CN103193761A - 2-phenyl-6-azolylpyridine ligand and group VIII transition metal complex formed by same - Google Patents

2-phenyl-6-azolylpyridine ligand and group VIII transition metal complex formed by same Download PDF

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CN103193761A
CN103193761A CN2012100328924A CN201210032892A CN103193761A CN 103193761 A CN103193761 A CN 103193761A CN 2012100328924 A CN2012100328924 A CN 2012100328924A CN 201210032892 A CN201210032892 A CN 201210032892A CN 103193761 A CN103193761 A CN 103193761A
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CN103193761B (en
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季昀
徐健维
何恕德
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The 2-phenyl-6-azolyl pyridine ligand has the structure shown in the formula , wherein X is C-R10Or a nitrogen atom; r1～R8And R10Are identical or different and are each hydrogen, halogen, cyano, amino, aryl, heteroaryl, sulfate, acetate, alkoxy, carbonyl, C1～C10Halogenoalkyl of, C1～C12Alkyl of (C)2～C10Alkenyl of, C2～C10Alkynyl of , C3～C20Cycloalkyl of, C3～C20Cycloalkenyl group of , C1～C20Heterocycloalkyl of , C1～C20Heterocycloalkenyl of , or a combination of the foregoing; r9Is hydrogen or an alkali metal; with the proviso that when X is C-R10When R is5And R7Not both fluorine and R6And R8Not both being hydrogen, or R6And R8Not both fluorine and R5And R7Not both may be hydrogen. The invention also provides a group VIII transition metal complex containing the ligand for a dye-sensitized solar cell.

Description

2-phenyl-6-azoles yl pyridines is that aglucon reaches by its formed the 8th group 4 transition metal complexes
Technical field
The present invention relates to a kind of pyridine compounds and their and contain the metal complexes of this pyridine compounds and their, particularly relating to a kind of 2-phenyl-6-azoles yl pyridines is that aglucon and a kind of this 2-phenyl-6-azoles yl pyridines that contains are the 8th group 4 transition metal complexes of aglucon.
Background technology
Along with the mankind are more and more to the demand of the energy, add that sun power is much accounted of gradually because having inexhaustible, nexhaustible advantage, and then promote the application development of solar cell.Wherein, dye sensitization solar battery (dye-sensitized solar cell, be called for short DSSC) is the solar battery technology of potentialization.DSSC is visible light and the near infrared light that utilizes in the dyestuff absorption sun power, and generation excitation electron, the quality of dye property this excitation electron injected on the conduction band of semi-conducting electrode effectively, and then produces photoelectric current, so can directly influence the photoelectric transformation efficiency of DSSC.The dyestuff that is widely used in solar cell at present is to be main research object with the ruthenium complexe.
TW200721559 discloses a kind of dyestuff, has the 8th group 4 transition metal complexes as the formula (1):
M 1(T 1) m1(T 2) m2G 1 m3G 2 m4(1)
Wherein, M 1Represent the 8th group 4 transition metal element; Each T 1And T 2Be independently selected from the group that the dentate of molecular formula (1a) is formed,
Figure BDA0000135693430000011
In the formula (1a), n represents 0～1 integer, and each r 1, r 2And r 3Be to be independently selected from down group: COOH, PO 3H, SO 3H, CO 2, PO 3, SO 3, C 1～C 20The alkyl that is substituted, C 1～C 20The alkyl that is unsubstituted, C 6～C 30The aromatic base that is substituted, C 6～C 30The alkyl that is unsubstituted, C 6～C 30The aryloxy that is substituted, C 6～C 30The aryloxy that is unsubstituted, C 6～C 30The arylidene that is substituted, C 6～C 30The arylidene that is unsubstituted, C 1～C 20The alkylene that is substituted (alkylene), C 1～C 20The alkylene that is unsubstituted (alkylene), C 1～C 20The alkene oxygen base, the C that are substituted 1～C 20The alkene oxygen base that is unsubstituted;
G 1Be selected from down group: hydrogen, NO 2, Cl, Br, I, CN, NCS, H 2O, NH 3, Cl, Br, I, CN, NCS and PF 6
G 2Be selected from down group: glyoxaline cation, pyridylium, Pyrrolizidine positively charged ion and quinine pyridine (quinolidinium) positively charged ion; And
M1 and m3 are from 0 to 3 integer; M2 is from 1 to 3 integer, and m4 is from 1 to 6 integer.
Yet the absorption in the photoelectric transformation efficiency that the metal complexes of above-mentioned patent application obtains in subsequent applications, visible region and near infrared light zone still has to be hoisted; Simultaneously, in the specific examples of this patent application, metal complexes is because containing two thiocyanate ion (NCS) aglucons that the coordinate bond knotting strength is more weak, be difficult for effectively and stably with the ruthenium metal-chelating, more cause dye sensitization solar battery when life-time service, its photoelectric transformation efficiency and work-ing life are not good.
Therefore, develop a kind of novelty and have the pyridine compounds and their of broader photo-absorption region and contain the 8th group 4 transition metal complexes of this pyridine compounds and their, and allow the dye sensitization solar battery that contains this 8th group 4 transition metal complexes when life-time service, can have preferable photoelectric transformation efficiency and work-ing life, become the target that those skilled in the art make great efforts to study.
Summary of the invention
First purpose of the present invention is that the 2-phenyl-6-azoles yl pyridines that a kind of novelty is provided and has wideer photo-absorption region is aglucon.2-phenyl of the present invention-6-azoles yl pyridines is aglucon, shown in formula (I):
In the formula (I), X is C-R 10Or nitrogen-atoms; R 1～R 8And R 10For identical or different, and be respectively hydrogen, halogen, cyano group, amido, aryl, heteroaryl, sulfate radical, acetate moiety, alkoxyl group, carbonyl, C 1～C 10Haloalkyl, C 1～C 12Alkyl, C 2～C 10Thiazolinyl, C 2～C 10Alkynyl, C 3～C 20Cycloalkyl, C 3～C 20Cycloalkenyl group, C 1～C 20Heterocyclylalkyl, C 1～C 20Heterocycloalkenyl, or the combination of above-mentioned group; R 9Be hydrogen or basic metal; Condition be when X be C-R 10The time, R 5And R 7Can not be fluorine and R simultaneously 6And R 8Can not be hydrogen simultaneously, or R 6And R 8Can not be fluorine and R simultaneously 5And R 7Can not be hydrogen simultaneously.
Second purpose of the present invention be to provide a kind of in the visible region and the near infrared light zone have the 8th group 4 transition metal complexes of preferable absorption, and be subsequently applied on the dye sensitization solar battery, can make this battery when life-time service, have preferable photoelectric transformation efficiency and work-ing life.
The present invention's the 8th group 4 transition metal complexes, shown in formula (II):
ML 1L 2(II)
In the formula (II), M represents ruthenium metal or osmium metal; L 1Be that as mentioned above a 2-phenyl-6-azoles yl pyridines is aglucon; L 2The two pyridines of expression carboxyl are aglucon.
Beneficial effect of the present invention is: relying on 2-phenyl-6-azoles yl pyridines is the structure design of aglucon, make this aglucon can be in the visible region and the near infrared light zone have preferable absorption, and after forming the 8th group 4 transition metal complexes with metal-complexing, absorption spectrum ranges and the solar spectrum of the 8th group 4 transition metal complexes are complementary, strengthen the 8th group 4 transition metal complexes to the absorption in visible region and near infrared light zone.In addition, the 8th group 4 transition metal complexes is subsequently applied in the dye sensitization solar battery, can makes this dye sensitization solar battery effectively utilize sun power, when life-time service, have preferable photoelectric transformation efficiency and work-ing life.
Description of drawings
Fig. 1 is the abosrption spectrogram of the N749 dyestuff of the absorption spectrum of the ruthenium complexe of preferred embodiment of the present invention and comparative example 1.
Fig. 2 is applied on the dye sensitization solar battery for the ruthenium complexe of preferred embodiment of the present invention, when life-time service, and the photoelectric transformation efficiency figure of this dye sensitization solar battery.
Embodiment
2-phenyl of the present invention-6-azoles yl pyridines is aglucon, shown in formula (I):
Figure BDA0000135693430000041
In the formula (I), X is C-R 10Or nitrogen-atoms; R 1～R 8And R 10For identical or different, and be respectively hydrogen, halogen, cyano group, amido, aryl, heteroaryl, sulfate radical, acetate moiety, alkoxyl group, carbonyl, C 1～C 10Haloalkyl, C 1～C 12Alkyl, C 2～C 10Thiazolinyl, C 2～C 10Alkynyl, C 3～C 20Cycloalkyl, C 3～C 20Cycloalkenyl group, C 1～C 20Heterocyclylalkyl, C 1～C 20Heterocycloalkenyl, or the combination of above-mentioned group; R 9Be hydrogen or basic metal; Condition be when X be C-R 10The time, R 5And R 7Can not be fluorine and R simultaneously 6And R 8Can not be hydrogen simultaneously, or R 6And R 8Can not be fluorine and R simultaneously 5And R 7Can not be hydrogen simultaneously.
At R 1～R 8Restriction in, described heteroaryl is selected from:
Figure BDA0000135693430000042
R 11～R 16Be hydrogen, halogen, cyano group, amido, aryl, heteroaryl, alkoxyl group, C 1～C 10Haloalkyl, C 1～C 12Alkyl, C 2～C 10Thiazolinyl, C 2～C 10Alkynyl, C 3～C 20Cycloalkyl, C 3～C 20Cycloalkenyl group, C 1～C 20Heterocyclylalkyl, C 1～C 20Heterocycloalkenyl, or the combination of above-mentioned group.
At R 1～R 8Restriction in, described amido is selected from: NR 17R 18,
Figure BDA0000135693430000044
Figure BDA0000135693430000051
R 17～R 22Be hydrogen, halogen, cyano group, amido, aryl, heteroaryl, alkoxyl group, C 1～C 10Haloalkyl, C 1～C 12Alkyl, C 2～C 10Thiazolinyl, C 2～C 10Alkynyl, C 3～C 20Cycloalkyl, C 3～C 20Cycloalkenyl group, C 1～C 20Heterocyclylalkyl, C 1～C 20Heterocycloalkenyl, or the combination of above-mentioned group.Preferably, described amido is
Figure BDA0000135693430000052
At R 1～R 8Restriction in, described alkoxyl group is including but not limited to OR 23R 23Be hydrogen, halogen, cyano group, amido, aryl, heteroaryl, alkoxyl group, C 1～C 10Haloalkyl, C 1～C 12Alkyl, C 2～C 10Thiazolinyl, C 2～C 10Alkynyl, C 3～C 20Cycloalkyl, C 3～C 20Cycloalkenyl group, C 1～C 20Heterocyclylalkyl, C 1～C 20Heterocycloalkenyl, or the combination of above-mentioned group.
Preferably, X is C-R 10
Preferably, X is nitrogen.
Preferably, R 1Be trifluoromethyl.
Preferably, R 5～R 8In any is fluorine or trifluoromethyl.
Preferably, R 1Be trifluoromethyl, and R 5～R 8In any is fluorine or trifluoromethyl.
Preferably, R 3Be hydrogen, aryl, heteroaryl, amido, C 1～C 12Alkoxyl group or
Figure BDA0000135693430000053
R 24Be hydrogen, halogen, cyano group, amido, aryl, heteroaryl, alkoxyl group, C 1～C 10Haloalkyl, C 1～C 12Alkyl, C 2～C 10Thiazolinyl, C 2～C 10Alkynyl, C 3～C 20Cycloalkyl, C 3～C 20Cycloalkenyl group, C 1～C 20Heterocyclylalkyl, C 1～C 20Heterocycloalkenyl, or the combination of above-mentioned group.
2-phenyl of the present invention-6-azoles yl pyridines be aglucon specific embodiment including but not limited to
Figure BDA0000135693430000061
Aglucon reason phenyl ring group of the present invention, azoles is group, the pyridine group is formed and is had asymmetry, and this characteristic can make metal-aglucon charge transfer (metal-to-ligand charge transfer, abbreviation MLCT) absorption peak of effect does not overlap each other each other, then make that the absorption region of the 8th group 4 transition metal complexes is broader, and the carbon by phenyl ring on the aglucon can form carboanion, and with the 8th group 4 transition metal bonding, compare in the nitrogen negatively charged ion that the nitrogenous aglucon that uses forms in the past, this carboanion and phenyl group thereof have higher electron density, increase the electron density of central metal jointly, therefore can effectively improve the 8th group 4 transition metal T 2gCan rank, dwindle HOMO highest occupied molecular orbital (the highest o ccupied molecular orbital of the 8th group 4 transition metal complexes, be called for short HOMO) and lowest unoccupied molecular orbital (lowe st unoccupied molecular orbital, be called for short LUMO) the energy jump, make the absorption spectrum red shift, and design by the group on the phenyl ring, can adjust the HOMO energy rank of the 8th group 4 transition metal complexes, make the HOMO of the 8th group 4 transition metal complexes and the jump distance can freely adjusting as required of LUMO, make the 8th group 4 transition metal complexes that visible region and near infrared light zone are had better absorption then.
In addition, this 2-phenyl-6-azoles yl pyridines is that nitrogen quantity number on the azoles group of aglucon is except the HOMO that can adjust the 8th group 4 transition metal complexes and LUMO energy jump distance, and at dye sensitization solar battery, the redox potential of electrolytic solution component is adjusted in this battery of can arranging in pairs or groups in subsequent applications.The HOMO energy rank current potentials (compared to NHE current potential numerical value) of general title complex, need the redox potential greater than the electrolytic solution component, and its energy rank potential difference is at least more than the 0.55V on the experience, can make title complex have preferable regeneration efficiency, for instance, when the redox potential of electrolytic solution component is 0.35V (NHE relatively), then the HOMO of title complex can need greater than 0.9V (NHE relatively) by the rank current potential at least.The HOMO of the 8th group 4 transition metal complexes can the rank current potential be 0.92V and 0.96V in the specific embodiments of the invention.
Above-mentioned 2-phenyl-6-azoles yl pyridines is that aglucon can select for use suitable reactant and reaction conditions to be prepared according to each substituent variation, and the prepared in reaction mode can change according to technology well known in the art.In following specification sheets, the substituting group of this reactant numbering is that the 2-phenyl-6-azoles yl pyridines according to formula (I) is that the substituting group of the identical limited range in the aglucon numbers to represent.
Preferably, preparation X is C-R 102-phenyl-6-azoles yl pyridines be that the reactions steps of aglucon comprises: (1) with first reactant and second reactant in the presence of alkaline condition and catalyzer, heat, reaction forms one first intermediate, then, (2) with first intermediate and Trifluoroacetic Acid Ethyl Ester in the presence of alkaline sodium salt, heat reaction, form one second intermediate, at last, (3) react this second intermediate and hydrazine compound, and making X of the present invention is C-R 102-phenyl-6-azoles yl pyridines be aglucon.
Preferably, preparation X is that the 2-phenyl-6-azoles yl pyridines of nitrogen is that the reactions steps of aglucon comprises: (1) with first reactant and second reactant in the presence of alkaline condition and catalyzer, heat, reaction, form one first intermediate, then, (2) with first intermediate and ammonium chloride in the presence of alkaline sodium salt, heat, reaction forms one second intermediate, and is last, (3) with this second intermediate, Trifluoroacetic Acid Ethyl Ester and hydrazine compound reaction, the 2-phenyl-6-azoles yl pyridines that makes X of the present invention and be nitrogen is aglucon.
Described first reactant is selected from:
Figure BDA0000135693430000071
Second reactant is Wherein L be CN,
Figure BDA0000135693430000073
Figure BDA0000135693430000081
Described alkaline sodium salt is including but not limited to sodium methylate or sodium ethylate.
Preferably, described catalyzer is selected from: tetrakis triphenylphosphine palladium [tetrakis (triphenylphosphine) palladium, Pd (PPh 3) 4], cuprous iodide (cuprous io dide), two (triphenylphosphine) palladium chloride [bis (triphenylphosphine) palladium (II) dichloride, PdCl 2(PPh 3) 2], two (tri-butyl phosphine) palladium [bis (tri-tert-butylpho sphine) palladium], or their combination.Preferably, described catalyzer is tetrakis triphenylphosphine palladium.
The present invention's the 8th group 4 transition metal complexes, shown in formula (II):
ML 1L 2 (II)
In the formula (II), M is ruthenium metal or osmium metal; L 1Be that as mentioned above a 2-phenyl-6-azoles yl pyridines is aglucon; L 2For the two pyridines of carboxyl are aglucon.
Preferably, M is the ruthenium metal.
Preferably, the two pyridines of carboxyl are aglucon, shown in formula (III):
Figure BDA0000135693430000082
In the formula (III), X 1～X 7For identical or different, and be respectively hydrogen, halogen, trifluoromethyl, C 1～C 12Straight chained alkyl, C 1～C 12Branched-chain alkyl, phosphate, phosphoric acid salt, boronate, borate, sulfonic group, sulfonate, or COOY, and condition is X 1～X 7In at least one is COOY; Y is hydrogen, basic metal, C 1～C 12Straight chained alkyl, C 1～C 12Branched-chain alkyl, or N (C 4H 9) 4 +X 8For
Figure BDA0000135693430000083
X 9～R 12Be hydrogen, halogen, trifluoromethyl, carboxylic acid group, C 1～C 8Straight chained alkyl, C 1～C 8Branched-chain alkyl,
Figure BDA0000135693430000084
X 13With X 14Be hydrogen, halogen, trifluoromethyl, carboxylic acid group, C 1～C 8Straight chained alkyl, C 1～C 8Branched-chain alkyl, or
Figure BDA0000135693430000091
X 15With X 16Be alkoxyl group, alkylthio, C 1～C 8Straight chained alkyl, or C 1～C 8Branched-chain alkyl.
Preferably, X 1～X 7In at least two be COOY.
Preferably, X 1～X 7In at least two be the carboxylic acid group
Figure BDA0000135693430000092
Preferably, X 8For
Figure BDA0000135693430000093
The two pyridines of carboxyl of the present invention be aglucon specific embodiment including but not limited to:
The present invention is by pyrazoles (pyrazole) or triazole (triazole), and the design of phenyl ring, make the HOMO of the 8th group 4 transition metal complexes and the jump distance can freely adjusting of LUMO, make the 8th group 4 transition metal complexes have better absorption in the near infrared light zone; And the carbon on the phenyl ring, compare with N, O, S or halogen etc., be difficult for being bonded on the metal, but the present invention still adopts with the part of phenyl ring as aglucon, and can make the 8th group 4 transition metal complexes that visible region and near infrared light zone are had better absorption really, different choice can be provided.
The 8th above-mentioned group 4 transition metal complexes can select for use suitable reactant and reaction conditions to be prepared according to the variation of each aglucon, and the prepared in reaction mode can change according to technology known in the art.The step of this reaction comprises: be that aglucon mixes with source metal with above-mentioned 2-phenyl-6-azoles yl pyridines, and heat in the presence of a catalyzer and react, make the 8th group 4 transition metal complexes of the present invention.Preferably, described source metal is selected from ruthenium source or osmium source.Preferably, described ruthenium source is selected from 4,4 ', 4 "-ethoxycarbonyl-three pyridine ruthenium trichloride [(4,4 ', 4 "-ethoxycarbonyl-terpyridine) RuCl 3], or 4,4 ', 4 "-methoxycarbonyl-three pyridine ruthenium trichloride [(4,4 ', 4 "-methoxycarbonyl-terpyridine) RuCl 3].Preferably, described osmium source is selected from 4,4 ', 4 "-ethoxycarbonyl-three pyridine osmium trichloride [(4,4 ', 4 "-ethoxycarbonyl-terpyridine) OsCl 3], or 4,4 ', 4 "-methoxycarbonyl-three pyridine osmium trichloride [(4,4 ', 4 "-methoxycarbonyl-terpyridine) OsCl 3].Preferably, described catalyst is selected from potassium acetate or sodium acetate.After treating that the preparation of the 8th group 4 transition metal complexes is finished, the ester acid functional group on this aglucon can be hydrolyzed to carboxylate radical (CO by the catalysis of bases reagent 2 -) or carboxylic acid group (COOH).Preferably, this bases reagent can be sodium hydroxide (NaOH) solution or tetrabutylammonium (TBAOH) solution.
Dye sensitization solar battery of the present invention comprises:
One electrolytic solution component;
One first electrode is arranged in the described electrolytic solution component, comprises that a transparent conductive substrate and is arranged at a lip-deep porous film of described transparent conductive substrate, described porous film absorption one the 8th group 4 transition metal complexes as mentioned above; And
One second electrode is arranged in the described electrolytic solution component, arranges with described first electrode space ground.
Preferably, described electrolytic solution component is 1 of 2M, 3-dimethyl-imidazoles iodine (1,3-dimethylimidazolium iodide, abbreviation DMII), the iodine (I of the lithium iodide of the guanidine thiocyanate (guanidinium thiocyanate) of 0.1M, 0.05M (lithium iodide is called for short LiI), 0.03M 2) and the tert .-butylpyridine of 0.5M is dissolved in the mixing solutions (volume ratio 85: 15) of acetonitrile (acetonitrile) and valeronitrile (valeronitrile), (tetrabutylammonium hexafluorophosphate is called for short TBAPF to the tetrabutyl ammonium hexafluorophosphate of 0.1M 6), or 2.0M 1,3-dimethyl-imidazoles iodine, 0.05M lithium iodide, 0.03M iodine, 0.1M guanidine thiocyanate, and 0.5MN-butyl benzoglyoxaline solution (N-butyl-1H-benzimidazole is called for short NBB, and solvent is the 3-methoxypropionitrile).
More preferably, described electrolytic solution component is 1 of 2M, the iodine (I of the guanidine thiocyanate of 3-dimethyl-imidazoles iodine, 0.1M, the lithium iodide of 0.05M, 0.03M 2) and the tert .-butylpyridine of 0.5M be dissolved in the mixing solutions (volume ratio 85: 15) of acetonitrile and valeronitrile.
Preferably, the material of described porous film is selected from: titanium dioxide is (hereinafter to be referred as TiO 2), zinc oxide (zinc oxide) or stannic oxide (tin oxide) etc.Preferably, the material of described transparent conductive substrate is to be selected from polymkeric substance or the rigid material with flexibility, wherein, described have the polymkeric substance of flexibility including but not limited to polyethylene, polypropylene, polyimide, polymethylmethacrylate, polycarbonate, polyethylene terephthalate etc.; Described rigid material is including but not limited to glass.
The preparation method of described dye sensitization solar battery is well known to those skilled in the art, so repeat no more.
What deserves to be explained is, the known thiocyanate ion aglucon (thiocyanate that contains, abbreviation NCS) the 8th group 4 transition metal complexes, easily because of single coordination bonding stability of this thiocyanate ion aglucon a little less than, under light and heat effect, be difficult for for a long time and stably with metal-chelating, decompose so very easily produce under battery operation, make the related dye sensitization solar battery then when life-time service, its photoelectric transformation efficiency is not good and work-ing life is not good.And the present invention's the 8th group 4 transition metal complexes not only in the visible region and the near infrared light zone have preferable absorption and have outside the high molar extinction coefficient, there is no the existence of thiocyanate ion aglucon because of the 8th group 4 transition metal complexes, compare, the 8th group 4 transition metal complexes can increase efficient and the life-span of dye sensitization solar battery effectively, use for this area has more important meaning and utilizability, and different choice is provided.
The present invention will be described further with regard to following examples, but will be appreciated that, this embodiment only is example explanation usefulness, and should not be interpreted as restriction of the invention process.
Embodiment preparation example 1
1-bromo-3-(trifluoromethyl) benzene of 5.00 grams (22mmol) is placed 250 milliliters of reaction flasks, and take out and irritate nitrogen three times, then add 100 milliliters of tetrahydrofuran (THF)s that dewatered (hereinafter to be referred as THF), and under-78 ℃, slowly add the 2.5M n-Butyl Lithium hexane solution (hereinafter to be referred as n-BuLi) of 9.8 milliliters (24mmol), and under this temperature, stirred 30 minutes, the 2-isopropoxy-4 that then adds 5.0 milliliters (24mmol), 4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane (2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane), be warming up to room temperature and under room temperature, stirred 12 hours.Then add the water termination reaction and with solvent removal.Add methylene dichloride and water and extract, and collect dichloromethane layer, then add sal epsom and dewater.Dewater finish after, filter and collect filtrate.Then utilize the underpressure distillation mode that dichloromethane layer is concentrated, can get the colourless oil liquid of 5.21 grams (19mmol), productive rate is 86%.
The spectroscopic analysis of this colourless oil liquid: 1H NMR (400MHz, CDCl 3, 298K), (ppm): 8.04 (s, 1H), 7.95 (d, J HH=7.6Hz, 1H), 7.68 (d, J HH=7.6Hz, 1H), 7.46 (t, J HH=7.6Hz, 1H), 1.34 (s, 12H).Chemical structure is:
Figure BDA0000135693430000121
Preparation example 2
4-bromo-1-fluoro-2-(trifluoromethyl) benzene of 2.00 grams (8.2mmol) is placed 150 milliliters of reaction flasks, and take out and irritate nitrogen three times, then add 50 milliliters of THF that dewatered, and under-78 ℃, the n-BuLi that slowly adds 3.62 milliliters (9.1mmol), and under this temperature, stirred 30 minutes, then add the 2-isopropoxy-4 of 1.85 milliliters (9.1mmol), 4,5,5-tetramethyl--1,3, the assorted oxygen pentaboranes of 2-two are warming up to room temperature and stirred 12 hours under room temperature.Then add the water termination reaction and with solvent removal.Add methylene dichloride and water and extract, and collect dichloromethane layer, then add sal epsom and dewater.Dewater finish after, filter and collect filtrate.Then utilize the underpressure distillation mode that dichloromethane layer is concentrated, can get the colourless oil liquid of 1.95 grams (6.7mmol), productive rate is 82%.
The spectroscopic analysis of this colourless oil liquid: 1H NMR (400MHz, CDCl 3, 298K), (ppm): 8.03 (d, J HF=7.6Hz, 1H), 7.98～7.90 (m, 1H), 7.16 (t, J HH=9.2Hz, 1H), 1.35 (s, 12H).
Chemical structure is:
Figure BDA0000135693430000122
Synthesis example 12-phenyl-6-azoles yl pyridines is the preparation of aglucon
With the tetrakis triphenylphosphine palladium of the preparation example 1 of 0.68 gram (2.5mmol), the 0.50 gram 6-ethanoyl-2-bromopyridine (6-acetyl-2-bromopyridine) of (2.5mmol) and 144 milligrams (0.13mmol) [hereinafter to be referred as Pd (PPh 3) 4] place 100 milliliters of single neck bottles, add 25 milliliters of THF, add wet chemical (salt of wormwood of 0.69 gram and 5 milliliters deionized water) again.Reflux is 16 hours under nitrogen.Be cooled to room temperature after reaction finishes, and in the underpressure distillation mode with solvent removal.Then add methylene dichloride and water extracts, and collect dichloromethane layer.Then adding sal epsom dewaters.Dewater finish after, filter and collect filtrate, and utilize the underpressure distillation mode that dichloromethane layer is concentrated, can get yellow crude product.The yellow crude product that obtains is again with ethyl acetate: hexane=1: 8 can get the white solid of 446 milligrams (1.7mmol), productive rate: 67% as carrying out the tubing string chromatography towards extract.
The spectroscopic analysis of this white solid: 1H NMR (400MHz, CDCl 3, 298K), (ppm): 8.34 (s, 1H), 8.27 (d, J HH=8.0Hz, 1H), 8.02 (dd, J HH=6.8Hz, 2.0Hz, 1H), 7.98～7.90 (m, 2H), 7.70 (d, J HH=8.0Hz, 1H), 7.63 (t, J HH=8.0Hz, 1H), 2.82 (s, 3H).
Chemical structure is:
The sodium ethylate of 116 milligrams (1.7mmol) placed 50 milliliters two-neck bottle, add 20 milliliters of THF that dewatered, and in 0 ℃ of above-mentioned white solid that slowly adds 300 milligrams (1.1mmol) down, after then stirring 20 minutes, be warming up to room temperature, and under room temperature, add the Trifluoroacetic Acid Ethyl Ester (ethyl trifluoroacetate) of 0.20 milliliter (1.7mmol).Be warming up to 80 ℃ and stir down and reacted in 4 hours, question response finishes, drip to pH with the 2N hydrogen chloride solution to be about about 4, and in the underpressure distillation mode with solvent removal.Add ethyl acetate and water and extract, and collect ethyl acetate layer, then add sal epsom and dewater.Dewater finish after, filter and collect filtrate, then utilize the underpressure distillation mode that ethyl acetate layer is concentrated, can get yellow solid.
Chemical structure is:
Figure BDA0000135693430000132
Above-mentioned yellow solid is placed 100 milliliters round-bottomed bottle, and add 30 milliliters ethanol and the hydrazine (hydrazine) of 0.33 milliliter (6.4mmol), then reflux was reacted in 12 hours.After reaction finishes, utilize the underpressure distillation mode to remove solvent, again with ethyl acetate: hexane=1: 3 is followed through the recrystallize mode as carrying out the tubing string chromatography towards extract, can get the white transparent crystals of 120 milligrams (0.34mmol), and productive rate is 30%.
The spectroscopic analysis of this white transparent crystals: 1H NMR (400MHz, CDCl 3, 298K), (ppm): 8.25 (s, 1H), 8.20 (d, J HH=7.6Hz, 1H), 7.90 (d, J HH=7.6Hz, 1H), 7.75 (d, J HH=7.6Hz, 1H), 7.71 (d, J HH=8.0Hz, 1H), 7.67～7.58 (m, 2H), 6.99 (s, 1H); MS (EI +): m/z 357 (M) +
Chemical structure is:
Figure BDA0000135693430000141
Synthesis example 2
With the 4-trifluoromethyl phenylo boric acid [4-(trifluoromethyl) phenylboronic acid] of the 2-bromo-6-cyanopyridine (6-bromo-2-cyanopyridine) of 424 milligrams (2.3mmol), 440 milligrams (2.3mmol) and the Pd (PPh of 134 milligrams (0.12mmol) 3) 4Place single neck bottle of 100 milliliters, add 30 milliliters of THF, then add wet chemical (salt of wormwood of 0.96 gram and 7 milliliters deionized water) again.Reflux is 6 hours under nitrogen.Be cooled to room temperature after reaction finishes, and in the underpressure distillation mode with solvent removal.Add methylene dichloride and water and extract, and collect dichloromethane layer, then add sal epsom and dewater.Dewater finish after, filter and collect filtrate, then utilize the underpressure distillation mode that dichloromethane layer is concentrated, can get yellow crude product.The yellow crude product that obtains is again with ethyl acetate: hexane=1: 4 can get the white solid of 460 milligrams (1.9mmol) as carrying out the tubing string chromatography towards extract, and productive rate is 80%.
The spectroscopic analysis of this white solid: 1H NMR (400MHz, CDCl 3, 298K), (ppm): 8.14 (d, J HH=8.0Hz, 2H), 8.02～7.90 (m, 2H), 7.75 (d, J HH=8.0Hz, 2H), 7.68 (d, J HH=7.2Hz, 1H).
Chemical structure is:
Figure BDA0000135693430000142
The above-mentioned white solid of 450 milligrams (1.8mmol) and the sodium methylate of 9.8 milligrams (0.18mmol) are placed single neck bottle of 50 milliliters, add 15 milliliters methyl alcohol, and under room temperature, stir and reacted in 12 hours.The ammonium chloride that then adds 107 milligrams (2.0mmol), and under nitrogen reflux 4 hours.Remove methyl alcohol and add 10 milliliters ethanol, then reheat refluxed 30 minutes under nitrogen.Cool the temperature to room temperature behind the question response, the filtration of then bleeding, collection filtrate also concentrates, and can get the yellow solid of 400 milligrams (1.3mmol), and productive rate is 70%.
With the Trifluoroacetic Acid Ethyl Ester of 0.26 milliliter (1.5mmol) and hydrazine hydrate (hydrazine monohydrate, the N of 0.10 milliliter (1.9mmol) 2H 4H 2O) be dissolved among 25 milliliters the THF, reflux is 1 hour under nitrogen.Then cool the temperature to room temperature, add the above-mentioned yellow solid of 400 milligrams (1.3mmol) and the sodium hydroxide of 76 milligrams (1.9mmol) again.Reflux is 8 hours under nitrogen.Question response, then neutralizes with saturated sodium bicarbonate aqueous solution solvent removal in the underpressure distillation mode after finishing.The ethyl acetate that then adds 30 milliliters, and extract with water, and collect ethyl acetate layer, then add sal epsom and dewater.Dewater finish after, filter and collect filtrate.Utilize the underpressure distillation mode that ethyl acetate layer is concentrated, can get yellow crude product.The yellow crude product that obtains is again with ethyl acetate: hexane=1: 2 then adds ethyl acetate and through the recrystallize mode, can get the white crystal of 190 milligrams (0.53mmol) as carrying out the tubing string chromatography towards extract, and productive rate is 40%.
The spectroscopic analysis of this white crystal: 1H NMR (400MHz, CDCl 3, 298K), (ppm): 12.0 (br, 1H), 8.23 (d, J HH=8.0Hz, 1H), 8.12 (d, J HH=8.0Hz, 2H), 8.01 (t, J HH=8.0Hz, 1H), 7.90 (d, J HH=8.0Hz, 1H), 7.77 (d, J HH=8.0Hz, 2H); MS (EI +): m/z 358 (M) +
Chemical structure is:
Figure BDA0000135693430000151
Synthesis example 3
With the 2-bromo-6-cyanopyridine of 0.50 gram (2.7mmol), the preparation example 1 of 0.89 gram (3.3mmol) and the Pd (PPh of 158 milligrams (0.14mmol) 3) 4Place single neck bottle of 100 milliliters, add 30 milliliters THF, then add wet chemical (salt of wormwood of 0.94 gram and 7 milliliters deionized water) again.Reflux is 4 hours under nitrogen.Be cooled to room temperature after reaction finishes, and in the underpressure distillation mode with solvent removal.Then add methylene dichloride and water extracts, and collect dichloromethane layer, then add sal epsom and dewater.Dewater finish after, filter and collect filtrate.Utilize the underpressure distillation mode that dichloromethane layer is concentrated, can get yellow solid.The yellow solid that obtains is again with ethyl acetate: hexane=1: 4 can get the white solid of 608 milligrams (2.4mmol) as carrying out the tubing string chromatography towards extract, and productive rate is 90%.
The spectroscopic analysis of this white solid: 1H NMR (400MHz, CDCl 3, 298K), (ppm): 8.27 (s, 1H), 8.22 (d, J HH=8.0Hz, 1H), 8.02～7.90 (m, 2H), 7.76～7.59 (m, 3H).
Chemical structure is:
Figure BDA0000135693430000161
The above-mentioned white solid of 600 milligrams (2.4mmol) and the sodium methylate of 13.1 milligrams (0.24mmol) are placed single neck bottle of 50 milliliters, add 15 milliliters methyl alcohol, and under room temperature, stir and reacted in 12 hours.The ammonium chloride that then adds 142 milligrams (2.7mmol), and under nitrogen reflux 4 hours, behind the question response, in the underpressure distillation mode methyl alcohol is removed.Cool the temperature to room temperature, the filtration of then bleeding, collection filtrate also concentrates, and can get the yellow solid of 700 milligrams (2.3mmol), and productive rate is 96%.
The hydrazine hydrate of the Trifluoroacetic Acid Ethyl Ester of 0.29 milliliter (1.5mmol) and 0.12 milliliter (2.3mmol) is dissolved among 30 milliliters the THF, reflux is 1 hour under nitrogen.Then cool the temperature to room temperature, add the above-mentioned yellow solid of 700 milligrams (2.3mmol) and the sodium hydroxide of 94 milligrams (2.3mmol) again.Reflux is 8 hours under nitrogen.Question response, then neutralizes with saturated sodium bicarbonate aqueous solution solvent removal in the underpressure distillation mode after finishing.The ethyl acetate that then adds 30 milliliters, and extract with water, and collect ethyl acetate layer, then add sal epsom and dewater.Dewater finish after, filter and collect filtrate.Utilize the underpressure distillation mode that ethyl acetate layer is concentrated, again with ethyl acetate: hexane=1: 2 is as carrying out the tubing string chromatography towards extract, then add ethyl acetate and through the recrystallize mode, can get the white crystal of 220 milligrams (0.61mmol), productive rate is 26%.
The spectroscopic analysis of this white crystal: 1H NMR (400MHz, CDCl 3, 298K), (ppm): 8.26 (s, 1H), 8.22 (d, J HH=7.6Hz, 1H), 8.18 (d, J HH=7.6Hz, 1H), 8.01 (t, J HH=7.6Hz, 1H), 7.89 (d, J HH=7.6Hz, 1H), 7.73 (d, J HH=7.6Hz, 1H), 7.63 (t, J HH=7.6Hz, 1H); MS (EI +): m/z 358 (M) +
Chemical structure is:
Figure BDA0000135693430000171
Synthesis example 4
With the 2-bromo-6-cyanopyridine of 1.10 grams (6.0mmol), the preparation example 2 of 2 grams (6.9mmol) and the Pd (PPh of 346 milligrams (0.30mmol) 3) 4Place single neck bottle of 100 milliliters, add 30 milliliters THF, then add wet chemical (salt of wormwood of 2.07 grams and 7 milliliters deionized water) again.Reflux is 5 hours under nitrogen.Be cooled to room temperature after reaction finishes, and in the underpressure distillation mode with solvent removal.Then add methylene dichloride and water extracts, and collect dichloromethane layer, and add sal epsom and dewater.Dewater finish after, filter and collect filtrate.Utilize the underpressure distillation mode that dichloromethane layer is concentrated, can get yellow solid.The yellow solid that obtains is again with ethyl acetate: hexane=1: 4 can get the white solid of 983 milligrams (3.7mmol) as carrying out the tubing string chromatography towards extract, and productive rate is 61%.
The spectroscopic analysis of this white solid: 1H NMR (400MHz, CDCl 3, 298K), (ppm): 8.30～8.21 (m, 2H), 7.96～7.91 (m, 2H), 7.70～7.63 (m, 1H), 7.33 (t, J HF=9.2Hz, 1H).
Chemical structure is:
Figure BDA0000135693430000172
The above-mentioned white solid of 703 milligrams (2.6mmol) and the sodium methylate of 14.3 milligrams (0.26mmol) are placed single neck bottle of 50 milliliters, add 20 milliliters methyl alcohol, and under room temperature, stir and reacted in 12 hours.The ammonium chloride that then adds 155 milligrams (2.9mmol), and under nitrogen reflux 4 hours.Behind the question response, in the underpressure distillation mode methyl alcohol is removed.Cool the temperature to room temperature, the filtration of then bleeding, collection filtrate also concentrates, and can get the yellow solid of 820 milligrams (2.6mmol), and productive rate is 97%.
The hydrazine hydrate of the Trifluoroacetic Acid Ethyl Ester of 0.315 milliliter (1.9mmol) and 0.129 milliliter (2.5mmol) is dissolved among 30 milliliters the THF, reflux is 1 hour under nitrogen.Then cool the temperature to room temperature, add the above-mentioned yellow solid of 820 milligrams (2.6mmol) and the sodium hydroxide of 106 milligrams (2.6mmol) again.Reflux is 8 hours under nitrogen.Question response, then neutralizes with saturated sodium bicarbonate aqueous solution solvent removal in the underpressure distillation mode after finishing.The ethyl acetate that then adds 30 milliliters, and extract with water, and collect ethyl acetate layer.Then adding sal epsom dewaters.Dewater finish after, filter and collect filtrate.Utilize the underpressure distillation mode that ethyl acetate layer is concentrated, again with ethyl acetate: hexane=1: 3 then adds ethyl acetate and through the recrystallize mode, can get the white crystal of 583 milligrams (1.5mmol) as carrying out the tubing string chromatography towards extract, and productive rate is 59%.
The spectroscopic analysis of this white crystal: 1H NMR (400MHz, CDCl 3, 298K), (ppm): 12.1 (br, 1H), 8.26 (d, J HF=6.8Hz, 1H), 8.24～8.16 (m, 2H), 8.00 (t, J HH=8.0Hz, 1H), 7.85 (d, J HH=8.0Hz, 1H), 7.35 (t, J HF=9.2Hz, 1H); MS (EI +): m/z 376 (M) +
Chemical structure is:
Figure BDA0000135693430000181
Synthesis example 5
With 2 of 1.61 grams (10.9mmol), the 4-trifluoromethyl phenylo boric acid of 4-dichloropyridine, 2.00 grams (10.9mmol) and the Pd (PPh of 0.38 gram (0.33mmol) 3) 4Place 100 milliliters of single neck bottles, add 40 milliliters THF, then add wet chemical (salt of wormwood of 3.76 grams and 10 milliliters deionized water) again.Reflux is 9 hours under the nitrogen.Be cooled to room temperature after reaction finishes, and in the underpressure distillation mode with solvent removal.Then add methylene dichloride and water extracts, and collect dichloromethane layer, and add sal epsom and dewater.Dewater finish after, filter and collect filtrate.Utilize the underpressure distillation mode that dichloromethane layer is concentrated, can get orange oily matter.The orange oily matter that obtains again with ethyl acetate as carrying out the tubing string chromatography towards extract, can get 2.18 the gram (8.4mmol) white solid, productive rate is 78%.
The spectroscopic analysis of this white crystal: 1H NMR (400MHz, CDCl 3, 298K), (ppm): 8.60 (d, J HH=5.2Hz, 1H), 8.08 (d, J HH=8.0Hz, 2H), 7.77～7.70 (m, 3H), 7.30 (dd, J HH=5.2,1.6Hz, 1H).
Chemical structure is:
Figure BDA0000135693430000191
The above-mentioned white solids of 2.15 grams (8.3mmol) are placed 150 milliliters of single neck bottles, and add 10 milliliters acetic acid, then, under ice bath, slowly add 10 milliliters and concentration and be 30% hydrogen peroxide, and stirred 24 hours down in 80 ℃.Reaction is neutralized to pH=7 with aqueous sodium hydroxide solution after finishing, and have a large amount of solids and separate out this moment.Cross filter solid, and clean for several times with water and ether, then, under vacuum, carry out drying, get final product the white product of 1.83 grams (6.7mmol), productive rate is 80%.
The above-mentioned white product of 1.83 grams (6.7mmol) is placed 100 milliliters of two-neck bottles, take out and irritate nitrogen three times, add 50 milliliters of methylene dichloride that dewatered, then slowly add the dimethyl amido formyl chloride (dimethylcarbamyl chloride) of 0.62 milliliter (6.7mmol) and the trimethylsilyl cyanide (trimethylsilyl cyanide) of 0.90 milliliter (7.0mmol), and under room temperature, stirred 2 days.Then reflux is 9 hours.After reaction finishes, under ice bath, slowly add 10% wet chemical and stirred 15 minutes.Then add water and extract, and collected organic layer, and add sal epsom and in organic layer, dewater.Dewater finish after, filter and collect filtrate.Utilize the underpressure distillation mode to remove solvent, again with ethyl acetate: hexane=1: 6 can get the white product of 0.71 gram (2.5mmol) as carrying out the tubing string chromatography towards extract, and productive rate is 91%.
The spectroscopic analysis of this white product: 1H NMR (400MHz, CDCl 3, 298K), (ppm): 8.12 (d, J HH=8.0Hz, 2H), 7.96 (d, J HH=1.6Hz, 1H), 7.75 (d, J HH=8.0Hz, 2H), 7.67 (d, J HH=1.6Hz, 1H).
Chemical structure is:
Figure BDA0000135693430000192
The above-mentioned white product of 698 milligrams (2.5mmol) is placed 100 milliliters of two-neck bottles, the 2-5 (hexyl-2-thiophene)-4,4,5 that adds 872 milligrams (3.0mmol), 5-tetramethyl--1,3,2-, two assorted oxygen pentaborane [2-(5-hexylthiophen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane], the Pd (PPh of 143 milligrams (0.12mmol) 3) 4And 30 milliliters THF, and add wet chemical (683 milligrams salt of wormwood and 6 milliliters deionized water) again.Be cooled to room temperature after reaction finishes, and in the underpressure distillation mode with solvent removal.Then add methylene dichloride and water extracts, and collect dichloromethane layer, and add sal epsom and dewater.Dewater finish after, filter and collect filtrate.Then utilize the underpressure distillation mode that dichloromethane layer is concentrated, can get orange oily matter.The orange oily matter that obtains is again with ethyl acetate: hexane=1: 5 can get the white solid of 850 milligrams (2.1mmol) as carrying out the tubing string chromatography towards extract, and productive rate is 83%.
The spectroscopic analysis of this white solid: 1H NMR (400MHz, CDCl 3, 298K), (ppm): 8.14 (d, J HH=8.0Hz, 2H), 7.98 (d, J HH=1.2Hz, 1H), 7.79～7.73 (m, 3H), 7.45 (d, J HH=3.6Hz, 1H), 6.86 (d, J HH=3.6Hz, 1H), 2.86 (t, J HH=7.6Hz, 2H), 1.71 (q, J HH=7.6Hz, 2H), 1.43～1.25 (m, 6H), 0.88 (t, J HH=6.8Hz, 3H).
Chemical structure is:
Figure BDA0000135693430000201
White solid and 8.1 milligrams of (0.15mmol) sodium methylates of 620 milligrams (1.5mmol) are placed 50 milliliters of single neck bottles, and add 30 milliliters methyl alcohol, under room temperature, stirred 12 hours.Then, add the ammonium chloride of 88 milligrams (1.7mmol) again, and under nitrogen reflux 4 hours, behind the question response, in the underpressure distillation mode methyl alcohol is removed.Cool the temperature to room temperature, the filtration of then bleeding, collection filtrate also concentrates, and can get the yellow solid of 609 milligrams (1.3mmol), and productive rate is 87%.
The hydrazine hydrate of the Trifluoroacetic Acid Ethyl Ester of 0.18 milliliter (1.1mmol) and 0.073 milliliter (1.4mmol) is dissolved among 30 milliliters the THF, reflux is 1 hour under nitrogen.Then cool the temperature to room temperature, add the above-mentioned yellow solid of 609 milligrams (1.3mmol) and the sodium hydroxide of 60 milligrams (1.5mmol) again.Reflux is 8 hours under nitrogen.Question response, then neutralizes with saturated sodium bicarbonate aqueous solution solvent removal in the underpressure distillation mode after finishing.The ethyl acetate that then adds 30 milliliters, and water extracts, and collect ethyl acetate layer.Adding sal epsom dewaters.Dewater finish after, filter and collect filtrate.Then utilize the underpressure distillation mode that ethyl acetate layer is concentrated, again with ethyl acetate: hexane=1: 5 is as carrying out the tubing string chromatography towards extract, then add ethyl acetate and through the recrystallize mode, can get the white crystal of 260 milligrams (0.05mmol), productive rate is 33%.
The spectroscopic analysis of this white crystal: 1H NMR (400MHz, CDCl 3, 298K), (ppm): 12.24 (br, 1H), 8.32 (d, J HH=1.6Hz, 1H), 8.13 (d, J HH=8.0Hz, 2H), 7.90 (d, J HH=1.6Hz, 1H), 7.76 (d, J HH=8.0Hz, 2H), 7.53 (d, J HH=3.6Hz, 1H), 6.85 (d, J HH=3.6Hz, 1H), 2.86 (t, J HH=7.6Hz, 2H), 1.71 (q, J HH=7.6Hz, 2H), 1.50～1.25 (m, 6H), 0.90 (t, J HH=7.6Hz, 3H).MS(EI +)：m/z 524(M) +。
Chemical structure is:
The preparation of ruthenium complexe
Embodiment 1
With 100 milligrams (0.15mmol) 4,4 '; 4 " the synthesis example 1 of-ethoxycarbonyl-three pyridine ruthenium trichloride, 54.4 milligrams (0.15mmol) and the Potassium ethanoate of 74.7 milligrams (0.76mmol) place single neck bottle of 50 milliliters, add 30 milliliters dimethylbenzene, and reflux is 20 hours under nitrogen.Be cooled to room temperature after reaction finishes, and in the underpressure distillation mode with solvent removal.Again with ethyl acetate: methylene dichloride=1: 6 can get 115 milligrams coffee-like solid as carrying out the tubing string chromatography towards extract, and productive rate is 83%.
The spectroscopic analysis of this coffee color solid: 1H NMR (400MHz, d 6-acetone, 298K), (ppm): 9.40 (s, 2H), 9.00 (s, 2H), 8.26 (t, J HH=5.6Hz, 1H), 8.21～8.13 (m, 2H), 8.00 (s, 1H), 7.83 (d, J HH=5.6Hz, 2H), 7.61 (d, J HH=5.6Hz, 2H), 7.30 (s, 1H), 6.58 (dd, J HH=7.6Hz, 1.2Hz, 1H), 5.44 (d, J HH=7.6Hz, 1H), 4.35～3.80 (m, 6H), 1.40～0.80 (m, 9H).
The above-mentioned coffee-like solid of 82.0 milligrams (0.090mmol) is placed single neck bottle of 50 milliliters, add 15 milliliters acetone and 1 milliliter 1M sodium hydroxide solution.Reflux is 2 hours under nitrogen, is cooled to room temperature after reaction finishes, and in the underpressure distillation mode with solvent removal.The water that then adds 5 milliliters, and adjust pH value with the 2N hydrogen chloride solution and be about 3～4, then clean several with deionized water, acetone and methylene dichloride, can get 63.0 milligrams brownish black solid (hereinafter to be referred as ruthenium complexe A-1), productive rate is 85%.
The spectroscopic analysis of this ruthenium complexe A-1: 1H NMR (400MHz, d 6-dimethyl sulfoxide (DMSO), 298K), (ppm): 9.28 (s, 2H), 9.14 (s, 2H), 8.36 (d, J HH=7.2Hz, 1H), 8.22～8.05 (m, 3H), 7.66 (d, J HH=6.0Hz, 2H), 7.61 (d, J HH=6.0Hz, 2H), 7.28 (s, 1H), 6.61 (d, J HH=7.6Hz, 1H), 5.52 (d, J HH=7.6Hz, 1H); 19F-{ 1H}NMR (470MHz, d 6-dimethyl sulfoxide (DMSO), 298K), (ppm) :-58.33 (s, 3F) ,-60.13 (s, 3F); MS (FAB, 102Ru): m/z 822 (M) +Ultimate analysis data: C:48.73%; N:9.59%; H:2.78%.
The chemical structure of this ruthenium complexe A-1 is:
Figure BDA0000135693430000221
Embodiment 2
With 100 milligrams (0.15mmol) 4,4 '; 4 " the synthesis example 2 of-ethoxycarbonyl-three pyridine ruthenium trichloride, 54.4 milligrams (0.15mmol) and the Potassium ethanoate of 74.7 milligrams (0.76mmol) place single neck bottle of 50 milliliters, add 25 milliliters dimethylbenzene, and reflux is 14 hours under nitrogen.Be cooled to room temperature after reaction finishes, and in the underpressure distillation mode with solvent removal.Again with ethyl acetate: methylene dichloride=1: 4 can get 112 milligrams coffee-like solid as carrying out the tubing string chromatography towards extract, and productive rate is 81%.
The spectroscopic analysis of this coffee color solid: 1H NMR (400MHz, d 6-acetone, 298K), (ppm): 9.37 (s, 2H), 9.10 (s, 2H), 8.36 (dd, J HH=6.4Hz, 2.4Hz, 1H), 8.30～8.22 (m, 2H), 8.02 (d, J HH=8.4Hz, 1H), 7.83 (d, J HH=5.6Hz, 2H), 7.67 (dd, J HH=5.6Hz, 1.2Hz, 2H), 6.95 (d, J HH=7.6Hz, 1H), 5.72 (s, 1H), 4.45～4.21 (m, 6H), 1.40～1.20 (m, 9H).
The above-mentioned coffee-like solid of 85.0 milligrams (0.094mmol) is placed single neck bottle of 50 milliliters, add 15 milliliters acetone and 1 milliliter 1M sodium hydroxide solution.Reflux is 2 hours under nitrogen, is cooled to room temperature after reaction finishes, and in the underpressure distillation mode with solvent removal.The water that then adds 5 milliliters, and adjust pH value with the 2N hydrogen chloride solution and be about 3～4, then clean several with deionized water, acetone and methylene dichloride, can get 90.0 milligrams brownish black solid (hereinafter to be referred as ruthenium complexe A-2), productive rate is 81%.
The spectroscopic analysis of this ruthenium complexe A-2: 1H NMR (400MHz, d 6-dimethyl sulfoxide (DMSO), 298K), (ppm): 9.40 (s, 2H), 9.16 (s, 2H), 8.42 (t, J HH=4.8Hz, 1H), 8.22 (d, J HH=4.8Hz, 2H), 8.06 (d, J HH=8.4Hz, 1H), 7.65 (d, J HH=5.6Hz, 2H), 7.61 (d, J HH=5.6Hz, 2H), 6.96 (d, J HH=5.6Hz, 1H), 5.60 (s, 1H); MS (FAB, 102Ru): m/z 823 (M) + 19F-{ 1H}NMR (470MHz, d 6-dimethyl sulfoxide (DMSO), 298K), (ppm) :-61.22 (s, 3F) ,-62.12 (s, 3F); Ultimate analysis data: C:48.06%; N:11.29%; H:2.56%.
The chemical structure of this ruthenium complexe A-2 is:
Figure BDA0000135693430000231
Embodiment 3
With 100 milligrams (0.15mmol) 4,4 '; 4 " the synthesis example 3 of-ethoxycarbonyl-three pyridine ruthenium trichloride, 54.4 milligrams (0.15mmol) and the Potassium ethanoate of 74.7 milligrams (0.76mmol) place single neck bottle of 50 milliliters, add 25 milliliters dimethylbenzene, and reflux is 14 hours under nitrogen.Be cooled to room temperature after reaction finishes, and in the underpressure distillation mode with solvent removal.Again with ethyl acetate: methylene dichloride=1: 5 can get 94.4 milligrams coffee-like solid as carrying out the tubing string chromatography towards extract, and productive rate is 68%.
The spectroscopic analysis of this coffee color solid: 1H NMR (400MHz, d 6-acetone, 298K), (ppm): 9.32 (s, 2H), 9.00 (s, 2H), 8.43 (dd, J HH=7.6Hz, 1.6Hz, 1H), 8.32～8.22 (m, 2H), 8.06 (s, 1H), 7.82 (d, J HH=5.6Hz, 2H), 7.62 (d, J HH=4.4Hz, 2H), 6.62 (d, J HH=8.0Hz, 1H), 5.56 (d, J HH=8.0Hz, 1H), 4.38～4.00 (m, 6H), 1.32～1.02 (m, 9H).
The above-mentioned coffee-like solid of 87.0 milligrams (0.096mmol) is placed single neck bottle of 50 milliliters, add 15 milliliters acetone and 1 milliliter 1M sodium hydroxide solution.Reflux is 2 hours under nitrogen, is cooled to room temperature after reaction finishes, and in the underpressure distillation mode with solvent removal.The water that then adds 5 milliliters, and adjust pH value with the 2N hydrogen chloride solution and be about 3～4, then clean several with deionized water, acetone and methylene dichloride, can get 69.4 milligrams brownish black solid (hereinafter to be referred as ruthenium complexe A-3), productive rate is 88%.
The spectroscopic analysis of this ruthenium complexe A-3: 1H NMR (400MHz, d 6-dimethyl sulfoxide (DMSO), 298K), (ppm): 9.38 (s, 2H), 9.14 (s, 2H), 8.51 (t, J HH=4.8Hz, 1H), 8.25～8.10 (m, 3H), 7.64 (d, J HH=6.0Hz, 2H), 7.61 (d, J HH=6.0Hz, 2H), 6.68 (d, J HH=7.6Hz, 1H), 5.59 (d, J HH=7.6Hz, 1H); MS (FAB, 102Ru): m/z 823 (M) + 19F-{ 1H}NMR (470MHz, d 6-dimethyl sulfoxide (DMSO), 298K), (ppm) :-60.21 (s, 3F) ,-62.11 (s, 3F); Ultimate analysis data: C:48.14%; N:11.25%; H:2.48%.
The chemical structure of this ruthenium complexe A-3 is:
Figure BDA0000135693430000241
Embodiment 4
With 120 milligrams (0.18mmol) 4,4 '; 4 " the synthesis example 4 of-ethoxycarbonyl-three pyridine ruthenium trichloride, 68.7 milligrams (0.18mmol) and the Potassium ethanoate of 89.6 milligrams (0.91mmol) place single neck bottle of 50 milliliters, add 30 milliliters dimethylbenzene, and reflux is 12 hours under nitrogen.Be cooled to room temperature after reaction finishes, and in the underpressure distillation mode with solvent removal.Again with ethyl acetate: methylene dichloride=1: 5 can get 115 milligrams coffee-like solid as carrying out the tubing string chromatography towards extract, and productive rate is 68%.
The spectroscopic analysis of this coffee color solid: 1H NMR (400MHz, d 6-acetone, 298K), (ppm): 9.34 (s, 2H), 9.07 (s, 2H), 8.42～8.36 (m, 1H), 8.25 (d, J HH=5.2Hz, 2H), 8.10 (d, J HF=6.8Hz, 1H), 7.81 (d, J HH=5.8Hz, 2H), 7.67 (d, J HH=5.6Hz, 2H), 5.37 (d, J HF=11.2Hz, 1H), 4.40～4.20 (m, 6H), 1.35～1.25 (m, 9H).
The above-mentioned coffee-like solid of 101 milligrams (0.11mmol) is placed single neck bottle of 50 milliliters, add 15 milliliters acetone and 1 milliliter 1M sodium hydroxide solution.Reflux is 2 hours under nitrogen, is cooled to room temperature after reaction finishes, and in the underpressure distillation mode with solvent removal.The water that then adds 5 milliliters, and adjust pH value with the 2N hydrogen chloride solution and be about 3～4, then clean several with deionized water, acetone and methylene dichloride, can get 76.0 milligrams brownish black solid (hereinafter to be referred as ruthenium complexe A-4), productive rate is 83%.
The spectroscopic analysis of this ruthenium complexe A-4: 1H NMR (400MHz, d 6-dimethyl sulfoxide (DMSO), 298K), (ppm): 9.37 (s, 2H), 9.13 (s, 2H), 8.49 (t, J HH=4.6Hz, 1H), 8.22～8.15 (m, 3H), 7.66 (d, J HH=5.6Hz, 2H), 7.58 (d, J HH=6.0Hz, 2H), 5.36 (d, J HF=10.8Hz, 1H); MS (FAB, 102Ru): m/z 842 (M+1) + 19F-{ 1H}NMR (470MHz, d 6-dimethyl sulfoxide (DMSO), 298K), (ppm) :-59.07 (s, 3F) ,-62.12 (s, 3F) ,-117.76 (s, 1F); Ultimate analysis data: C:46.08%; N:11.15%; H:233%.
The chemical structure of this ruthenium complexe A-4 is:
Figure BDA0000135693430000251
Embodiment 5
With 120 milligrams (0.18mmol) 4,4 '; 4 " the synthesis example 5 of-ethoxycarbonyl-three pyridine ruthenium trichloride, 95.8 milligrams (0.18mmol) and the Potassium ethanoate of 89.6 milligrams (0.91mmol) place single neck bottle of 50 milliliters, add 30 milliliters dimethylbenzene, and reflux is 12 hours under nitrogen.Be cooled to room temperature after reaction finishes, and in the underpressure distillation mode with solvent removal.Again with ethyl acetate: methylene dichloride=1: 8 can get 113 milligrams coffee-like solid as carrying out the tubing string chromatography towards extract, and productive rate is 58%.
The spectroscopic analysis of this coffee color solid: 1H NMR (400MHz, CDCl 3, 298K), (ppm): 9.03 (s, 2H), 8.81 (s, 2H), 8.51 (s, 1H), 8.07 (s, 1H), 7.77 (d, J HH=8.0Hz, 1H), 7.68 (d, J HH=3.6Hz, 1H), 7.64 (d, J HH=6.0Hz, 2H), 7.59 (d, J HH=6.0Hz, 2H), 6.95 (d, J HH=3.6Hz, 1H), 6.91 (d, J HH=8.0Hz, 1H), 5.54 (s, 1H), 4.64 (q, J HH=7.2Hz, 2H), 4.40 (q, J HH=7.2Hz, 4H), 2.95 (t, J HH=7.6Hz, 2H), 1.78 (q, J HH=7.6Hz, 2H), 1.60 (t, J HH=7.2Hz, 3H), 1.50～1.30 (m, 12H), 0.92 (t, J HH=6.8Hz, 3H).
The above-mentioned coffee-like solid of 101 milligrams (0.11mmol) is placed single neck bottle of 50 milliliters, add 15 milliliters acetone and 1 milliliter 1M sodium hydroxide solution.Reflux is 2 hours under nitrogen, is cooled to room temperature after reaction finishes, and in the underpressure distillation mode with solvent removal.The water that then adds 5 milliliters, and adjust pH value with the 2N hydrogen chloride solution and be about 3～4, then clean several with deionized water, acetone and methylene dichloride, can get 94.0 milligrams brownish black solid (hereinafter to be referred as ruthenium complexe A-5), productive rate is 83%.
The spectroscopic analysis of this ruthenium complexe A-5: 1H NMR (400MHz, d 6-dimethyl sulfoxide (DMSO), 298K), (ppm): 9.36 (s, 2H), 9.11 (s, 2H), 8.61 (s, 1H), 8.29 (s, 1H), 8.25 (d, J HH=8.0Hz, 1H), 8.15 (d, J HH=3.6Hz, 1H), 7.69 (d, J HH=6.0Hz, 2H), 7.62 (d, J HH=6.0Hz, 2H), 7.10 (d, J HH=3.6Hz, 1H), 6.97 (d, J HH=8.0Hz, 1H), 5.61 (s, 1H), 2.95 (t, J HH=6.8Hz, 2H), 1.74 (q, J HH=6.8Hz, 2H), 1.48～1.25 (m, 6H), 0.89 (t, J HH=6.8Hz, 3H); MS (FAB, 102Ru): m/z 989 (M) + 19F-{ 1H}NMR (470MHz, d 6-dimethyl sulfoxide (DMSO), 298K), (ppm) :-61.20 (s, 3F) ,-62.07 (s, 3F); Ultimate analysis data: C:46.47; N:9.19; H:3.75.
The chemical structure of this ruthenium complexe A-5 is:
Figure BDA0000135693430000271
Comparative example 1
N749 is available from Switzerland Solaronix SA company, model: Ruthenizer 620-1H3TBA.When the present invention carries out every detection, with dehydrated alcohol its concentration is transferred to 0.3mM earlier, and add the Chenodiol (chenodeoxycholic acid is called for short CDCA) of 20mM.
Detection
1. molar extinction coefficient (molar extinction coefficient) is measured:
The ruthenium complexe of embodiment 1～5 and the N749 of comparative example 1 are dissolved with DMF, and with UV-light/visible spectrometry (manufacturer: Hitachi Spectrophotometer, model: U-3900) measure the molar extinction coefficient value.
2. redox potential is measured:
The ruthenium complexe of embodiment 1～5 and the N749 of comparative example 1 are dissolved in dimethyl formamide (dimethylformamide), and add the TBAPF of 0.1M 6Solution, then adopt electrochemical analyser with cycle potentials method (manufacturer: CH Instrumewnts, model: ElectrochemicalAnalyzer CHI621a) measure.And with Fc/Fc +Be internal standard product, Ag/AgNO 3Be reference electrode, Pt is supporting electrode, and vitreous carbon is working electrode, and scanning speed is 20mVs -1And with Fc/Fc +As the internal standard product, measured numerical value is added 0.630V can be converted into the NHE current potential.This E 0-0Be to be tried to achieve with the intersection point of the spectrum of giving out light by the absorption of solution state.
3. photoelectric transformation efficiency is measured:
The production method of this dye sensitization solar battery is known by those skilled in the art, and this embodiment only is example explanation usefulness, and should not be interpreted as restriction of the invention process.
The making of this dye sensitization solar battery is that the slurry with titania nanoparticles prints to conducting glass substrate, in High Temperature Furnaces Heating Apparatus, behind the sintering, make its total thickness reach about 20 microns, then, be soaked in the titanium tetrachloride aqueous solution of concentration 40mM again, and place 75 ℃ baking oven 30 minutes.Then with deionized water, ethanol rinse, form the electrically-conductive backing plate that contains titanium dioxide.Use 6 electrically-conductive backing plates that contain titanium dioxide to be placed in respectively in the solution of the ruthenium complexe that contains the embodiment of the invention 1～5 and comparative example 1, at room temperature soaked 18 hours, again with the dehydrated alcohol flushing, form 6 first electrodes after the taking-up.
Get the fin oxide condutire glass of 6 doped with fluorine elements, drip the platinum acid chloride solution (solvent is Virahol) of the 50mM of 10 microlitres respectively, and under 450 ℃, carried out heat scission reaction 15 minutes, be reduced to platinum, form 6 second electrodes.
First electrode and second electrode are melted the macromolecule membrane encapsulation with heat in couples, and electrolytic solution component pre-drilled small holes from second electrode is injected.Then reusable heat melts macromolecule membrane and little sheet glass seals small holes, finishes the making of 6 dye sensitization solar batterys.This electrolytic solution component is the TBAPF of 0.1M 6Solution.
With above-mentioned dye sensitization solar battery respectively with solar simulator (150W xenon lamp, label: Class A, Newport Oriel; Model: 91159) irradiation provides one to meet air mas s (AM) 1.5Global spectrum and intensity is 100mW/cm 2Simulated light.Use external numerical digit ammeter (label: Keithley; Model: 2400) respectively dye sensitization solar battery is applied an impressed voltage, and record its electric current simultaneously, collect data, can draw voltage and current density graphic representation.In voltage-current curve figure, with the transverse axis intersection point be that open circuit voltage (is called for short V OC), and with longitudinal axis intersection point be that short-circuit current (is called for short J SC), and electric current and voltage density maximum product (is called for short P Max) divided by incident intensity, can obtain photoelectric transformation efficiency.
4. the long-acting stability measurement of solar cell:
Utilize the mode of the 3rd described dye sensitization solar battery in the test item to prepare dye sensitization solar battery, wherein, the electrolytic solution component replaces with 1 of 2.0M, 3-dimethyl-imidazoles iodine, 0.05M lithium iodide, 0.03M iodine, 0.1M guanidine thiocyanate, and 0.5M nitrogen-butyl benzoglyoxaline solution.
But dye sensitization solar battery is covered the macromolecule membrane of a ultraviolet shielding respectively, and place the long-acting testing apparatus of solar cell (label: ATLAS GmbH; Model: Suntest CPS+).Then use the solar simulator Continuous irradiation, and in enclosed environment, feed hot blast, make envrionment temperature maintain 60 ℃, every through after the irradiation in 100 hours, take out and measure its voltage and current data, and calculate photoelectric transformation efficiency, reach 1,000 hour up to irradiation time.
Table 1 detected result
Figure BDA0000135693430000291
By the result of Fig. 1 as can be known, the ruthenium complexe of the embodiment of the invention 1～5 not only absorption near infrared light zone is suitable with the N749 dyestuff, and absorption and molar extinction coefficient in the visible region more are better than N749.
In addition, by the data results of table 1 as can be known, the electrical properties (E of the ruthenium complexe of the embodiment of the invention 2～5 OxAnd E 0-0) not only suitable with the N749 dyestuff, and it also is suitable with N749 dyestuff (8.75%) that the photoelectric transformation efficiency of the ruthenium complexe of this embodiment 2～3 is respectively 8.76% and 8.18%, and the photoelectric transformation efficiency of the ruthenium complexe of embodiment 4 (9.04%) is better than N749 dyestuff (8.75%) especially.
Electrical properties and the N749 of the ruthenium complexe of embodiment 1 are suitable, and photoelectric transformation efficiency is 4.76%, though photoelectric transformation efficiency is not as good as the N749 dyestuff, but there is no the existence of thiocyanate ion dentate because of such ruthenium complexe, compare, such ruthenium complexe can increase the life-span of dye sensitization solar battery effectively, has more important meaning and utilizability for the use of this area.
Nitrogen-atoms on the azoles group of the embodiment of the invention 2,3,4 and 5 ruthenium complexe has three, and its E OxAll greater than 0.9V, show that ruthenium complexe of the present invention can cooperate the energy rank of electrolytic solution component, to reach best regeneration efficiency.
By the data results of the photoelectric transformation efficiency of Fig. 2 as can be known, test after 1,000 hour, using the photoelectric transformation efficiency decline amplitude of the dye sensitization solar battery of N749 is 39% (being down to 4.42% by 7.25%); The photoelectric transformation efficiency of the dye sensitization solar battery of the ruthenium complexe of use embodiment 1 does not have decline (remaining on about 5.05%); The photoelectric transformation efficiency decline amplitude of the dye sensitization solar battery of the ruthenium complexe of use embodiment 2 is 2.7% (being down to 7.5% by 7.71%); The photoelectric transformation efficiency decline amplitude of the dye sensitization solar battery of the ruthenium complexe of use embodiment 3 is 5.7% (being down to 7.06% by 7.49%); The photoelectric transformation efficiency decline amplitude of the dye sensitization solar battery of the ruthenium complexe of use embodiment 4 is the rate of falling 3.9% (being down to 7.76% by 8.07%), therefore, use ruthenium complexe of the present invention to be applied on the dye sensitization solar battery, really can allow make dye sensitization solar battery when life-time service, have preferable photoelectric transformation efficiency and preferable work-ing life.By synthetic method of the present invention, the productive rate of such ruthenium complexe is reached more than sixty percent in addition, be applied in the dye sensitization solar battery ruthenium complexe of low-yield with other and compare, the present invention more can quantize preparation and commercial applications greatly.
In sum, be the structure design of aglucon by 2-phenyl-6-azoles yl pyridines, make this aglucon can be in the visible region and the near infrared light zone have preferable absorption, and after forming the 8th group 4 transition metal complexes with metal-complexing, absorption spectrum ranges and the solar spectrum of the 8th group 4 transition metal complexes are complementary, strengthen the 8th group 4 transition metal complexes to the absorption in visible region and near infrared light zone.In addition, the 8th group 4 transition metal complexes is subsequently applied in the dye sensitization solar battery, can make this dye sensitization solar battery effectively utilize sun power, when life-time service, has preferable photoelectric transformation efficiency and work-ing life, for this area provides different choice, so can reach purpose of the present invention really.

Claims (15)

1. 2-phenyl-6-azoles yl pyridines is aglucon, it is characterized in that, structure is by shown in the formula (I):
Figure FDA0000135693420000011
In the formula (I),
X is C-R 10Or nitrogen-atoms;
R 1～R 8And R 10For identical or different, and be respectively hydrogen, halogen, cyano group, amido, aryl, heteroaryl, sulfate radical, acetate moiety, alkoxyl group, carbonyl, C 1～C 10Haloalkyl, C 1～C 12Alkyl, C 2～C 10Thiazolinyl, C 2～C 10Alkynyl, C 3～C 20Cycloalkyl, C 3～C 20Cycloalkenyl group, C 1～C 20Heterocyclylalkyl, C 1～C 20Heterocycloalkenyl, or the combination of above-mentioned group;
R 9Be hydrogen or basic metal;
Condition be when X be C-R 10The time, R 5And R 7Can not be fluorine and R simultaneously 6And R 8Can not be hydrogen simultaneously, or R 6And R 8Can not be fluorine and R simultaneously 5And R 7Can not be hydrogen simultaneously.
2. 2-phenyl as claimed in claim 1-6-azoles yl pyridines is aglucon, it is characterized in that: X is C-R 10
3. 2-phenyl as claimed in claim 1-6-azoles yl pyridines is aglucon, it is characterized in that: X is nitrogen.
4. 2-phenyl as claimed in claim 1-6-azoles yl pyridines is aglucon, it is characterized in that: R 1Be trifluoromethyl.
5. 2-phenyl as claimed in claim 1-6-azoles yl pyridines is aglucon, it is characterized in that: R 5～R 8In any is fluorine or trifluoromethyl.
6. 2-phenyl as claimed in claim 1-6-azoles yl pyridines is aglucon, it is characterized in that: R 1Be trifluoromethyl, and R 5～R 8In any is fluorine or trifluoromethyl.
7. 2-phenyl as claimed in claim 1-6-azoles yl pyridines is aglucon, and it is characterized in that: described heteroaryl is selected from:
R 11～R 16Be hydrogen, halogen, cyano group, amido, aryl, heteroaryl, alkoxyl group, C 1～C 10Haloalkyl, C 1～C 12Alkyl, C 2～C 10Thiazolinyl, C 2～C 10Alkynyl, C 3～C 20Cycloalkyl, C 3～C 20Cycloalkenyl group, C 1～C 20Heterocyclylalkyl, C 1～C 20Heterocycloalkenyl, or the combination of above-mentioned group.
8. 2-phenyl as claimed in claim 1-6-azoles yl pyridines is aglucon, and it is characterized in that: described amido is selected from-NR 17R 18,
Figure FDA0000135693420000022
Figure FDA0000135693420000023
R 17～R 22Be hydrogen, halogen, cyano group, amido, aryl, heteroaryl, alkoxyl group, C 1～C 10Haloalkyl, C 1～C 12Alkyl, C 2～C 10Thiazolinyl, C 2～C 10Alkynyl, C 3～C 20Cycloalkyl, C 3～C 20Cycloalkenyl group, C 1～C 20Heterocyclylalkyl, C 1～C 20Heterocycloalkenyl, or the combination of above-mentioned group.
9. 2-phenyl as claimed in claim 1-6-azoles yl pyridines is aglucon, it is characterized in that: described alkoxyl group is OR 23R 23Be hydrogen, halogen, cyano group, amido, aryl, heteroaryl, alkoxyl group, C 1～C 10Haloalkyl, C 1～C 12Alkyl, C 2～C 10Thiazolinyl, C 2～C 10Alkynyl, C 3～C 20Cycloalkyl, C 3～C 20Cycloalkenyl group, C 1～C 20Heterocyclylalkyl, C 1～C 20Heterocycloalkenyl, or the combination of above-mentioned group.
10. 2-phenyl as claimed in claim 1-6-azoles yl pyridines is aglucon, it is characterized in that: R 3Be hydrogen, aryl, heteroaryl, amido, C 1～C 12Alkoxyl group, or R 24Be hydrogen, halogen, cyano group, amido, aryl, heteroaryl, alkoxyl group, C 1～C 10Haloalkyl, C 1～C 12Alkyl, C 2～C 10Thiazolinyl, C 2～C 10Alkynyl, C 3～C 20Cycloalkyl, C 3～C 20Cycloalkenyl group, C 1～C 20Heterocyclylalkyl, C 1～C 20Heterocycloalkenyl, or the combination of above-mentioned group.
11. a group 4 transition metal complexes is characterized in that, structure is by shown in the formula (II):
ML 1L 2 (II)
In the formula (II), M is ruthenium metal or osmium metal; L 1For being aglucon just like each described 2-phenyl-6-azoles yl pyridines in the claim 1 to 10; L 2For the two pyridines of carboxyl are aglucon.
12. the 8th group 4 transition metal complexes as claimed in claim 11 is characterized in that: M is the ruthenium metal.
13. the 8th group 4 transition metal complexes as claimed in claim 11 is characterized in that: M is the osmium metal.
14. the 8th group 4 transition metal complexes as claimed in claim 11 is characterized in that: the two pyridines of described carboxyl are aglucon, and structure is by shown in the formula (III):
Figure FDA0000135693420000032
In the formula (III), X 1～X 7For identical or different, and be respectively hydrogen, halogen, trifluoromethyl, C 1～C 12Straight chained alkyl, C 1～C 12Branched-chain alkyl, phosphate, phosphoric acid salt, boronate, borate, sulfonic group, sulfonate, or COOY, and condition is X 1～X 7In at least one is COOY; Y is hydrogen, basic metal, C 1～C 12Straight chained alkyl, C 1～C 12Branched-chain alkyl, or N (C 4H 9) 4 +
X 8For
Figure FDA0000135693420000041
X 9～R 12Be hydrogen, halogen, trifluoromethyl, carboxylic acid group, C 1～C 8Straight chained alkyl, C 1～C 8Branched-chain alkyl,
Figure FDA0000135693420000042
X 13With X 14Be hydrogen, halogen, trifluoromethyl, carboxylic acid group, C 1～C 8Straight chained alkyl, C 1～C 8Branched-chain alkyl, or
Figure FDA0000135693420000043
X 15With X 16Be alkoxyl group, alkylthio, C 1～C 8Straight chained alkyl, or C 1～C 8Branched-chain alkyl.
15. the 8th group 4 transition metal complexes as claimed in claim 14 is characterized in that: X 1～X 7In at least two be COOY.
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