CN107602619A - A kind of Ru-polypyridine complex sensitising agent and preparation method thereof - Google Patents
A kind of Ru-polypyridine complex sensitising agent and preparation method thereof Download PDFInfo
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- CN107602619A CN107602619A CN201710747659.7A CN201710747659A CN107602619A CN 107602619 A CN107602619 A CN 107602619A CN 201710747659 A CN201710747659 A CN 201710747659A CN 107602619 A CN107602619 A CN 107602619A
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- sensitising agent
- polypyridine complex
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Abstract
The present invention relates to a kind of Ru-polypyridine complex sensitising agent and preparation method thereof.Intermediate Ru (bpy) is made with ruthenium trichloride reaction in the 2,2` bipyridyls that are prepared as of the Ru-polypyridine complex sensitising agent of the present invention2Cl2, then with the ferrosin of 5 amino 1,10 react [Ru (bpy)2(PhenNH2)][PF6]2, then itself and succinic anhydride, N, N' dicyclohexylcarbodiimides and N HOSu NHSs reacted into obtain Ru-polypyridine complex sensitising agent, the Ru-polypyridine complex sensitising agent has efficient absorbability in 350~550nm visible region.Ru-polypyridine complex of the present invention has that preparation method is simple, equipment is simple, cost is low, is adapted to application and the numerous areas in photochemical reaction, has a extensive future.
Description
Technical field
The present invention relates to being a kind of Ru-polypyridine complex sensitising agent and preparation method thereof, belong to organic synthesis field.
Background technology
Powerful sound system effectively is developed to drive catalysis to need using solar energy, wherein electricity can be triggered by illumination
Son transfer causes the mode of the activation of catalytic center finally to convert light energy into storable chemical energy；Ruthenium is in platinum group metal
A kind of yttrium, vital effect is all played in catalysis, industrial production etc., ruthenium outermost layer has 4d75s1
Structure, its common valence state is Ru (I), Ru (II) and Ru (III), and is easily formed the complex of hexa-coordinate, has excited state reaction
Active height, long lifespan, thermodynamic stability are good, photochemical light physical message is abundant and the characteristic such as good luminous performance, at present
It is many to be widely used in nonlinear optical material, chemiluminescence, molecular recognition, the transfer of molecular light switch electronics and photocatalysis drop
The research in the field such as Xie Shui and organic matter.In addition, some bipyridyl rutheniums have excellent stability, to 400~600nm can
See that light has efficient absorbability, be widely used in the numerous areas of light-catalyzed reaction, such as photolysis water hydrogen, and
Promote electronics between the two to shift with some enzymes synergy, in order to improve photochemical conversion efficiency, design the property of synthesizing new
The more excellent ruthenium complex of energy has very important practical significance, and the synthesis technique of exploitation more practicality also becomes particularly
Urgently.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of Ru-polypyridine complex sensitising agent and preparation method thereof.Should
The preparation of Ru-polypyridine complex sensitising agent has the characteristics of method is simple, equipment is simple, cost is low.
A kind of preparation method of Ru-polypyridine complex sensitising agent, comprises the following steps：
(1)Ru(bpy)2Cl2Synthesis：By hydrate ruthenium trichloride and 2,2`- bipyridyls are dissolved in N, N`- dimethylformamides,
4h is heated to reflux, boils off most of solvent, adds a small amount of acetone, is stood, decompression filters out product, thick with appropriate distillation water washing
Product twice, is re-dissolved in ethanol/water mixed solution, continues to be heated to reflux 1 hour, and filtering, filtrate adds lithium chloride, fully stirs
Mix, after boiling off ethanol, be placed in ice bath and cool down, stand 2 hours, filtering, be dried in vacuo to obtain black product Ru (bpy)2Cl2。
(2)[Ru(bpy)2(PhenNH2)][PF6]2Synthesis：By Ru (bpy)2Cl2Exist with 5- amino -1,10- ferrosins
Stirring reaction is heated to reflux in methanol aqueous solution, methanol is boiled off after cooling down room temperature, by adding saturation into the remaining aqueous solution
Hexafluorophosphoric acid aqueous ammonium makes complex compound form orange precipitation, then to it by using toluene and acetonitrile on aluminum oxide column chromatography
Mixed liquor mutually carries out column chromatography for elution and purifies to obtain orange product [Ru (bpy)2(PhenNH2)][PF6]2。
(3) synthesis of final product：By orange solids [Ru (bpy)2(PhenNH2)](PF6)2With succinic anhydride in N, N`-
Stirring reaction in dimethylformamide, solvent is removed by rotary evaporation, obtains dark red residue.Then under agitation by N,
N'- dicyclohexylcarbodiimides and n-hydroxysuccinimide are dissolved in dimethylformamide, are cooled down in ice bath.Add
Dark red residue obtained above, stir the mixture for being filtered to remove the precipitation to be formed by syringe type filter after reacting
Obtain product.
Preferably, in the preparation method of described Ru-polypyridine complex sensitising agent, the hydration three described in step (1)
Ruthenic chloride is the hydrate ruthenium trichloride that ruthenium weight content is 37%；Described addition acetone stands and need to be placed under the conditions of 0 DEG C；Institute
The volume ratio of the mixed liquor for the second alcohol and water stated is 1:1.
Preferably, in the preparation method of described Ru-polypyridine complex sensitising agent, the Ru described in step (2)
(bpy)2Cl2It is 3h to be heated to reflux the stirring reaction time in methanol aqueous solution with 5- amino -1,10- ferrosins；In step (2)
The volume ratio of the mixing eluent of described toluene and acetonitrile is 1：2.
Preferably, it is orange solid described in step (3) in the preparation method of described Ru-polypyridine complex sensitising agent
Body [Ru (bpy)2(PhenNH2)](PF6)2It is 1h with the succinic anhydride reaction time；Red residue and N, N'- bis- hexamethylene
The reaction time of base carbodiimide and n-hydroxysuccinimide is 3h.
A kind of purposes of Ru-polypyridine complex sensitising agent, described Ru-polypyridine complex sensitising agent are visible for preparing
The application of optical drive enzyme-sensitising agent.
The present invention synthesizes Ru-polypyridine complex sensitising agent in a mild condition, and the raw material of selection is simple and easy to get, preparation side
Method is simple, has the low advantage of cost.Ru-polypyridine complex sensitising agent of the present invention can pass through 1- (3- dimethylaminos
Propyl group) -3- ethyl-carbodiimide hydrochlorides are by the amino and zymoprotein on Ru-polypyridine complex sensitising agent on amino acid
Carboxyl be covalently attached, so as to form the photocatalytic system of visible optical drive enzyme-sensitising agent.
Brief description of the drawings
Fig. 1 is the chemical structural formula of Ru-polypyridine complex sensitising agent of the present invention.
Fig. 2 is Ru-polypyridine complex sensitising agent uv absorption spectra of the present invention.
Embodiment
The present invention is further illustrated with reference to embodiment.
Embodiment 1
(1) ruthenium trichloride 1.56g and 2,2`- bipyridyl 1.87g are weighed, adds and dries, in clean flask, then add
60mlN, N`- dimethylformamide, after being heated to reflux 4h, most of solvent is boiled off, after remaining solution is cooled to room temperature, then added
Enter 50mL acetone, 0 DEG C of temperature control, stand 24h, decompression filters out product, with appropriate distillation water washing crude product twice, is re-dissolved in
250mL ethanol/waters (1:1) in mixed solution, continue to be heated to reflux 1h, filter, filtrate adds 20g lithium chlorides, is sufficiently stirred, and steams
After removing ethanol, it is placed in ice bath and cools down, stands 2h, filter to obtain black crystals, vacuum drying product.
(2) 0.97g (2mmol) Ru (bpy) will be amounted to2Cl2With 0.4g 9- amino -1,10- phenanthroline in 30ml MeOH/
H2O(1:2) backflow a few hours in.After being cooled to room temperature, MeOH is removed by rotary evaporation, by adding into the remaining aqueous solution
Enter excessive NH4PF6Make complex compound sediment, be orange solids [Ru (bpy)2(PhenNH2)](PF6)2.By in alumina column color
Toluene is used in spectrum：Acetonitrile (1:2) column chromatography purifying is carried out as eluent, collects the first band.
(3) by orange solids [Ru (bpy)2(PhenNH2)](PF6)2With succinic anhydride in N, N`- dimethylformamides
Stirring reaction 1h, solvent is removed by rotary evaporation, obtains dark red residue.Then under agitation by N, N'- dicyclohexyls
Carbodiimide and n-hydroxysuccinimide are dissolved in dimethylformamide, are cooled down in ice bath.Add obtained above
Dark red residue, stir the mixture for being filtered to remove the precipitation to be formed after reacting 3h by syringe type filter and being produced
Thing.
Claims (2)
1. a kind of Ru-polypyridine complex sensitising agent, it is characterised in that its chemical structural formula is：
2. the Ru-polypyridine complex sensitising agent described in claim 1, it is characterised in that its preparation method comprises the following steps：
(1) it will be that ruthenium weight content is that 37% hydrate ruthenium trichloride and 2,2`- bipyridyl are dissolved in N, N`- dimethylformamides, add
Heat backflow 4h, boils off most of solvent, adds a small amount of acetone, stood under the conditions of being placed on 0 DEG C, and decompression filters out product, with suitable
Amount distillation water washing crude product twice, is re-dissolved in volume ratio as 1:In 1 ethanol/water mixed solution, continue to be heated to reflux 1h, mistake
Filter, filtrate add lithium chloride, are sufficiently stirred, after boiling off ethanol, are placed in ice bath and cool down, and stand 2h, filtering, are dried in vacuo black
Color product Ru (bpy)2Cl2。
(2) by Ru (bpy)2Cl2Stirring reaction 3h is heated to reflux in methanol aqueous solution with 5- amino -1,10- ferrosins, is cooled down
Methanol is boiled off after room temperature, complex compound is formed orange sink by adding saturation hexafluorophosphoric acid aqueous ammonium into the remaining aqueous solution
Form sediment, then to it by using volume ratio on aluminum oxide column chromatography as 1：2 toluene mutually carry out post color with the mixed liquor of acetonitrile for elution
Spectrum purifies to obtain orange product [Ru (bpy)2(PhenNH2)][PF6]2。
(3) by orange solids [Ru (bpy)2(PhenNH2)](PF6)2Stirred instead in N, N`- dimethylformamides with succinic anhydride
1h is answered, solvent is removed by rotary evaporation, obtains dark red residue.Then it is under agitation that N, N'- dicyclohexyls carbon two is sub-
Amine and n-hydroxysuccinimide, which are dissolved in dimethylformamide, reacts 3h, is cooled down in ice bath.Add obtained above
Dark red residue, the precipitation to be formed is filtered to remove by syringe type filter finally produced after stirring the mixture for reaction
Thing.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535066A (en) * | 2019-01-24 | 2019-03-29 | 南京邮电大学 | Based on the molecular group and preparation method thereof for utilizing photosensitizer triplet excited states under oxygen free condition |
| CN111686821A (en) * | 2020-06-22 | 2020-09-22 | 南京邮电大学 | Ruthenium complex and molybdenum-sulfur cluster dye-sensitized photocatalytic hydrogen production system reaction liquid |
| CN111825603A (en) * | 2019-04-18 | 2020-10-27 | 中国科学院理化技术研究所 | Ruthenium polypyridine complex and preparation method and application thereof |
| CN113321687A (en) * | 2021-05-27 | 2021-08-31 | 广西医科大学 | Preparation method of ruthenium-based photosensitizer and application of ruthenium-based photosensitizer in photodynamic therapy of breast cancer |
| CN114392774A (en) * | 2022-01-28 | 2022-04-26 | 合肥工业大学 | Preparation method of polymer supported synergistic catalyst and application of polymer supported synergistic catalyst in carbon dioxide photoreduction catalysis |
| CN115612090A (en) * | 2022-10-20 | 2023-01-17 | 中国科学院长春应用化学研究所 | Pegylated ruthenium terpyridyl, preparation method and application of ruthenium terpyridyl as electrochemical luminescence reagent |
-
2017
- 2017-08-28 CN CN201710747659.7A patent/CN107602619A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| CONOR W. CREAN ET AL.: "Targeting of photooxidative damage on single-stranded DNA representing the bcr-abl chimeric gene using oligonucleotide conjugates containing [Ru(phen）3]2+ -like photosensitiser groups", 《PHOTOCHEM. PHOTOBIOL. SCI.》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535066A (en) * | 2019-01-24 | 2019-03-29 | 南京邮电大学 | Based on the molecular group and preparation method thereof for utilizing photosensitizer triplet excited states under oxygen free condition |
| CN109535066B (en) * | 2019-01-24 | 2021-10-01 | 南京邮电大学 | Molecular group based on photosensitizer triplet excited state under anaerobic condition and preparation method thereof |
| CN111825603A (en) * | 2019-04-18 | 2020-10-27 | 中国科学院理化技术研究所 | Ruthenium polypyridine complex and preparation method and application thereof |
| CN111825603B (en) * | 2019-04-18 | 2023-04-28 | 中国科学院理化技术研究所 | Ruthenium polypyridine complex and preparation method and application thereof |
| CN111686821A (en) * | 2020-06-22 | 2020-09-22 | 南京邮电大学 | Ruthenium complex and molybdenum-sulfur cluster dye-sensitized photocatalytic hydrogen production system reaction liquid |
| CN113321687A (en) * | 2021-05-27 | 2021-08-31 | 广西医科大学 | Preparation method of ruthenium-based photosensitizer and application of ruthenium-based photosensitizer in photodynamic therapy of breast cancer |
| CN114392774A (en) * | 2022-01-28 | 2022-04-26 | 合肥工业大学 | Preparation method of polymer supported synergistic catalyst and application of polymer supported synergistic catalyst in carbon dioxide photoreduction catalysis |
| CN114392774B (en) * | 2022-01-28 | 2024-01-23 | 湖南天氟新材料有限公司 | Preparation method of polymer supported synergistic catalyst and application of polymer supported synergistic catalyst in carbon dioxide photo-reduction catalysis |
| CN115612090A (en) * | 2022-10-20 | 2023-01-17 | 中国科学院长春应用化学研究所 | Pegylated ruthenium terpyridyl, preparation method and application of ruthenium terpyridyl as electrochemical luminescence reagent |
| CN115612090B (en) * | 2022-10-20 | 2023-08-04 | 中国科学院长春应用化学研究所 | Pegylated terpyridyl ruthenium, preparation method and application as electrochemiluminescence reagent |
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