) after building-up reactions terminates, under magnetic agitation condition, reaction solution is naturally cooled to room temperature in lucifuge and Ar gas atmosphere.
Step B) deionized water is placed in-18 DEG C of refrigerator and cooled in advance freezes 2h, pour the frozen water higher than solvent volume in reaction solution more than 8 times into steps A) in cooled reaction solution, fully shake up and separate out Ru [(dcbpy) (abtpy) (NCS) 2] precipitation.
Step C) elutriation on the rocks is gone out precipitation after mixed solution be placed in freeze overnight under 0 DEG C of condition, solid phase is fully precipitated.
Step D) mixed solution is thawed in 25 DEG C after reclaim solid with filter funnel, and fully wash this solid with the deionized water higher than solvent volume in reaction solution 2 times.By this solid dry 24h in 40 DEG C of vacuum driers, obtain Ru [(dcbpy) (abtpy) (NCS) 2] thick product.
Ru [(dcbpy) (abtpy) (NCS) of embodiment 9 gained as can be seen from Figure 9 2] purity of thick product reaches 80.55%, the content of Main By product impurity is 5.15%.
Embodiment 10
Steps A) after building-up reactions terminates, under magnetic agitation condition, reaction solution is naturally cooled to room temperature in lucifuge and Ar gas atmosphere.
Step B) deionized water is placed in-18 DEG C of refrigerator and cooled in advance freezes 2h, pour the frozen water higher than solvent volume in reaction solution more than 8 times into steps A) in cooled reaction solution, fully shake up and separate out Ru [(dcbpy) (abtpy) (NCS) 2] precipitation.
Step C) elutriation on the rocks is gone out precipitation after mixed solution be placed in freeze overnight under-45 DEG C of conditions, solid phase is fully precipitated.
Step D) mixed solution is thawed in 25 DEG C after reclaim solid with filter funnel, and fully wash this solid with the deionized water higher than solvent volume in reaction solution 2 times.By this solid dry 24h in 40 DEG C of vacuum driers, obtain Ru [(dcbpy) (abtpy) (NCS) 2] thick product.
Ru [(dcbpy) (abtpy) (NCS) of embodiment 10 gained as can be seen from Figure 10 2] purity of thick product reaches 81.90%, the content of Main By product impurity is 3.66%.
Comparing embodiment
Steps A) after building-up reactions terminates, by reaction solution naturally cooling in lucifuge and Ar gas atmosphere under magnetic agitation condition.
Step B) at 65 DEG C ~ 70 DEG C bath temperatures, 25 ~ 30mbar vacuum tightness, under 75 ~ 85rpm speed conditions, revolves and steams except desolventizing.
Step C) add after deionized water separates out precipitation, precipitation mixed solution is placed in freeze overnight under-18 DEG C of conditions, solid phase is fully precipitated.
Step D) mixed solution is thawed in 25 DEG C after reclaim this solid with filter funnel, and fully wash this solid with the deionized water higher than solvent volume in reaction solution 2 times.By this solid, dry 24h in 40 DEG C of vacuum driers, obtains thick product.
As can be seen from Figure 11, Ru [(dcbpy) (abtpy) (NCS) of obtaining of comparing embodiment 2] purity of thick product is 79.51%, the content of Main By product impurity is 6.51%.
Conclusion: cooled reaction solution removes desolventizing without rotary evaporation, but add solvent freezing in advance and precipitate, not only save time and energy consumption that aftertreatment spends, and Ru [(dcbpy) (abtpy) (NCS) can have been made 2] high purity 82.09% of thick product, effectively inhibit the generation of Main By product impurity, make the content of by-product impurities reduce more than 50%.Therefore, by ruthenium complex Ru [(dcbpy) (abtpy) (NCS) that the present invention manufactures 2] thick product suitably can be applied to the dye sensitization photoelectric converters such as dye-sensitized solar cell.

Claims (8)

1. a post-treating method for ruthenium complex reaction solution, it comprises the steps:
Steps A), ruthenium complex reaction solution is cooled to 10 DEG C ~ 50 DEG C;
Step B), adding the solvent for precipitating being refrigerated to-50 DEG C ~ 0 DEG C, separating out ruthenium complex precipitation, obtain ruthenium complex precipitation mixed solution;
Step C), by step B) ruthenium complex that obtains precipitation mixed solution fully precipitates under being placed in-50 DEG C ~ 0 DEG C temperature; And
Step D), thaw, filter, wash, drying obtains Ruthenium complex crude product;
Wherein, described ruthenium complex is Ru [(dcbpy) (abtpy) (NCS) 2], structural formula is
Described is water, dust technology or dehydrated alcohol for the solvent precipitated.
2. method according to claim 1, is characterized in that, steps A) in, ruthenium complex reaction solution is cooled to room temperature.
3. method according to claim 1, is characterized in that, step B), adding the solvent for precipitating being refrigerated to-45 DEG C ~ 0 DEG C, separating out ruthenium complex precipitation, obtain ruthenium complex precipitation mixed solution; Step C), by step B) ruthenium complex that obtains precipitation mixed solution fully precipitates under being placed in-45 DEG C ~ 0 DEG C temperature.
4. method according to claim 1, is characterized in that, step B) in, the described volume for the solvent precipitated is 5 ~ 10 times of the volume of solvent in described ruthenium complex reaction solution.
5. method according to claim 3, is characterized in that, the described volume for the solvent precipitated is 8 times of the volume of solvent in described ruthenium complex reaction solution.
6. method according to claim 1, is characterized in that, step C) in, carry out fully precipitating 12 ~ 48 hours under ruthenium complex precipitation mixed solution is placed in-50 DEG C ~ 0 DEG C temperature.
7. method according to claim 6, is characterized in that, step C) in, carry out fully precipitating 24 ~ 36 hours under ruthenium complex precipitation mixed solution is placed in-20 DEG C ~-16 DEG C temperature.
8. method according to claim 1, is characterized in that, step D) in, described in thaw and to carry out at 20 DEG C ~ 40 DEG C, the described washing water washing of 2 ~ 5 times, described drying is dry 24h ~ 48h at 30 DEG C ~ 50 DEG C.
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