CN104231001A - Symmetrical binuclear ruthenium complex and preparation method utilizing microwave - Google Patents
Symmetrical binuclear ruthenium complex and preparation method utilizing microwave Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000012327 Ruthenium complex Substances 0.000 title abstract 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 52
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003446 ligand Substances 0.000 claims abstract description 12
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 claims abstract description 11
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims abstract description 9
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 claims abstract description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 35
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 32
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- WCGIGOVLOFXAMG-UHFFFAOYSA-N silver;trifluoromethanesulfonic acid Chemical compound [Ag].OS(=O)(=O)C(F)(F)F WCGIGOVLOFXAMG-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000005227 gel permeation chromatography Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 6
- 229940125904 compound 1 Drugs 0.000 claims description 6
- 229940125782 compound 2 Drugs 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 5
- 101150003085 Pdcl gene Proteins 0.000 claims description 5
- 229910003691 SiBr Inorganic materials 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 238000003828 vacuum filtration Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 4
- 150000003303 ruthenium Chemical class 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000006880 cross-coupling reaction Methods 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract 1
- 238000007144 microwave assisted synthesis reaction Methods 0.000 abstract 1
- -1 phosphoryl groups Chemical group 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- 230000005526 G1 to G0 transition Effects 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 9
- 238000000746 purification Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 230000001235 sensitizing effect Effects 0.000 description 5
- 239000000499 gel Substances 0.000 description 4
- VANSZAOQCMTTPB-SETSBSEESA-N hypocrellin Chemical compound C1[C@@](C)(O)[C@@H](C(C)=O)C2=C(OC)C(O)=C3C(=O)C=C(OC)C4=C3C2=C2C3=C4C(OC)=CC(=O)C3=C(O)C(OC)=C21 VANSZAOQCMTTPB-SETSBSEESA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- KGHNSNSWRMJVND-UHFFFAOYSA-N Hypocrellin Natural products COC1=CC(=O)C2=C3C4C(C(C(=O)C)C(C)(O)Cc5c(OC)c(O)c6C(=O)C=C(OC)C(=C13)c6c45)C(=C2O)OC KGHNSNSWRMJVND-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 210000003608 fece Anatomy 0.000 description 3
- 238000006053 organic reaction Methods 0.000 description 3
- BQJKVFXDDMQLBE-UHFFFAOYSA-N shiraiachrome A Natural products COC1=C2C3=C(OC)C=C(O)C4=C3C3=C5C(CC(C)(O)C(C(C)=O)C3=C(OC)C4=O)=C(OC)C(=O)C(C(O)=C1)=C25 BQJKVFXDDMQLBE-UHFFFAOYSA-N 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 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 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- AVFIYMSJDDGDBQ-UHFFFAOYSA-N Parthenium Chemical compound C1C=C(CCC(C)=O)C(C)CC2OC(=O)C(=C)C21 AVFIYMSJDDGDBQ-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- WCYJXDMUQGVQQS-UHFFFAOYSA-N pyridine;ruthenium Chemical compound [Ru].C1=CC=NC=C1 WCYJXDMUQGVQQS-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical class [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention relates to a symmetrical binuclear ruthenium complex and a preparation method utilizing microwave, belonging to the technical field of synthetic chemistry. The preparation method comprises the following steps: firstly reacting 2-acetylpyridine with 4-bromobenzaldehye as a starting raw material, wherein traditional NaOH and CH3OH are respectively replaced with KOH and EtOH to further shorten reaction time; performing cross-coupling reaction to the obtained terpyridyl compound and diethyl phosphite, wherein the P-H bond in diethyl phosphite is cut off by taking triethylamine as a salt base; then synthesizing an intermediate complex together with ruthenium trichloride hydrate RuCl3.3H2O, and then synthesizing a target product under microwave conditions. The complex molecules can be adsorbed onto a conductive substrate such as an ITO and the like by taking phosphoryl groups at two ends of the complex molecules as fixed ligands and layer-by-layer self assembling can be realized, and the symmetrical binuclear ruthenium complex is an excellent photosensitive dye. The symmetrical binuclear ruthenium complex is simple in design synthesis process and low in cost, and the microwave-assisted synthesis technology is fast and efficient.
Description
Technical field
The present invention relates to a kind of symmetry binuclear ruthenium and utilize microwave preparation, belonging to synthesising chemical technology field.
Background technology
Society, along with becoming increasingly conspicuous of energy problem, finding clean and sustainable energy just becomes one of critical problem that the mankind face.In numerous clean energies, sun power is because it is general, harmless, huge and permanence and be subject to the favor of investigator.Sun power can be described as inexhaustible and also do not have region to limit, can directly development and utilization, need not exploit and transport, and exploitation sun power does not pollute the environment, and this, in environmental pollution more and more serious today, seems particularly important.Dye-sensitized solar cells mainly imitates photosynthesis principle, the novel solar cell of the one developed, and is one of main path utilizing sun power.
Dye sensitizing agent, as the important component part of battery, can absorb sunlight effectively, produces excitation electron.Therefore, the photoelectric transformation efficiency of dye sensitizing agent on dye sensitization solar battery has vital impact.Effective and the most stable sensitizing agent of generally acknowledging at present is the pyridine ruthenium complexe dyestuff with phosphate or carboxyl, electronic cloud overlap can be there is in its phosphate or carboxyl, form good electron transfer pathways, carboxyl is the first-selected fixed group that people study dye sensitizing agent always, is also that current result of study it seems best a kind of fixed group.Ruthenium complexe becomes sensitizing agent first-selected in solar cell because the oxidation-reduction quality of its uniqueness, chemical stability, excited state reaction are active and lifetime of excited state is shown one's talent in numerous dyestuffs, and prepare ruthenium complexe how efficiently, rapidly, become the study hotspot in this field.
Under the condition of microwave, utilize its heating fast, the advantage such as homogeneous and selectivity, be applied to modern organic synthesis study in technology, be called Microwave synthesize.Research in microwave assisted organic reaction is a focus in organic chemistry filed.By means of microwave technology, the heating means that the speed of response of organic reaction is more traditional can improve decades of times even thousands of times, and easy and simple to handle, productive rate is high, easy purification of products, safety and sanitation, thus facilitate and make developing rapidly of microwave organic reaction.
The research of the domestic preparation method to utilizing Microwave synthesize symmetry binuclear ruthenium at present have not been reported.The method of the preparation of disclosed ruthenium complexe mainly contains:
Publication number is in the Chinese patent disclosed " ruthenium complexes in dipyridine group of hypocrellin and preparation method thereof " of CN 1660863 A, dichloro second bipyridine conjunction ruthenium and hypocrellin are carried out coordination and synthesizes the difunctional ruthenium complexe of dipyridine group of hypocrellin class, maintain the photosensitive activity of hypocrellin, improve medicine in blood transmission or enter intracellular ability and station-keeping ability.
Publication number is in the Chinese patent disclosed " preparation method of New Ruthenium title complex and the optical activity alkylol cpd using this title complex as catalyzer " of CN 103443111 A, there is provided a kind of synthetic method of New Ruthenium title complex, this ruthenium complexe shows excellent catalytic activity in the reduction of multiple bond, asymmetric reduction reaction particularly at carbonyl compound.
Publication number is in the Chinese patent disclosed " synthetic method of Ru-polypyridine complex and derivative thereof " of CN 101215298 A, by the company many pyridine ligand of ruthenium source material from different the position of substitution, different ligands type, one step or be divided into some steps, in the closed reactor of pressurized, heated, be obtained by reacting target product, the high pressure synthesis method of the Ru-polypyridine complex that this invention provides requires height to reactor.
The synthetic method of at present conventional ruthenium complexe normally with ruthenium source materials such as ruthenium trichlorides for starting raw material, in atmospheric conditions, carry out several times complex reaction by reflux mode, obtain the title complex between specific part and ruthenium.
Summary of the invention
For above-mentioned prior art Problems existing and deficiency, the invention provides a kind of symmetry binuclear ruthenium and utilize microwave preparation.The phosphate group of the two ends symmetry in the symmetry binuclear ruthenium that the present invention prepares makes this complex molecule can be adsorbed onto on the electrically-conductive backing plates such as ITO also can realize layer-by-layer, it is a kind of excellent light-sensitive coloring agent, the advantage of preparation method is to adopt microwave process for synthesizing to prepare symmetry binuclear ruthenium, has that rate of heating is fast, heat utilization rate is high, is quick on the draw and quality product high.Compared with traditional ruthenium complexe preparation method, microwave radiation can make temperature of reaction system raise rapidly at short notice, thus Reaction time shorten, reduce the generation of side reaction, and improve the transformation efficiency of reaction, the present invention is achieved through the following technical solutions.
A kind of symmetry binuclear ruthenium, this ruthenium complexe is using the phosphate group of two ends symmetry as fixed ligands, and 3 atom N on the imidazole ring of benzimidizole derivatives and terpyridyl ring and metal Ru ion coordination form title complex, and its chemical general formula is as follows:
A kind of symmetry binuclear ruthenium utilizes microwave preparation, and its concrete steps are as follows:
(1) first 4-bromobenzaldehyde is dissolved in EtOH, adds 2-acetylpyridine, KOH and NH continuously
4oH, be heated to 80 ~ 100 DEG C of backflows and separate out through vacuum filtration after yellow solids, washing, recrystallization obtains 4-(4-bromophenyl)-2,2:6,2-terpyridyls, and wherein the mol ratio of 4-bromobenzaldehyde and 2-acetylpyridine is 1:2 ~ 3;
(2) under protective atmosphere, 4-(4-bromophenyl)-2,2:6,2-terpyridyls step (1) obtained are dissolved in dry toluene, add diethyl phosphite, triethylamine and PdCl continuously
2(dppf) CH
2cl
2, stirring heating under temperature is 90 ~ 120 DEG C of conditions, filters reaction soln, distillation, adopts column chromatography to purify and obtain 4-(2,2 ' after dry; 6 ', 2 ' '-terpyridyl-4 '-phenyl)-diethyl phosphoric acid; Wherein the mol ratio of 4-(4-bromophenyl)-2,2:6,2-terpyridyls and diethyl phosphite is 1:1 ~ 2;
(3) under protective atmosphere, by the 4-(2,2 ' that dry ruthenium trichloride hydrate and step (2) obtain; 6 ', 2 ' '-terpyridyl-4 '-phenyl)-diethyl phosphoric acid is dissolved in ethanolic soln, and filter after heated and stirred under temperature is 90 ~ 120 DEG C of conditions and obtain reddish-brown intermediate compound 1, wherein 4-(2,2 '; 6 ', 2 ' '-terpyridyl-4 '-phenyl) mol ratio of-diethyl phosphoric acid and ruthenium trichloride hydrate is 1:1 ~ 2;
(4) under protective atmosphere, the intermediate compound 1 obtain step (3) and trifluoro-methane sulfonic acid silver are dissolved in acetone, lucifuge backflow is until produce white precipitate, after diatomite filtration, through distillation, washing obtains purple intermediate compound 2, and wherein the mol ratio of intermediate compound 1 and trifluoro-methane sulfonic acid silver is 1:2 ~ 3;
(5) Pyromellitic Acid is dissolved in hot PPA, adds O-Phenylene Diamine (mol ratio of Pyromellitic Acid and O-Phenylene Diamine is 1:8 ~ 12), at 200 DEG C, stir 16h, after being cooled to room temperature, pour H into
2in O, use 10% NaHCO
3solution regulates PH to obtain middle part 3 to neutral rear filtration, drying, and be dissolved in ethylene glycol by the intermediate compound 2 that middle part 3 and step (4) obtain, 1 ~ 3min is reacted in microwave heating temperature to 140 ~ 160 DEG C then, adds excessive KPF after being cooled to room temperature
6after solution in impouring water, filter, adopt dextrane gel gel chromatography to purify after dry and obtain purple intermediate compound 4, wherein the mol ratio of Pyromellitic Acid and O-Phenylene Diamine is 1:8 ~ 12, and the mol ratio of middle part 3 and intermediate compound 2 is 1:2 ~ 3;
(6) title complex intermediate 4 is dissolved in anhydrous DMF solution, drips Me
3siBr solution, adds MeOH after stirring, continues stirring underpressure distillation after 10 ~ 15 hours, is dissolved in ammoniacal liquor, adds excessive KPF after washing
6solution, regulates pH value with acid until produce purple precipitation, filters and obtain ruthenium complexe, wherein title complex intermediate 4 and Me
3the mol ratio of SiBr is 1:250 ~ 350.
The temperature of reaction of described step (1) is 80 ~ 100 DEG C of steps; The temperature of reaction of step (2) is 90 ~ 120 DEG C; The temperature of reaction of step (3) is 90 ~ 120 DEG C; The temperature of reaction of step (4) is 60 ~ 80 DEG C.
The above-mentioned method utilizing Microwave synthesize symmetry binuclear ruthenium, the reaction formula of step (1) is as follows:
The reaction formula of step (2) is as follows:
The reaction formula of step (3) is as follows:
The reaction formula of step (4) is as follows:
The reaction formula of step (5) is as follows:
The reaction formula of step (6) is as follows:
The invention has the beneficial effects as follows:
1, the present invention KOH and EtOH when synthesizing 4-(4-bromophenyl)-2,2:6,2-terpyridine ligand substitutes traditional NaOH and CH respectively
3oH, thus Reaction time shorten.
2, the present invention adopts microwave process for synthesizing to prepare symmetry binuclear ruthenium, has that rate of heating is fast, heat utilization rate is high, is quick on the draw and quality product high.Compared with traditional ruthenium complexe preparation method, microwave radiation can make temperature of reaction system raise rapidly at short notice, thus Reaction time shorten, reduce the generation of side reaction, and improve the transformation efficiency of reaction.
3, the binuclear ruthenium prepared of the present invention is because having the feature of three tooth chelatings and stability, and easily synthesize in preparation technology and modify, preparation method is simple to operate, and preparation cost is low, and raw material is easy to get, and the product purity obtained is higher.
The phosphate group of the two ends symmetry 4, in this complex molecule makes this complex molecule can be adsorbed onto on the electrically-conductive backing plates such as ITO and can realize layer-by-layer, is a kind of excellent light-sensitive coloring agent.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
This symmetry binuclear ruthenium utilizes microwave preparation, and its concrete steps are as follows:
(1) synthetic ligands 4-(4-bromophenyl)-2,2:6,2-terpyridyls, are designated as tpyBr.
The synthesis of part tpyBr: by 1g; the 4-bromobenzaldehyde of 5.4mmol is dissolved in 120mlEtOH; add 1.31g continuously, the 2-acetylpyridine (mol ratio of 4-bromobenzaldehyde and 2-acetylpyridine is 1:2) of 10.8mmol, KOH and the 30ml NH of 0.3g, 5.4mmol
4oH, at room temperature stirs 3 hours after reflux 24h at 90 DEG C, separates out yellow solid after vacuum filtration with MeOH and H
2o washs, and the white crude MeOH obtained carries out recrystallization and obtains high pure white product tpyBr.
1H-NMR（500MHz，CDCl
3）：δ(ppm)=?8.73(2H,d)，8.70(2H,s)，8.68(2H,d)，7.88(2H,m)，7.79(2H,d)，7.65(2H,d)，7.36(2H,m)。
(2) synthetic ligands 4-(2,2 '; 6 ', 2 ' '-terpyridyl-4 '-phenyl)-diethyl phosphoric acid, be designated as tpyPO (OEt)
2.
Part tpyPO (OEt)
2synthesis: under nitrogen atmosphere, the tpyBr of 1.94g, 5.0mmol is dissolved in the dry toluene of 50ml, adds 0.76g continuously, the diethyl phosphite HPO (OEt) of 5.5mmol
2(tpyBr and HPO (OEt)
2mol ratio be 1:1.1), the triethylamine of 0.56g, 5.5mmol and the PdCl of 204mg, 0.25mmol
2(dppf) CH
2cl
2, stirring heating 24h at 90 DEG C.Through distillation after being filtered by reacted solution, adopt column chromatography to purify after dry, stationary phase uses the spherical silica gel of 63 ~ 210um, and stationary phase height is 10cm, and moving phase is the CH of 90/10
2cl
2/ MeOH solution, carries out purification through column chromatography and obtains crystallized product tpyPO (OEt)
2.
1H-NMR（500MHz，CDCl
3）：δ(ppm)=?8.76(2H,s)，8.74(2H,d,J=3.8Hz)，8.69(2H,d,J=8.1Hz)，8.00-7.94(4H,m)，7.90(2H,td,J=7.7,1.7Hz)，?7.38(2H,ddd,J=6.9,4.1,2.1Hz)，?4.16(4H,m)，1.36(6H,t,J=9.3Hz)。
(3) synthetic mesophase title complex Ru (tpyPOEt) Cl
3.
Intermediate compound Ru (tpyPOEt) Cl
3synthesis: before experiment, get 0.38mmol, the RuCl of 99.56mg
33H
2o carries out vacuum-drying 0.5h, during experiment in a nitrogen atmosphere, by dry RuCl
33H
2the tpyPO (OEt) of O and 0.35mmol, 153.88mg
2(tpyPO (OEt)
2with RuCl
33H
2the mol ratio of O is 1:1.1) be dissolved in 20ml ethanolic soln, filter after heated and stirred 3h at 90 DEG C and obtain brown intermediate compound Ru (tpyPOEt) Cl
3.
(4) this experiment synthetic mesophase title complex Ru (tpyPOEt) Cl
2cF
3sO
3.
Intermediate compound Ru (tpyPOEt) Cl
2cF
3sO
3synthesis: under nitrogen atmosphere, by Ru (tpyPOEt) Cl of 0.76mmol, 0.5g
3and the trifluoro-methane sulfonic acid silver of 1.60mmol, 0.41g (Ru (tpyPOEt) Cl
3be 1:2.1 with the mol ratio of trifluoro-methane sulfonic acid silver) be dissolved in 60ml acetone, at 70 DEG C, lucifuge backflow 3h is until produce white precipitate, and after diatomite filtration, through distillation, EtOH washing obtains purple intermediate compound Ru (tpyPOEt) Cl
2cF
3sO
3.
(5) synthetic mesophase title complex [Ru
2(tpyPOEt)
2] (PF
6)
2.
Intermediate compound [Ru
2(tpyPOEt)
2] (PF
6)
2synthesis: the Pyromellitic Acid of 88.95mg, 0.35mmol is dissolved in the hot PPA of 10ml, adds 0.34ml, 0.36g, the O-Phenylene Diamine (mol ratio of Pyromellitic Acid and O-Phenylene Diamine is 1:8 ~ 12) of 2.96mmol, stirs 16h, pours H into after being cooled to room temperature at 200 DEG C
2in O, use 10% NaHCO
3the middle part 3 that solution regulates PH to obtain to neutral rear filtration, drying, with Ru (tpyPOEt) Cl of 0.76mmol, 0.58mg
2cF
3sO
3be dissolved in 25ml ethylene glycol, at 150 DEG C, microwave heating 3min, the solution obtained is cooled to room temperature, adds excessive KPF
6after solution in impouring water, the solid obtained after filtration, obtain purple crude product after drying.The purification of gained crude product adopts dextrane gel gel chromatography, stationary phase uses Sephadex LH-20, stationary phase diameter is 3cm is highly 15cm, and moving phase is the MeOH/ MeCN solution of 50/50, after gel chromatography is purified, obtain purple intermediate compound [Ru
2(tpyPOEt)
2] (PF
6)
2, wherein the mol ratio of Pyromellitic Acid and O-Phenylene Diamine is 1:8.5, middle part 3 and Ru (tpyPOEt) Cl
2cF
3sO
3mol ratio be 1:2 ~ 2.2.
1H-NMR（500MHz，CH
3CN-d
3）：δ(ppm)=10.35(4H,s)，9.20(4H,s)，8.66(4H,d,J=7.7Hz)，8.56-8.53(4H,m)，8.28-8.22(4H,m)，7.91(4H,t,J=7.0Hz)，7.65(4H,d,J=8.2Hz)，7.61(4H,d,J=6.3Hz)，7.37(4H,t,J=7.6Hz)，7.19(4H,t,J=6.3Hz)，7.06(4H,t,J=7.6Hz)，6.30(4H,d,J=8.9Hz)，4.34-4.23(8H,m)，1.43(12H,t,J=6.9Hz)。
(6) synthetic compound [Ru
2(tpyPOH)
2] (PF
6)
2.
[Ru
2(tpyPOH)
2] (PF
6)
2synthesis: in a nitrogen atmosphere, by [the Ru of 0.20g, 0.12mmol
2(tpyPOEt)
2] (PF
6)
2be dissolved in the anhydrous DMF solution of 50ml, the Me of point three droppings 4.80g, 4.14ml, 31.2mmol
3siBr solution ([Ru
2(tpyPOEt)
2] (PF
6)
2with Me
3the mol ratio of SiBr is 1:260), each dropping interval 30min, at room temperature stirs after 48 hours and adds 15mlMeOH, at room temperature stirs decompression after 12 hours and heats up in a steamer MeOH and DMF, be dissolved in (PH=10) in ammoniacal liquor, add excessive KPF after MeCN washing
6solution, regulates pH value with hydrochloric acid until produce purple precipitation, filters and obtain purple product [Ru
2(tpyPOH)
2] (PF
6)
2.
1H-NMR（500MHz，DMSO-d
6）：δ(ppm)=?10.43(4H,s)，9.26(4H,s)，8.59(4H,d,J=7.3Hz)，8.53-8.50(4H,m)，8.32-8.28(4H,m)，7.95?(4H,t,J=7.4Hz)，7.69(4H,d,J=8.3Hz)，7.67(4H,d,J=6.3Hz)，7.39(4H,t,J=7.6Hz)，7.25(4H,t,J=6.0Hz)，7.11(4H,t,J=7.2Hz)，6.36(4H,d,J=9.3Hz)。
Title complex [the Ru prepared
2(tpyPOH)
2] (PF
6)
2general formula is as follows:
Embodiment 2
This symmetry binuclear ruthenium utilizes microwave preparation, and its concrete steps are as follows:
(1) synthetic ligands 4-(4-bromophenyl)-2,2:6,2-terpyridyls, are designated as tpyBr.
The synthesis of part tpyBr: by 1.3g; the 4-bromobenzaldehyde of 7.02mmol is dissolved in 120mlEtOH; add 2.13g continuously, the 2-acetylpyridine (mol ratio of 4-bromobenzaldehyde and 2-acetylpyridine is 1:2.5) of 17.56mmol, KOH and the 30ml NH of 0.39g, 7.02mmol
4oH, at room temperature stirs 3 hours after reflux 24h at 90 DEG C, separates out yellow solid after vacuum filtration with MeOH and H
2o washs, and the white crude MeOH obtained carries out recrystallization and obtains high pure white product tpyBr.
1H-NMR（500MHz，CDCl
3）：δ(ppm)=8.75(2H,d)，8.71(2H,s)，8.69(2H,d)，7.83(2H,m)，7.75(2H,d)，7.62(2H,d)，7.37(2H,m)。
(2) synthetic ligands 4-(2,2 '; 6 ', 2 ' '-terpyridyl-4 '-phenyl)-diethyl phosphoric acid, be designated as tpyPO (OEt)
2.
Part tpyPO (OEt)
2synthesis: under nitrogen atmosphere, the tpyBr of 1.56g, 4.01mmol is dissolved in the dry toluene of 50ml, adds 0.83g continuously, the diethyl phosphite HPO (OEt) of 6.03mmol
2(tpyBr and HPO (OEt)
2mol ratio be 1:1.5), the triethylamine of 0.46g, 4.5mmol and the PdCl of 491mg, 0.60mmol
2(dppf) CH
2cl
2, stirring heating 24h at 90 DEG C.Through distillation after being filtered by reacted solution, adopt column chromatography to purify after dry, stationary phase uses the spherical silica gel of 63 ~ 210um, and stationary phase height is 10cm, and moving phase is the CH of 90/10
2cl
2/ MeOH solution, carries out purification through column chromatography and obtains crystallized product tpyPO (OEt)
2.
1H-NMR（500MHz，CDCl
3）：δ(ppm)=8.73(2H,s)，8.71(2H,d,J=3.8Hz)，8.64(2H,d,J=8.6Hz)，8.04-7.99(4H,m)，7.94(2H,td,J=7.2,1.9Hz)，7.32(2H,ddd,J=6.4,4.2,2.4Hz)，4.17(4H,m)，1.31(6H,t,J=9.7Hz)。
(3) synthetic mesophase title complex Ru (tpyPOEt) Cl
3.
Intermediate compound Ru (tpyPOEt) Cl
3synthesis: before experiment, get 0.47mmol, the RuCl of 123.14mg
33H
2o carries out vacuum-drying 0.5h, during experiment in a nitrogen atmosphere, by dry RuCl
33H
2the tpyPO (OEt) of O and 0.31mmol, 139.57mg
2(tpyPO (OEt)
2with RuCl
33H
2the mol ratio of O is 1:1.5) be dissolved in 20ml ethanolic soln, filter after heated and stirred 3h at 90 DEG C and obtain brown intermediate compound Ru (tpyPOEt) Cl
3.
(4) this experiment synthetic mesophase title complex Ru (tpyPOEt) Cl
2cF
3sO
3.
Intermediate compound Ru (tpyPOEt) Cl
2cF
3sO
3synthesis: under nitrogen atmosphere, by Ru (tpyPOEt) Cl of 0.95mmol, 0.62g
3and the trifluoro-methane sulfonic acid silver of 2.38mmol, 0.61g (Ru (tpyPOEt) Cl
3be 1:2.5 with the mol ratio of trifluoro-methane sulfonic acid silver) be dissolved in 60ml acetone, at 70 DEG C, lucifuge backflow 3h is until produce white precipitate, and after diatomite filtration, through distillation, EtOH washing obtains purple intermediate compound Ru (tpyPOEt) Cl
2cF
3sO
3.
(5) synthetic mesophase title complex [Ru
2(tpyPOEt)
2] (PF
6)
2.
Intermediate compound [Ru
2(tpyPOEt)
2] (PF
6)
2synthesis: the Pyromellitic Acid of 121.99mg, 0.48mmol is dissolved in the hot PPA of 10ml, adds 0.54ml, 0.58g, the O-Phenylene Diamine (mol ratio of Pyromellitic Acid and O-Phenylene Diamine is 1:8 ~ 12) of 2.96mmol, stirs 16h, pours H into after being cooled to room temperature at 200 DEG C
2in O, use 10% NaHCO
3the middle part 3 that solution filters after regulating PH to neutrality, drying obtains and Ru (tpyPOEt) Cl of 0.95mmol, 0.73mg
2cF
3sO
3be dissolved in 25ml ethylene glycol, at 150 DEG C, microwave heating 3min, the solution obtained is cooled to room temperature, adds excessive KPF
6after solution in impouring water, the solid obtained after filtration, obtain purple crude product after drying.The purification of gained crude product adopts dextrane gel gel chromatography, stationary phase uses Sephadex LH-20, stationary phase diameter is 3cm is highly 15cm, and moving phase is the MeOH/ MeCN solution of 50/50, after gel chromatography is purified, obtain purple intermediate compound [Ru
2(tpyPOEt)
2] (PF
6)
2, wherein the mol ratio of Pyromellitic Acid and O-Phenylene Diamine is 1:10, middle part 3 and Ru (tpyPOEt) Cl
2cF
3sO
3mol ratio be 1:2.5.
1H-NMR（500MHz，CH
3CN-d
3）：δ(ppm)=10.31(4H,s)，9.25(4H,s)，8.69(4H,d,J=7.2Hz)，8.57-8.56(4H,m)，8.22-8.29(4H,m)，7.96(4H,t,J=7.0Hz)，7.64(4H,d,J=8.5Hz)，7.67(4H,d,J=6.2Hz)，7.38(4H,t,J=7.9Hz)，7.12(4H,t,J=6.5Hz)，7.04(4H,t,J=7.9Hz)，6.31(4H,d,J=8.5Hz)，4.38-4.22(8H,m)，1.47(12H,t,J=6.39Hz)。
(6) synthetic compound [Ru
2(tpyPOH)
2] (PF
6)
2.
[Ru
2(tpyPOH)
2] (PF
6)
2synthesis: in a nitrogen atmosphere, by [the Ru of 0.20g, 0.12mmol
2(tpyPOEt)
2] (PF
6)
2be dissolved in the anhydrous DMF solution of 50ml, the Me of point three droppings 5.54g, 4.78ml, 36mmol
3siBr solution ([Ru
2(tpyPOEt)
2] (PF
6)
2with Me
3the mol ratio of SiBr is 1:300), each dropping interval 30min, at room temperature stirs after 48 hours and adds 15mlMeOH, at room temperature stirs decompression after 12 hours and heats up in a steamer MeOH and DMF, be dissolved in (PH=10) in ammoniacal liquor, add excessive KPF after MeCN washing
6solution, regulates pH value with hydrochloric acid until produce purple precipitation, filters and obtain purple product [Ru
2(tpyPOH)
2] (PF
6)
2.
1H-NMR（500MHz，DMSO-d
6）：δ(ppm)=?10.42(4H,s)，9.27(4H,s)，8.51(4H,d,J=7.8Hz)，8.59-8.50(4H,m)，8.34-8.21(4H,m)，7.98(4H,t,J=7.2Hz)，7.64(4H,d,J=8.1Hz)，7.69(4H,d,J=6.2Hz)，7.33(4H,t,J=7.8Hz)，7.23(4H,t,J=6.4Hz)，7.14(4H,t,J=7.7Hz)，6.35(4H,d,J=9.1Hz)。
Embodiment 3
This symmetry binuclear ruthenium utilizes microwave preparation, and its concrete steps are as follows:
(1) synthetic ligands 4-(4-bromophenyl)-2,2:6,2-terpyridyls, are designated as tpyBr.
The synthesis of part tpyBr: by 1.8g; the 4-bromobenzaldehyde of 9.7mmol is dissolved in 120ml EtOH; add 1.313.41g continuously, the 2-acetylpyridine (mol ratio of 4-bromobenzaldehyde and 2-acetylpyridine is 1:2.9) of 28.13mmol, KOH and the 30ml NH of 0.54g, 9.7mmol
4oH, at room temperature stirs 3 hours after reflux 24h at 90 DEG C, separates out yellow solid after vacuum filtration with MeOH and H
2o washs, and the white crude MeOH obtained carries out recrystallization and obtains high pure white product tpyBr.
1H-NMR（500MHz，CDCl
3）：δ(ppm)=?8.79(2H,d)，8.72(2H,s)，8.65(2H,d)，7.83(2H,m)，7.78(2H,d)，7.61(2H,d)，7.39(2H,m)。
(2) synthetic ligands 4-(2,2 '; 6 ', 2 ' '-terpyridyl-4 '-phenyl)-diethyl phosphoric acid, be designated as tpyPO (OEt)
2.
Part tpyPO (OEt)
2synthesis: under nitrogen atmosphere, the tpyBr of 2.50g, 6.44mmol is dissolved in the dry toluene of 50ml, adds 1.69g continuously, the diethyl phosphite HPO (OEt) of 12.23mmol
2(tpyBr and HPO (OEt)
2mol ratio be 1:1.9), the triethylamine of 2.47g, 12.75mmol and the PdCl of 788.87mg, 0.97mmol
2(dppf) CH
2cl
2, stirring heating 24h at 90 DEG C.Through distillation after being filtered by reacted solution, adopt column chromatography to purify after dry, stationary phase uses the spherical silica gel of 63 ~ 210um, and stationary phase height is 10cm, and moving phase is the CH of 90/10
2cl
2/ MeOH solution, carries out purification through column chromatography and obtains crystallized product tpyPO (OEt)
2.
1H-NMR（500MHz，CDCl
3）：δ(ppm)=8.72(2H,s)，8.71(2H,d,J=3.8Hz)，8.64(2H,d,J=8.1Hz)，8.03-7.91(4H,m)，7.95(2H,td,J=7.3,1.8Hz)，?7.35(2H,ddd,J=6.2,4.7,2.3Hz)，4.19(4H,m)，1.32(6H,t,J=9.5Hz)。
(3) synthetic mesophase title complex Ru (tpyPOEt) Cl
3.
Intermediate compound Ru (tpyPOEt) Cl
3synthesis: before experiment, get 0.57mmol, the RuCl of 149.34mg
33H
2o carries out vacuum-drying 0.5h, during experiment in a nitrogen atmosphere, by dry RuCl
33H
2the tpyPO (OEt) of O and 0.30mmol, 133.64mg
2(tpyPO (OEt)
2with RuCl
33H
2the mol ratio of O is 1:1.9) be dissolved in 20ml ethanolic soln, filter after heated and stirred 3h at 90 DEG C and obtain brown intermediate compound Ru (tpyPOEt) Cl
3.
(4) this experiment synthetic mesophase title complex Ru (tpyPOEt) Cl
2cF
3sO
3.
Intermediate compound Ru (tpyPOEt) Cl
2cF
3sO
3synthesis: under nitrogen atmosphere, by Ru (tpyPOEt) Cl of 0.50mmol, 0.33g
3and the trifluoro-methane sulfonic acid silver of 1.45mmol, 0.37g (Ru (tpyPOEt) Cl
3be 1:2.9 with the mol ratio of trifluoro-methane sulfonic acid silver) be dissolved in 60ml acetone, at 70 DEG C, lucifuge backflow 3h is until produce white precipitate, and after diatomite filtration, through distillation, EtOH washing obtains purple intermediate compound Ru (tpyPOEt) Cl
2cF
3sO
3.
(5) synthetic mesophase title complex [Ru
2(tpyPOEt)
2] (PF
6)
2.
Intermediate compound [Ru
2(tpyPOEt)
2] (PF
6)
2synthesis: the Pyromellitic Acid of 43.21mg, 0.17mmol is dissolved in the hot PPA of 7ml, adds 0.22ml, 0.24g, the O-Phenylene Diamine (mol ratio of Pyromellitic Acid and O-Phenylene Diamine is 1:8 ~ 12) of 1.96mmol, stirs 16h, pours H into after being cooled to room temperature at 200 DEG C
2in O, use 10% NaHCO
3the middle part 3 that solution filters after regulating PH to neutrality, drying obtains and Ru (tpyPOEt) Cl of 0.50mmol, 0.38mg
2cF
3sO
3solution is in 25ml ethylene glycol, and at 150 DEG C, microwave heating 3min, the solution obtained is cooled to room temperature, adds excessive KPF
6after solution in impouring water, the solid obtained after filtration, obtain purple crude product after drying.The purification of gained crude product adopts dextrane gel gel chromatography, stationary phase uses SephadexLH-20, stationary phase diameter is 3cm is highly 15cm, and moving phase is the MeOH/ MeCN solution of 50/50, after gel chromatography is purified, obtain purple intermediate compound [Ru
2(tpyPOEt)
2] (PF
6)
2.Wherein the mol ratio of Pyromellitic Acid and O-Phenylene Diamine is 1:11.5, middle part 3 and Ru (tpyPOEt) Cl
2cF
3sO
3mol ratio be 1:2.9.
1H-NMR（500MHz，CH
3CN-d
3）：δ(ppm)=10.32(4H,s)，9.27(4H,s)，8.69(4H,d,J=7.2Hz)，8.58-8.50(4H,m)，8.29-8.19(4H,m)，7.94(4H,t,J=7.1Hz)，7.669(4H,d,J=8.2Hz)，7.63(4H,d,J=6.2Hz)，7.38(4H,t,J=7.2Hz)，7.18(4H,t,J=6.2Hz)，7.07(4H,t,J=7.3Hz)，6.31(4H,d,J=8.6Hz)，4.35-4.22(8H,m)，1.41(12H,t,J=6.5Hz)。
(6) synthetic compound [Ru
2(tpyPOH)
2] (PF
6)
2.
[Ru
2(tpyPOH)
2] (PF
6)
2synthesis: in a nitrogen atmosphere, by [the Ru of 0.25g, 0.21mmol
2(tpyPOEt)
2] (PF
6)
2be dissolved in the anhydrous DMF solution of 50ml, the Me of point three droppings 9.37g, 8.08ml, 60.9mmol
3siBr solution ([Ru
2(tpyPOEt)
2] (PF
6)
2with Me
3the mol ratio of SiBr is 1:290), each dropping interval 30min, at room temperature stirs after 48 hours and adds 15mlMeOH, at room temperature stirs decompression after 12 hours and heats up in a steamer MeOH and DMF, be dissolved in (PH=10) in ammoniacal liquor, add excessive KPF after MeCN washing
6solution, regulates pH value with hydrochloric acid until produce purple precipitation, filters and obtain purple product [Ru
2(tpyPOH)
2] (PF
6)
2.
1H-NMR（500MHz，DMSO-d
6）：δ(ppm)=?10.41(4H,?s)，9.286(4H,s)，8.544H,d,J=7.3Hz)，8.55-8.52(4H,m)，8.32-8.27(4H,m)，7.98(4H,t,J=7.3Hz)，7.62(4H,d,J=8.6Hz)，7.65(4H,d,J=6.1Hz)，7.37(4H,t,J=7.1Hz)，7.23(4H,t,J=6.2Hz)，7.13(4H,t,J=7.7Hz)，6.33(4H,d,J=9.1Hz)。
Above the specific embodiment of the present invention is explained in detail, but the present invention is not limited to above-mentioned embodiment, in the ken that those of ordinary skill in the art possess, various change can also be made under the prerequisite not departing from present inventive concept.
Claims (3)
1. a symmetry binuclear ruthenium, it is characterized in that: this ruthenium complexe is using the phosphate group of two ends symmetry as fixed ligands, 3 atom N on the imidazole ring of benzimidizole derivatives and terpyridyl ring and metal Ru ion coordination form title complex, and its chemical general formula is as follows:
。
2. symmetry binuclear ruthenium as claimed in claim 1 utilizes a microwave preparation, it is characterized in that concrete steps are as follows:
(1) first 4-bromobenzaldehyde is dissolved in EtOH, adds 2-acetylpyridine, KOH and NH continuously
4oH, be heated to 80 ~ 100 DEG C of backflows and separate out through vacuum filtration after yellow solids, washing, recrystallization obtains 4-(4-bromophenyl)-2,2:6,2-terpyridyls, and wherein the mol ratio of 4-bromobenzaldehyde and 2-acetylpyridine is 1:2 ~ 3;
(2) under protective atmosphere, 4-(4-bromophenyl)-2,2:6,2-terpyridyls step (1) obtained are dissolved in dry toluene, add diethyl phosphite, triethylamine and PdCl continuously
2(dppf) CH
2cl
2, stirring heating under temperature is 90 ~ 120 DEG C of conditions, filters reaction soln, distillation, adopts column chromatography to purify and obtain 4-(2,2 ' after dry; 6 ', 2 ' '-terpyridyl-4 '-phenyl)-diethyl phosphoric acid; Wherein the mol ratio of 4-(4-bromophenyl)-2,2:6,2-terpyridyls and diethyl phosphite is 1:1 ~ 2;
(3) under protective atmosphere, by the 4-(2,2 ' that dry ruthenium trichloride hydrate and step (2) obtain; 6 ', 2 ' '-terpyridyl-4 '-phenyl)-diethyl phosphoric acid is dissolved in ethanolic soln, and filter after heated and stirred under temperature is 90 ~ 120 DEG C of conditions and obtain reddish-brown intermediate compound 1, wherein 4-(2,2 '; 6 ', 2 ' '-terpyridyl-4 '-phenyl) mol ratio of-diethyl phosphoric acid and ruthenium trichloride hydrate is 1:1 ~ 2;
(4) under protective atmosphere, the intermediate compound 1 obtain step (3) and trifluoro-methane sulfonic acid silver are dissolved in acetone, lucifuge backflow is until produce white precipitate, after diatomite filtration, through distillation, washing obtains purple intermediate compound 2, and wherein the mol ratio of intermediate compound 1 and trifluoro-methane sulfonic acid silver is 1:2 ~ 3;
(5) Pyromellitic Acid is dissolved in hot PPA, adds O-Phenylene Diamine (mol ratio of Pyromellitic Acid and O-Phenylene Diamine is 1:8 ~ 12), at 200 DEG C, stir 16h, after being cooled to room temperature, pour H into
2in O, use 10% NaHCO
3solution regulates PH to obtain middle part 3 to neutral rear filtration, drying, and be dissolved in ethylene glycol by the intermediate compound 2 that middle part 3 and step (4) obtain, 1 ~ 3min is reacted in microwave heating temperature to 140 ~ 160 DEG C then, adds excessive KPF after being cooled to room temperature
6after solution in impouring water, filter, adopt dextrane gel gel chromatography to purify after dry and obtain purple intermediate compound 4, wherein the mol ratio of Pyromellitic Acid and O-Phenylene Diamine is 1:8 ~ 12, and the mol ratio of middle part 3 and intermediate compound 2 is 1:2 ~ 3;
(6) title complex intermediate 4 is dissolved in anhydrous DMF solution, drips Me
3siBr solution, adds MeOH after stirring, continues stirring underpressure distillation after 10 ~ 15 hours, is dissolved in ammoniacal liquor, adds excessive KPF after washing
6solution, regulates pH value with acid until produce purple precipitation, filters and obtain ruthenium complexe, wherein title complex intermediate 4 and Me
3the mol ratio of SiBr is 1:250 ~ 350.
3. symmetry binuclear ruthenium according to claim 2 utilizes microwave preparation, it is characterized in that: the temperature of reaction of described step (1) is 80 ~ 100 DEG C of steps; The temperature of reaction of step (2) is 90 ~ 120 DEG C; The temperature of reaction of step (3) is 90 ~ 120 DEG C; The temperature of reaction of step (4) is 60 ~ 80 DEG C.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104558050A (en) * | 2015-02-28 | 2015-04-29 | 山东师范大学 | Bimetal Ru supramolecular macrocyclic compound and synthetic method and application thereof |
| CN115197127A (en) * | 2022-06-14 | 2022-10-18 | 广州大学 | Ruthenium-containing complex, preparation method and application thereof |
-
2014
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| HENRIETTE WOLPHER等,: "Synthesis and Electron Transfer Studies of Ruthenium-Terpyridine-Based Dyads Attached to Nanostructured TiO2", 《INORG. CHEM.》 * |
| MASA-AKI HAGA等,: "Molecular design of a proton-induced molecular switch based on rod-shaped Ru dinuclear complexes with bis-tridentate 2,6-bis(benzimidazol-2-yl)pyridine derivatives", 《DALTON TRANS.》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558050A (en) * | 2015-02-28 | 2015-04-29 | 山东师范大学 | Bimetal Ru supramolecular macrocyclic compound and synthetic method and application thereof |
| CN104558050B (en) * | 2015-02-28 | 2017-04-12 | 山东师范大学 | Bimetal Ru supramolecular macrocyclic compound and synthetic method and application thereof |
| CN115197127A (en) * | 2022-06-14 | 2022-10-18 | 广州大学 | Ruthenium-containing complex, preparation method and application thereof |
| CN115197127B (en) * | 2022-06-14 | 2023-09-29 | 广州大学 | Ruthenium-containing complex, preparation method and application thereof |
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