CN104497053B - Utilize the method for back extraction purification Ruthenium complex crude product - Google Patents
Utilize the method for back extraction purification Ruthenium complex crude product Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000012327 Ruthenium complex Substances 0.000 title claims abstract description 43
- 238000000746 purification Methods 0.000 title claims abstract description 38
- 239000012043 crude product Substances 0.000 title claims abstract description 35
- 238000000605 extraction Methods 0.000 title claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 49
- 239000000047 product Substances 0.000 claims abstract description 24
- 239000012535 impurity Substances 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000009835 boiling Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 230000008859 change Effects 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000005311 nuclear magnetism Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000008247 solid mixture Substances 0.000 claims description 2
- 238000001514 detection method Methods 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000003960 organic solvent Substances 0.000 abstract description 7
- 239000000945 filler Substances 0.000 abstract description 6
- XELZGAJCZANUQH-UHFFFAOYSA-N methyl 1-acetylthieno[3,2-c]pyrazole-5-carboxylate Chemical compound CC(=O)N1N=CC2=C1C=C(C(=O)OC)S2 XELZGAJCZANUQH-UHFFFAOYSA-N 0.000 abstract description 6
- 230000003321 amplification Effects 0.000 abstract description 3
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 3
- 238000004262 preparative liquid chromatography Methods 0.000 abstract description 3
- 238000000638 solvent extraction Methods 0.000 abstract description 3
- 239000000975 dye Substances 0.000 description 19
- 239000007788 liquid Substances 0.000 description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052707 ruthenium Inorganic materials 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical group COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 6
- -1 bipyridyl ruthenium Chemical compound 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 230000005693 optoelectronics Effects 0.000 description 4
- 230000001172 regenerating effect Effects 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 238000004847 absorption spectroscopy Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FXPLCAKVOYHAJA-UHFFFAOYSA-N 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylic acid Chemical compound OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1 FXPLCAKVOYHAJA-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- ABMDIECEEGFXNC-UHFFFAOYSA-N n-ethylpropanamide Chemical compound CCNC(=O)CC ABMDIECEEGFXNC-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011403 purification operation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003303 ruthenium Chemical class 0.000 description 2
- 150000003304 ruthenium compounds Chemical class 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NMOJAXCSURVGEY-UHFFFAOYSA-N N#CC#N.[S] Chemical compound N#CC#N.[S] NMOJAXCSURVGEY-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- IGSKHXTUVXSOMB-UHFFFAOYSA-N cyclopropylmethanamine Chemical compound NCC1CC1 IGSKHXTUVXSOMB-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000858 thiocyanato group Chemical group *SC#N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
The method that the present invention relates to the use of back extraction purification Ruthenium complex crude product, the method flowed back by heated solvent is stripped the impurity in Ruthenium complex crude product with the solvent close to boiling point, so that impurity and target compound separation.According to the present invention, using the nuance of target product and impurity solubility in a solvent in the purification process of bipyridyl ruthenium complex compound, high temperature solvent extraction crude product is used repeatedly, the product of high-purity is obtained.The filler chromatographic columns of Sephadex LH 20 or preparative liquid chromatography and the organic solvent of substantial amounts of high-purity of costliness are not used, only need most basic heating, and drying plant, consume a small amount of common solvent, cost is low, equipment is simple, easy to operate, yield is high, purity is high, excellent device performance, the feasibility with further amplification production.
Description
Technical field
The present invention relates to a kind of method for purifying Ruthenium complex crude product.
Background technology
Because oil crisis grows in intensity, solar energy is as one of regenerative resource more and more by the extensive of countries in the world
Pay attention to., Lausanne, SUI engineering college in 1991And O ' Regan publish an article on world-renowned periodical Nature, report
A kind of novel solar battery, using nano-crystalline titanium dioxide as opto-electronic conversion semiconductor, dyestuff is photosensitizer, battery efficiency
It is record-breaking to have reached 7.1%~7.9%.2011,Et al. with the oxidation based on Co (II/III) four (bipyridyl)
Reduction is to for electrolyte, with porphyrin as sensitizer, photoelectric transformation efficiency has reached 12.3%, is the highest reported at present
Value.DSSC has all started research heat in the world as solar photo-electric conversion device of new generation
Tide, actively prepares to gain the initiative.
In DSSC, titanium dioxide semiconductor film has the spy of opto-electronic conversion as working electrode
Property, but be due to the limitation of self character, it is impossible to using the visible ray and near infrared light in solar spectrum, so in work electricity
In the manufacturing process of pole, it is desirable to which titanium dioxide electrodes are soaked in 0.1~0.3M dye solution, sensitizer is adsorbed, to open up
The light abstraction width of wide solar cell.
Dyestuff as DSSC key components, for solar cell opto-electronic conversion imitate
Rate, life-span, cost and the feasibility of large-scale production suffer from vital influence.Bipyridyl ruthenium complex compound is earliest should
For the sensitizer of DSSC, Stability Analysis of Structures, efficiency high, the feasibility with practical application are used as photoelectricity
The star molecule of conversion, research enthusiasm does not go downhill permanently.During bipyridyl ruthenium (Ru) complex compound for example shown in formula (I) is exactly dyestuff
It is a kind of；
Wherein, X1For one of formula (2)~(19) and X2For hydrogen, or X1With X2Be all formula (2)~(19) wherein it
One；
Wherein, R1~R40It is each independently H, CtH2t+1(t=1~15), OCvH2v+1(v=1~15), SCwH2w+1(w=1
One of~15) or for expression (36)~(37), and it is 1~4 that n, which is 0~2, m, wherein, Y1For sulphur (S), methene
(CH2), ammonium (N-R) (R be H or CxH2x+1One of (x=1~15)), one of oxygen (O) or selenium (Se)；
Y wherein in formula (2)~(19)2One of formula (20)~(37) can be each independently；
Wherein, i=1~15 in formula (21), and wherein, k=1~15 in j=1~15 in formula (22), and (23),
Wherein R41~R45、R48~R58It is each independently H, CAH2A+1(A=1~15), OCBH2B+1(B=1~15), SCDH2D+1(D=1~
15) or for expression (36)~(37)；Wherein, R46~R47, it is each independently H, CEH2E+1(E=1~6) or OCFH2F+1(F=1
~6) or SCGH2G+1(G=1~15), wherein formula (36) and the R in formula (37)59With R60It is each independently H or CJH2J+1(J=1
~15) and r is C in 0~6, and formula (24), formula (26), formula (27), formula (28) and formula (29)qH2qQ=1~3；
Wherein Z1For one of formula (38)~(44).Wherein Z2For one of hydrogen or formula (38)~(44) or
It is Z1With Z2For identical group；
Wherein, R61With R62It is each independently H, CIH2I+1(I=1~15), OCJH2J+1(J=1~15) or SCKH2K+1(K=
One of 1~15)；Wherein A1Represent hydrogen, lithium, sodium, potassium, quarternary ammonium salt (as shown in formula (45)) or it is other it is positively charged from
Son or group；
Wherein, R63~R66It is each independently H or CyH2y+1(y=1~15).
It is important to note that as the X in formula (I)2For H, Z1With Z2It is all formula (38), X1For formula (2)~(5) wherein
One of, and n=0, Y in formula (2)~(5)1During for sulphur (S), then the Y in formula (2)~(5)2It is not formula (20), formula (21) or formula
(22)。
In addition, as the Z in formula (I)1With Z2It is all formula (38) and X1With X2It is all one of formula (2)~(5), and
N=0, Y in formula (2)~(5)1During for sulphur (S), then the Y in formula (2)~(5)2It is not formula (20), formula (21) or formula (22).
Specifically, shown in the structure of bipyridyl ruthenium Complex dyes such as following formula (61)~(76), Z1With Z2It is all formula (38)
Or formula (40)；
Wherein, the R in formula (61)67、R68、R69With R70It is each independently H, CEH2E+1(E=1~6), OCFH2F+1(F=1~
6)、SCGH2G+1(G=1~15) or it is one of formula (36)~(37)；R in formula (62)71、R72、R73With R74Independently
For H, CAH2A+1(A=1~15), OCBH2B+1(B=1~15) or SCDH2D+1(D=1~15) or for formula (36)~(37) wherein
One of；R in formula (63)75With R76It is each independently H, CtH2t+1(t=1~15), OCvH2v+1(v=1~15) or SCwH2w+1
(w=1~15) or it is one of formula (36)~(37)；R in formula (64)~(66)77、R78、R79、R80、R81With R82It is only respectively
Stand as SCGH2G+1(G=1~15) or it is one of formula (36)~(37)；R in formula (67)83、R84、R85With R86Independently
For H, CAH2A+1(A=1~15), OCBH2B+1(B=1~15), SCDH2D+1(D=1~15) or for formula (36)~(37) wherein it
One；R in formula (75)~(76)87、R88、R89With R90It is each independently H or CJH2J+1One of (J=1~15).
A in formula (61)~(76)1It is each independently hydrogen, lithium, sodium, potassium, quarternary ammonium salt (as shown in formula (45))；
Wherein, R63、R64、R65With R66It is each independently H or CyH2y+1(y=1~20).
The bipyridyl ruthenium Complex dyes synthesized in document are had in part not purify further, but are directly used as too
It is positive can battery sensitizer, such as non-patent literature 1, non-patent literature 2, non-patent literature 3, patent document 1, patent document 2, specially
Sharp document 3.But pass through experimental verification, dyestuff crude product is due to containing unreacted raw material, accessory substance and some other different
Structure body so that power conversion efficiency (pce) is low, stability is poor.But the bipyridyl ruthenium Complex dyes of high-purity are expensive, whole
Very big share is occupied in the production cost of individual solar module, the application of DSSC is constrained.
And purification spends more than half for occupying cost in the manufacturing process of dyestuff.Bipyridyl ruthenium Complex dyes have crystal property
Difference, the characteristics of polarity is big, these all cause the difficulty of purification.Have no idea to be purified by common silicagel column, document
In separated generally by Sephadex LH-20 for the chromatographic column of filler, such as non-patent literature 4, non-patent literature 5, special
Sharp document 4.The filler is expensive, and material is easily deteriorated, and rear refining effect is used for multiple times and is difficult to ensure that.In purification process
A large amount of high-purity solvents of middle consumption further make cost remain high.On the other hand, not only material cost is high, and post layer
The product yield that analysis is provided is limited by equipment for purifying, and yield can not still meet requirement.
Although other patent document 5 is there is provided a kind of side that the light-sensitive coloring agents such as Z907 are purified with preparative high-performance liquid chromatographic
Method, the light-sensitive coloring agent such as the Z907 so as to obtain high-purity, high-quality.Shown in Z907 structural formula such as formula (1),
Wherein, Z1With Z2It is all-COOH, and X1With X2It is all-C9H19。
But preparative high-performance liquid chromatographic is bigger than Sephadex LH-20 chromatographic column limitations, such as requirement of environmental condition
Compare harsh, instrument maintenance cost etc., a large amount of high-purities consumed in preparation scale performance liquid chromatographic column and purification
Efficient liquid phase level reagent makes cost higher.Preparation scale performance liquid chromatographic column diameter is no more than 5 centimetres, each sample introduction simultaneously
Amount is no more than 20 milliliters, and the product obtained after primary purification is less than Sephadex LH-20 chromatographic columns.
This just causes difficulty to large-scale production, and with the raising of yield, equipment cost, material cost and manpower
The space that cost does not decline significantly.
Prior art literature：
Non-patent literature 1：P.Liska et al,“cis-Diaquabis(2,2'-bipyridyl-4,4’-dicarbo
xylate)-ruthenium(II)Sensitizes Wide Band Gap Oxide Semiconductors Very
Efficiently over a Broad Spectral Range in the Visible”,J.Am.Chem.Soc.1988,
110,3686~3687 (p3686)；
Non-patent literature 2：M.K.Nazeeruddin et al,“Conversion of Light to Electricity
by cis-X2Bis(2,2’-bipyridyl-4,4’-dicarboxylate)ruthenium(II)Charge-Transfer
Sensitizers (X=Cl-, Br-, I-, CN-, and SCN-) on Nano crystalline TiO2 Electrodes”,
J.Am.Chem.Soc.1993,115,6382~6390 (p6383:Materials)；
Non-patent literature 3：Md.K.Nazeeruddin et al,“Acid-Base Equilibria of(2,2'-
bipyridyl-4,4'-dicarboxylic acid)ruthenium(II)Complexes and the Effect of
Protonation on Charge-Transfer Sensitization of Nanocrystalline Titania”,
Inorg.Chem.1999,38,6298~6305 (p6299:Synthesis of complexs 1,and 2,p6303:HPLC
of complex 2)；
Non-patent literature 4：M.K.Nazeeruddin et al,“Engineering of efficient
panchromatic sensitizers for nanocrystalline TiO2-based solar cells”,
J.Am.Chem.2001,123,1613-1624(p483:Synthesis)
Non-patent literature 5：Peng Wang et al,“A stable quasi-solid-state dye-
sensitized solar cell with an amphiphilic ruthenium sensitizer and polymer
Gel electrolyte " Nature materials, 2003,402~407 (p406:Methods)；
Patent document 1：No. 5463057 specifications of U.S. Patent No. (embodiment 1, embodiment 2)；
Patent document 2：Unexamined Patent 11-279188 publications (paragraph 0004 to 0005)；
Patent document 3：JP 2001-139587 publications (paragraph 0004 to 0005)；
Patent document 4：United States Patent (USP) US2007/0265443A1；
Patent document 5：United States Patent (USP) US2010/0275391A1.
The content of the invention
In view of the above-mentioned problems, improving bipyridyl ruthenium complex compound it is an object of the invention to provide a kind of new method of purification
The purity of dyestuff, the opto-electronic conversion after the dyestuff after making up to and being purified more than column chromatography is applied on the solar cell is imitated
Rate.Production efficiency is increased substantially simultaneously, yield is improved, and reduces material cost, equipment cost and human cost.
Here, the present invention provides a kind of method using back extraction purification Ruthenium complex crude product, methods described is to pass through
Heated solvent backflow method, with close to boiling point solvent be stripped Ruthenium complex crude product in impurity so that impurity and
Target compound is separated.
According to the present invention, dissolved in a solvent using target product and impurity in the purification process of bipyridyl ruthenium complex compound
The nuance of degree, uses high temperature solvent extraction crude product repeatedly, obtains the product of high-purity.Costliness is not used
The organic solvent of SephadexLH-20 fillers chromatographic column or preparative liquid chromatography and substantial amounts of high-purity, it is only necessary to most
Basic heating, and drying plant, consume a small amount of common solvent, cost is low, equipment is simple, easy to operate, yield is high, purity
Height, excellent device performance, the feasibility with further amplification production.
In one preferred embodiment, methods described comprises the following steps：
Step A) by Ruthenium complex crude product be placed in filter paper bucket in, by the filter paper bucket be put into cable type extractor according, with
Appropriate solvent is added in the ground flask of set, from the top down condenser pipe, cable type extractor according, ground flask, thermal source is assembled in
Together；
Step B) heat source temperature is adjusted to flask heating so that and the solvent in flask does not stop backflow, into cable type extractor according,
Extract and enter flask after the impurity in Ruthenium complex crude product, be heated to reflux 1~5 hour, stop heating, be progressively cooled to room
Temperature；
Step C) collect the solid remained in filter paper bucket, the product after being purified after drying.
The present invention utilizes cable type extractor according solid-liquid stripping process purification Ruthenium complex crude product.Cable type extractor according extensive use
In biological field, the target components in animal vegetable tissue, organic solvent distillation placed below are extracted with specific organic solvent
In flask, thing to be extracted is placed in cable type extractor according, is flowed back by heated solvent, and thing to be extracted is extracted repeatedly, by target components
Enrichment is into the distilling flask of lower section.
The present invention, come the impurity in back extraction ruthenium dye, reaches raising ruthenium class dyestuff creatively using cable type extractor according
The purpose of purification.It is with traditional different part of cable type extractor according application method, raw material to be separated is chemical synthesis
Crude product, and non-natural biological tissue；Target product solid after separation is stayed in cable type extractor according, rather than is dissolved in down
In the solution of square flask, so being solid-liquid back extraction.
Another preferred embodiment in, methods described comprises the following steps：
Step 1) Ruthenium complex crude product and appropriate solvent are placed in ground flask, from the top down by supporting condensation
Pipe, ground flask, thermal source are fitted together；
Step 2) material in flask is carried out to be heated to reflux stirring 1~5 hour, it is cooled to room temperature after stopping heating；
Step 3) material in flask is filtered, solid is collected, is dried；
Step 4) repeat step 1) to step 3) 2~10 times, that is, the product after being purified.
Purifying plant in the above method is relatively simple, but compared to the method for cable type extractor according, repeatedly to enter repeatedly
The purification of row identical, drying process, it is time-consuming longer, and need a large amount of solvents, cost increase, so more preferably using cable-styled
The method of purification of extractor solid-liquid back extraction.
It is preferred that the solvent is tetrahydrofuran, N, N '-dimethyl formamide, N, N '-diethylformamide, N, N '-two
Cyclopropylmethylamide, tetramethyl ammonium hydroxide solution, tetraethyl ammonium hydroxide solution, TBAH solution, acetone, fourth
Ketone, ethyl acetate, petroleum ether, ether, methyl phenyl ethers anisole, phenetole, chloroform, dichloromethane, acetonitrile, ethanol, methanol, formaldehyde, formic acid,
At least one of acetic acid, benzene, toluene, benzoic acid, n-hexane, hexamethylene, chlorobenzene, iodobenzene and water.
It is preferred that step A) and/or step 1) in, the consumption of the solvent for every gram of Ruthenium complex crude product 10~
50ml。
It is preferred that step B) in, can be until the solute and its content that detect in the solution in flask no longer change
Or filter paper bucket in solid composition and its content no longer change after stop heating.
It is preferred that step C) and/or step 3) in, the drying be at 30 DEG C~70 DEG C dry 12~48 hours or
Person is dried in vacuo.Being dried in the case of relatively low temperature or vacuum can prevent from regenerating isomers or other are miscellaneous
Matter.
It is preferred that step 4) in, can be repeat step 1) to step 3) until detecting step 3) and in filtrate in
The composition and its content for the solid that solute and its content no longer change or collected no longer change.
It is preferred that step B) and/or step 4) in, detected with the method for ultraviolet, nuclear-magnetism or HPLC.
Method is simple by the present invention, it is adaptable to mass produces, high with yield, and cost is low, the features such as taking short,
Product purity after purification is high, and quality better can significantly improve the photoelectric transformation efficiency of DSSC, booster
Part stability, has broad application prospects.
Brief description of the drawings
Fig. 1 is the HPLC spectrograms for using solution in flask after cable type extractor according solid-liquid back extraction；
Fig. 2 is the HPLC spectrograms (purity 95.1%) that solid is collected into after being purified with cable type extractor according solid-liquid back extraction；
Fig. 3 is the change of the uv-visible absorption spectroscopy of solid in purification process；
Fig. 4 is the proton nmr spectra of ruthenium complex before and after purification；
Fig. 5 is the schematic device of cable type extractor according solid-liquid back extraction.
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing and following embodiments, it should be appreciated that accompanying drawing and following embodiments
The present invention is merely to illustrate, is not intended to limit the present invention.
The purity of bipyridyl ruthenium Complex dyes is improved the invention provides a kind of new method of purification, is made up to simultaneously
And the photoelectric transformation efficiency after being applied on the solar cell more than the dyestuff after column chromatography purification.Increase substantially production simultaneously
Efficiency, improves yield, reduces material cost, equipment cost and human cost.Specifically, the present invention utilizes target product and miscellaneous
The nuance of matter solubility in a solvent, the method flowed back with heated solvent is relatively easy to the solvent back extraction close to boiling point
Each impurity of dissolving in a solvent, reaches the purpose for separating impurity and target compound, so as to increase substantially product product
Matter.
The applicable Ruthenium complex crude product to be purified of the method for the present invention can be by after the synthesis of various methods, separation
Obtained ruthenium complex crude product.For example can be according to document (Chia-Yuan Chen et
Al.Angew.Chem.Int.Ed., 2006,45 (35), 5822-5825) in one pot process Ruthenium complex crude product.
I.e., the present invention is not limited the source of Ruthenium complex crude product to be purified.In addition, in the present invention, bipyridyl to be purified
Ruthenium complex includes but is not limited to all compounds shown in above-mentioned formula (I).
In the present invention, the solvent used can be the solvent readily soluble to impurity to target compound indissoluble, including but
It is not limited to tetrahydrofuran, N, N '-dimethyl formamide, N, N '-diethylformamide, N, N '-dipropyl formamide, tetramethyl hydrogen
Ammonium hydroxide solution, tetraethyl ammonium hydroxide solution, TBAH solution, acetone, butanone, ethyl acetate, petroleum ether, second
Ether, methyl phenyl ethers anisole, phenetole, chloroform, dichloromethane, acetonitrile, ethanol, methanol, formaldehyde, formic acid, acetic acid, benzene, toluene, benzoic acid,
At least one of n-hexane, hexamethylene, chlorobenzene, iodobenzene and water.These solvents can utilize deliquescent different points well
From target product and impurity.
In the present invention, the high-temperature solvent close to boiling point produced by being heated to reflux by solvent enters to Ruthenium complex crude product
Row extraction, compared to normal temperature extraction, effect of extracting is more preferably, more efficient.
The present invention one preferred embodiment in, utilize cable type extractor according solid-liquid stripping process purification ruthenium complex
Crude product.
Cable type extractor according is widely used in biological field, and the target group in animal vegetable tissue is extracted with specific organic solvent
Point, in organic solvent distilling flask placed below, thing to be extracted is placed in cable type extractor according, is flowed back by heated solvent, instead
Thing to be extracted is extracted again, and target components are enriched with into the distilling flask of lower section.
The present invention, come the impurity in back extraction ruthenium dye, reaches raising ruthenium class dyestuff creatively using cable type extractor according
The purpose of purification.It is with traditional different part of cable type extractor according application method, raw material to be separated is chemical synthesis
Crude product, and non-natural biological tissue；Target product solid after separation is stayed in cable type extractor according, rather than is dissolved in down
In the solution of square flask, so being solid-liquid back extraction.
Moreover, using cable type extractor according can be formed it is continual extract repeatedly, take that short, solvent load is few, operation is simple
Just.
More specifically, as an example, above-mentioned utilization cable type extractor according solid-liquid stripping process may include steps of：
Step A) as shown in figure 5, bipyridyl Ruthenium complex crude product is placed in filter paper bucket, filter paper bucket is then put into rope
In formula extractor, appropriate solvent is added in supporting ground flask, from the top down by condenser pipe, cable type extractor according, ground
Flask, thermal source is fitted together；
Step B) regulation heat source temperature so that the solvent in flask does not stop backflow, into cable type extractor according, extracts in dyestuff
Impurity after enter flask；
Step C) heat after appropriate time, thermal source is removed, room temperature is progressively cooled to；
Step D) collect the solid remained in filter paper bucket, the product after being purified after drying.
Wherein, step A) in, the solvent used is as described above.
Wherein, step A) in, solvent load can be every gram of ruthenium crude product 10-50ml in flask.
Wherein, step C) in, solute in solution and its content preferably in flask no longer change or filter paper bucket in
The composition and its content of solid terminate heating after no longer changing.For example can be with ultraviolet, nuclear-magnetism or HPLC method determine flask
The spectrogram of solid terminates heating after no longer changing in middle solution or filter paper bucket.When spectrogram does not change, illustrate that impurity is complete
It is complete to remove, or can not further remove, stop purification operations.For example, can be 1~5 hour the time required to heating.
Wherein, step D) in, the drying is that 12h~48h is dried at 30 DEG C~70 DEG C, or the drying is vacuum
Dry.Being dried in the case of relatively low temperature or vacuum can prevent from regenerating isomers or other impurities.
Fig. 1 is the HPLC spectrograms for using solution in flask after cable type extractor according solid-liquid back extraction, and Fig. 2 is to use cable type extractor according
The HPLC spectrograms (purity 95.1%) of solid, the flask it can be seen from Fig. 1 and Fig. 2 are collected into after the purification of solid-liquid back extraction
Target compound is practically free of in solution, illustrates the loss very little of target compound in purification process, and the solid being collected into is pure
Degree is high, quality better.Fig. 3 is the change of the uv-visible absorption spectroscopy of solid in purification process, as seen from Figure 3, purification
Process can be controlled simply by absorption spectrum, the absworption peak at 350nm gradually to long wave direction move, 540nm
The absworption peak at place gradually strengthens, and back extraction process can be just terminated when absorption spectrum no longer changes.Fig. 4 is ruthenium complexing before and after purification
The proton nmr spectra of thing, as seen from Figure 4, after purification, the purity of ruthenium complex is greatly improved.
In another embodiment, directly Ruthenium complex crude product is placed in high-temperature solvent and extracted.Specifically,
As an example, may include following steps：
Step 1) bipyridyl Ruthenium complex crude product is placed in ground flask, appropriate solvent is added, from the top down will
Supporting condenser pipe, ground flask, thermal source is fitted together；
Step 2) heating flask in solution, stop heating after, be cooled to room temperature；
Step 3) filtering solution, solid is collected, is dried；
Step 4) repeat step 1) -3).
Wherein, step 1) in, the solvent used is as described above.
Wherein, step 1) in, solvent load is every gram of ruthenium crude product 10-50ml in flask.
Wherein, step 2) in, heating-up temperature can be to make the temperature of solvent refluxing.Heat time can be 1~5 hour.In addition,
In heating process, the material in flask can be stirred.
Wherein, step 3) in, the drying is that 12h~48h is dried at 30 DEG C~70 DEG C, or the drying is vacuum
Dry.Being dried in the case of relatively low temperature or vacuum can prevent from regenerating isomers or other impurities.
Wherein, step 4) in, preferably step 3) in filtrate in solute and its content consolidating of no longer changing or collect
The composition and its content of body stop repeat step 1 after no longer changing) -3).For example can be with ultraviolet, nuclear-magnetism or HPLC method are true
Determine the solid of filtrate or collection spectrogram no longer change after stop repeat step 1) -3).When spectrogram does not change, illustrate impurity
Remove, or can not further remove completely, stop purification operations.For example, according to circumstances repeating 2~10 times.
Identical purification, drying process will be repeatedly repeated in this method, time-consuming extremely long, and needs a large amount of solvents, into
This increase, it is advantageous to the method for purification for use cable type extractor according solid-liquid back extraction.But this method also has purification dress
Put more simple advantage.
According to the present invention, dissolved in a solvent using target product and impurity in the purification process of bipyridyl ruthenium complex compound
The nuance of degree, using cable type extractor according, it is only necessary to the solvent of two siphons, uses high temperature solvent extraction crude product, obtains repeatedly
The product of high-purity.The Sephadex LH-20 fillers chromatographic columns or preparative liquid chromatography of costliness are not used and a large amount of
High-purity organic solvent, it is only necessary to most basic heating, and drying plant, consume that a small amount of common solvent, cost be low, equipment
Simply, easy to operate, yield is high, purity is high, excellent device performance, the feasibility with further amplification production.
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made belong to protection scope of the present invention.Following examples are specific
Technological parameter etc. is also only that an example in OK range, i.e. those skilled in the art can be done properly by this paper explanation
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.
In the following example 1,2,3,4 and comparative example, the bipyridyl ruthenium complex compound used is cis- two (different sulphur cyanogen
Base)-two (4,4 '-two (2- (the own sulfenyl-phenyl of 4-) vinyl) -2,2 '-bipyridyls) conjunction ruthenium (II) complex compound (cis-bis
(thiocyanato)(2,2’-bipyridyl-4,4’-dicarboxylato){4,4’-bis[2-(4-
Hexylsulfanylphenyl) vinyl] -2,2 '-bipyridine } ruthenium (II)), its code name is TG6, its structure
Formula is as follows：
TG6 is synthesized by the method for document (J.Mater.Chem., 2008,18,4246-4253).
Comparative example
It is filler with Sephadex LH-20 according to non-patent literature 4 and non-patent literature 5, methanol, water enters for eluant, eluent
Row column chromatography is purified, and it is 95% to obtain purity, the TG6 solids that purification yield is 80%.
Embodiment 1
By 50g cis- two (isothiocyano)-two (4,4 '-two (2- (the own sulfenyl-phenyl of 4-) vinyl) -2,2 '-bipyridyl)
Close ruthenium (II) complex compound (purity 82%) to be placed in cable type extractor according, 250ml dichloromethane is placed in 500mL flasks.Collocation
Device, as shown in Figure 5.Heated solvent is to seething with excitement, the ruthenium compound constantly in extraction cable type extractor according.Stop heating after 2 hours,
After cooling, the solid in cable type extractor according is collected, 42g products (purity 95%, yield 84%) are obtained after drying.After purification terminates
The HPLC spectrograms of solution are as shown in Figure 1 in flask.The HPLC spectrograms for the solid being collected into are as shown in Figure 2.Solid in purification process
Uv-visible absorption spectroscopy change it is as shown in Figure 3.The proton nmr spectra of ruthenium complex is as shown in Figure 4 before and after purification.
Embodiment 2
By 50g cis- two (isothiocyano)-two (4,4 '-two (2- (the own sulfenyl-phenyl of 4-) vinyl) -2,2 '-bipyridyl)
Close ruthenium (II) complex compound (purity 82%) to be placed in cable type extractor according, 250ml chloroforms (chloroform) are placed in 500mL flasks
In.Adaptation arrangement, as shown in Figure 5.Heated solvent is to seething with excitement, the ruthenium compound constantly in extraction cable type extractor according.Stop after 2 hours
Only heat, after cooling, collect the solid in cable type extractor according, 45g products (purity 95%, yield 90%) are obtained after drying.
Embodiment 3
By 50g cis- two (isothiocyano)-two (4,4 '-two (2- (the own sulfenyl-phenyl of 4-) vinyl) -2,2 '-bipyridyl)
Close ruthenium (II) complex compound (purity 82%) and 250ml dichloromethane is placed in 500mL flasks, be heated to reflux, stir 2 hours.It is cold
But filter afterwards, collect solid, dry；
After repetition said process 5 times, 40g products (purity 95%, yield 80%) are obtained.
Embodiment 4
By 50g cis- two (isothiocyano)-two (4,4 '-two (2- (the own sulfenyl-phenyl of 4-) vinyl) -2,2 '-bipyridyl)
Close ruthenium (II) complex compound (purity 82%) and 250ml chloroforms are placed in 500mL flasks, be heated to reflux, stir 2 hours.It is cold
But filter afterwards, collect solid, dry；
After repetition said process 4 times, 41g products (purity 95%, yield 82%) are obtained.
Claims (8)
1. a kind of method using back extraction purification Ruthenium complex crude product, it is characterised in that the side flowed back by heated solvent
Method, the impurity in Ruthenium complex crude product is stripped with the solvent close to boiling point, so that impurity and target compound separation；
The solvent is at least one of chloroform, dichloromethane, and the ruthenium complex is cis- two（Isothiocyano）- two（4,
4 '-two（2- (the own sulfenyl-phenyl of 4-) vinyl）- 2,2 '-bipyridyl）Close ruthenium（II）Complex compound.
2. according to the method described in claim 1, it is characterised in that methods described comprises the following steps：
Step A）Ruthenium complex crude product is placed in filter paper bucket, filter paper bucket is put into cable type extractor according, supporting
Appropriate solvent is added in ground flask, from the top down condenser pipe, cable type extractor according, ground flask, thermal source is fitted together；
Step B）Adjust heat source temperature to heat flask so that the solvent in flask does not stop backflow, into cable type extractor according, extraction
Enter flask after impurity in Ruthenium complex crude product, be heated to reflux 1~5 hour, stop heating, be progressively cooled to room temperature；
Step C）Collect the solid remained in filter paper bucket, the product after being purified after drying.
3. according to the method described in claim 1, it is characterised in that methods described comprises the following steps：
Step 1）Ruthenium complex crude product and appropriate solvent are placed in ground flask, from the top down by supporting condenser pipe,
Ground flask, thermal source are fitted together；
Step 2）Material in flask is carried out to be heated to reflux stirring 1~5 hour, room temperature is cooled to after stopping heating；
Step 3）Material in flask is filtered, solid is collected, dried；
Step 4）Repeat step 1）To step 3）2~10 times, that is, the product after being purified.
4. according to the method in claim 2 or 3, it is characterised in that step A）And/or step 1）In, the use of the solvent
Measure as every gram of 10~50ml of Ruthenium complex crude product.
5. method according to claim 2, it is characterised in that step B）In, until detecting in the solution in flask
Solute and its content no longer change or filter paper bucket in solid composition and its content no longer change after stop heating.
6. method according to claim 3, it is characterised in that step 4）In, repeat step 1）To step 3）Until detection
To step 3）In filtrate in solute and its content composition of solid that no longer changes or collect and its content no longer change.
7. the method according to claim 5 or 6, it is characterised in that step B）And/or step 4）In, with ultraviolet, nuclear-magnetism or
Person HPLC method is detected.
8. according to the method in claim 2 or 3, it is characterised in that step C）And/or step 3）In, the drying be
Dried 12~48 hours at 30 DEG C~70 DEG C or vacuum drying.
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Effective date of registration: 20230726 Address after: 215400 No.6 Liangfu Road, Taicang City, Suzhou City, Jiangsu Province Patentee after: Jiangsu Institute of advanced inorganic materials Address before: 200050 No. 1295 Dingxi Road, Shanghai, Changning District Patentee before: SHANGHAI INSTITUTE OF CERAMICS, CHINESE ACADEMY OF SCIENCES |
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