Preparation method of dichlorotris (1, 10-phenanthroline) ruthenium (II) hydrate

Abstract

The invention belongs to the technical field of coordination compound synthesis, and provides a preparation method of a dichlorotris (1, 10-phenanthroline) ruthenium (II) hydrate. The dichloro tris (1, 10-phenanthroline) ruthenium (II) hydrate is prepared by taking ruthenium trichloride and 1, 10-phenanthroline as raw materials, ethylene glycol dimethyl ether as a solvent and monohydric alcohol with the carbon atom number of 1-3 as a reducing agent. The raw materials have the advantages of good thermal stability and strong solubility in ethylene glycol dimethyl ether, the reaction efficiency of ruthenium trichloride and 1, 10-phenanthroline can be improved, the reaction time can be shortened, and finally the yield of the dichloro tris (1, 10-phenanthroline) ruthenium (II) hydrate is improved. In addition, ruthenium (III) can be reduced to ruthenium (II) by using a monohydric alcohol having 1-3 carbon atoms as a reducing agent. And the solubility of the raw materials in monohydric alcohol is also high, so that the yield of the dichlorotris (1, 10-phenanthroline) ruthenium (II) hydrate is also favorably improved.

Description

Technical Field

[0001] The present invention relates to the technical field of coordination compound synthesis, and particularly relates to a preparation method of dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate. Background Art

[0002] Dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate has remarkable optoelectronic properties (such as high charge separation efficiency and broad spectral absorption) and chemical stability, can be used as a photosensitizer to improve the energy conversion efficiency, and can also be used as an efficient catalyst in water splitting for oxygen production and organic synthesis redox reactions, and is also used as a targeted photosensitizer for photodynamic therapy and a fluorescence imaging probe.

[0003] Although dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate has significant application achievements, there are still problems of low yield in its preparation process. Summary of the Invention

[0004] In view of this, the purpose of the present invention is to provide a preparation method of dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate. The preparation method provided by the present invention has a high yield of dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate.

[0005] In order to achieve the above invention purpose, the present invention provides the following technical solutions:

[0006] The present invention provides a preparation method of dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate, including the following steps:

[0007] Adding a monohydric alcohol solution of 1,10-phenanthroline to a 1,2-dimethoxyethane solution of ruthenium(III) chloride, and performing a redox-coordination reaction on the obtained mixed system under reflux conditions to obtain the dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate;

[0008] The monohydric alcohol has 1 to 3 carbon atoms.

[0009] Preferably, the concentration of the 1,2-dimethoxyethane solution of ruthenium(III) chloride is 0.1 to 0.2 g / mL, and the ruthenium(III) chloride is ruthenium(III) chloride hydrate.

[0010] Preferably, the preparation temperature of the 1,2-dimethoxyethane solution of ruthenium(III) chloride is 75 to 90 °C.

[0011] Preferably, the monohydric alcohol includes one or more of methanol, ethanol, and propanol.

[0012] Preferably, the concentration of the monohydric alcohol solution of 1,10-phenanthroline is 0.1 to 1 g / mL.

[0013] Preferably, the 1,10-phenanthroline monohydric alcohol solution is added at a rate of 30-50 mL / min.

[0014] Preferably, in the mixed system, the molar ratio of ruthenium(III) chloride to 1,10-phenanthroline is 1:3-6.

[0015] Preferably, the redox-coordination reaction is carried out for 3-6 h under a protective atmosphere.

[0016] Preferably, after the redox-coordination reaction, the following steps are further included: the obtained reaction liquor is concentrated, washed, and dried in sequence to obtain dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate.

[0017] Preferably, the concentration is to remove the solvent in the reaction liquor; the washing reagent is ice-cold diethyl ether, and the temperature of the ice-cold diethyl ether is 0-2 °C; the drying temperature is 40-60 °C, and the time is 4-6 h.

[0018] The present invention provides a method for preparing dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate.

[0019] The preparation method provided by the present invention uses ruthenium(III) chloride and 1,10-phenanthroline as raw materials, ethylene glycol dimethyl ether as a solvent, and a monohydric alcohol with 1-3 carbon atoms as a reducing agent, and dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate is prepared in high yield by a one-pot method. The raw materials (ruthenium(III) chloride and 1,10-phenanthroline) of the present invention have the advantages of good thermal stability and strong solubility in ethylene glycol dimethyl ether, which can improve the reaction efficiency of ruthenium(III) chloride and 1,10-phenanthroline, shorten the reaction time, and finally improve the yield of dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate; at the same time, ethylene glycol dimethyl ether is safe, environmentally friendly, and reduces environmental pollution; and ethylene glycol dimethyl ether is cheap, reducing the preparation cost. In addition, using a monohydric alcohol with 1-3 carbon atoms as a reducing agent can reduce ruthenium(III) to ruthenium(II); at the same time, the solubility of the raw materials in the monohydric alcohol is also high, increasing the contact probability of the raw materials, thereby improving the reaction efficiency, and finally also being beneficial to improving the yield of dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate; adding the 1,10-phenanthroline monohydric alcohol solution to the ruthenium(III) chloride ethylene glycol dimethyl ether solution for a redox-coordination reaction, the reaction conditions are mild. In summary, the preparation method of the present invention uses a one-pot method for the redox-coordination reaction, has few steps, is easy to operate, and has a high yield of dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate; has low requirements for equipment, the raw material amount can reach the kilogram level, and can realize batch industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 11H NMR spectrum of dichlorotris(1,10 - phenanthroline)ruthenium(II) hydrate prepared in Example 1;

[0021] Figure 2 13C NMR spectrum of dichlorotris(1,10 - phenanthroline)ruthenium(II) hydrate prepared in Example 1;

[0022] Figure 3 Mass spectrum of dichlorotris(1,10 - phenanthroline)ruthenium(II) hydrate prepared in Example 1. Detailed implementation manners

[0023] The present invention provides a preparation method of dichlorotris(1,10 - phenanthroline)ruthenium(II) hydrate, comprising the following steps:

[0024] Adding a monohydric alcohol solution of 1,10 - phenanthroline to a 1,2 - dimethoxyethane solution of ruthenium(III) chloride, and performing a redox - coordination reaction on the obtained mixed system under reflux conditions to obtain the dichlorotris(1,10 - phenanthroline)ruthenium(II) hydrate;

[0025] The monohydric alcohol has 1 - 3 carbon atoms.

[0026] Unless otherwise specified, the raw materials used in the present invention are preferably commercially available products.

[0027] In the present invention, the monohydric alcohol preferably includes one or more of methanol, ethanol, and propanol, and is further preferably ethanol. In the present invention, while the monohydric alcohol with 1 - 3 carbon atoms serves as a solvent for dissolving 1,10 - phenanthroline, it also serves as a reducing agent, capable of reducing ruthenium(III) to ruthenium(II). The raw materials of the present invention have high solubility in the monohydric alcohol, which is beneficial to increasing the contact and reaction probability of the raw materials, improving the reaction efficiency, and thus increasing the yield of dichlorotris(1,10 - phenanthroline)ruthenium(II) hydrate; in addition, the monohydric alcohol as a reducing agent is also beneficial to shortening the time of the redox - coordination reaction, greatly reducing the production cost, and enabling green and environmentally friendly production.

[0028] In the present invention, the concentration of the monohydric alcohol solution of 1,10 - phenanthroline is preferably 0.1 - 1 g / mL, specifically preferably 0.1 g / mL, 0.11 g / mL, 0.125 g / mL, 0.14 g / mL, 0.17 g / mL, 0.2 g / mL, 0.25 g / mL, 0.3 g / mL, 0.33 g / mL, 0.4 g / mL, 0.5 g / mL, 0.6 g / mL, 0.7 g / mL, 0.8 g / mL, 0.9 g / mL, or 1 g / mL.

[0029] In the present invention, the preparation method of the monohydric alcohol solution of 1,10-phenanthroline is preferably: dissolving 1,10-phenanthroline in monohydric alcohol to obtain the monohydric alcohol solution of 1,10-phenanthroline. In the present invention, the dosage ratio of 1,10-phenanthroline to monohydric alcohol is preferably 1 g: 1-10 mL, specifically preferably 1 g: 1 mL, 1 g: 2 mL, 1 g: 3 mL, 1 g: 4 mL, 1 g: 5 mL, 1 g: 6 mL, 1 g: 7 mL, 1 g: 8 mL, 1 g: 9 mL or 1 g: 10 mL.

[0030] In the present invention, the addition rate of the monohydric alcohol solution of 1,10-phenanthroline is preferably 30-50 mL / min, specifically preferably 30 mL / min, 35 mL / min, 40 mL / min, 45 mL / min or 50 mL / min.

[0031] In the present invention, the concentration of the ethylene glycol dimethyl ether solution of ruthenium(III) chloride is preferably 0.1-0.2 g / mL, specifically preferably 0.1 g / mL, 0.11 g / mL, 0.12 g / mL, 0.125 g / mL, 0.13 g / mL, 0.14 g / mL, 0.15 g / mL, 0.16 g / mL, 0.167 g / mL, 0.17 g / mL, 0.18 g / mL, 0.19 g / mL or 0.2 g / mL.

[0032] In the present invention, the ruthenium(III) chloride is preferably hydrated ruthenium(III) chloride, more preferably ruthenium(III) chloride monohydrate or ruthenium(III) chloride trihydrate, and still more preferably ruthenium(III) chloride trihydrate. In the present invention, the mass percentage content of ruthenium in the ruthenium(III) chloride trihydrate is preferably 35-40%, more preferably 37.24-37.75%, and specifically preferably 37.24%, 37.45% or 37.75%. In the present invention, hydrated ruthenium(III) chloride has good solubility, which is conducive to the progress of the redox-coordination reaction.

[0033] In the present invention, the preparation temperature of the ethylene glycol dimethyl ether solution of ruthenium(III) chloride is preferably 75-90 °C, specifically preferably 75 °C, 80 °C, 85 °C or 90 °C.

[0034] In the present invention, the preparation method of the ruthenium(III) chloride ethylene glycol dimethyl ether solution preferably comprises the following steps: dissolving ruthenium(III) chloride in ethylene glycol dimethyl ether to obtain the ruthenium(III) chloride ethylene glycol dimethyl ether solution. In the present invention, the dosage ratio of the hydrated ruthenium(III) chloride to ethylene glycol dimethyl ether is preferably 1 g:5-10 mL, specifically preferably 1 g:5 mL, 1 g:6 mL, 1 g:7 mL, 1 g:8 mL, 1 g:9 mL or 1 g:10 mL. In the present invention, the temperature of the dissolution is preferably the same as the preparation temperature of the ruthenium(III) chloride ethylene glycol dimethyl ether solution, which will not be elaborated herein. In the present invention, the dissolution is preferably carried out under reflux and stirring conditions.

[0035] In the present invention, in the said mixed system, the molar ratio of ruthenium(III) chloride to 1,10-phenanthroline is preferably 1:3-6, specifically preferably 1:3, 1:3.9, 1:4, 1:4.6, 1:4.8, 1:5, 1:5.9 or 1:6.

[0036] In the present invention, the time of the redox-coordination reaction is preferably 3-6 h, specifically preferably 3 h, 4 h, 5 h or 6 h. In the present invention, the temperature of the reflux is preferably the same as the temperature of the dissolution of ruthenium(III) chloride, which will not be elaborated herein; the temperature of the reflux is the temperature of the redox-coordination reaction. In the present invention, the redox-coordination reaction is preferably carried out under a protective atmosphere, and the protective atmosphere is preferably nitrogen or argon.

[0037] After the redox-coordination reaction, the present invention preferably further comprises: successively concentrating, washing and drying the obtained reaction stock solution to obtain the dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate.

[0038] In the present invention, the concentration is preferably to remove the solvent in the reaction stock solution, specifically preferably to remove 90% of the solvent in the reaction stock solution. In the present invention, the concentration method is preferably rotary evaporation.

[0039] In the present invention, the washing reagent is preferably ice-cold diethyl ether, and the temperature of the ice-cold diethyl ether is preferably 0-2 °C, specifically preferably 0 °C, 1 °C or 2 °C. In the present invention, the number of washing times is preferably 1-2 times, specifically preferably 1 time or 2 times. In the present invention, the target product dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate is insoluble in ice-cold diethyl ether, but can wash away the unreacted 1,10-phenanthroline, and can improve the purity of the target product.

[0040] In the present invention, the drying temperature is preferably 40-60 °C, specifically preferably 40 °C, 45 °C, 50 °C, 55 °C or 60 °C; the time is preferably 4-6 h, specifically preferably 4 h, 4.5 h, 5 h, 5.5 h or 6 h.

[0041] In the present invention, during the redox - coordination reaction, ruthenium(III) in ruthenium(III) chloride is reduced to ruthenium(II). At the same time, the reduced ruthenium(II) chloride coordinates with 1,10 - phenanthroline to form dichlorotris(1,10 - phenanthroline)ruthenium(II) hydrate.

[0042] The following examples are used to illustrate in detail the preparation method of dichlorotris(1,10 - phenanthroline)ruthenium(II) hydrate provided by the present invention, but they should not be construed as limiting the scope of protection of the present invention.

[0043] The ruthenium(III) chloride trihydrate, 1,10 - phenanthroline, ethylene glycol dimethyl ether, and ethanol used in the following examples are all commercially available analytical pure products.

[0044] Example 1

[0045] (1) Add 500 g of ruthenium(III) chloride trihydrate (ruthenium mass content is 37.24%) and 2500 mL of ethylene glycol dimethyl ether to a reaction vessel, stir and heat to 75 °C to obtain a ruthenium(III) chloride solution.

[0046] (2) Dissolve 1328 g of 1,10 - phenanthroline in 1328 mL of ethanol to obtain a 1,10 - phenanthroline solution.

[0047] (3) Under an argon atmosphere for the entire reaction system, add the 1,10 - phenanthroline solution prepared in (2) to the ruthenium(III) chloride solution prepared in (1) at a rate of 30 mL / min. After the addition of the 1,10 - phenanthroline solution is complete, the resulting mixed system is maintained under reflux for 3 h for the redox - coordination reaction. After the reaction is completed, approximately 90% of the solvent in the resulting reaction liquor is removed by rotary evaporation, filtered, and the obtained solid product is washed once with 0 °C ether and then dried at 40 °C for 4 h to obtain 1398.5 g of a red solid, which is dichlorotris(1,10 - phenanthroline)ruthenium(II) hydrate with a purity of 99.1%; upon determination, the mass percentage of ruthenium in the obtained dichlorotris(1,10 - phenanthroline)ruthenium(II) hydrate is 13.19%. Based on ruthenium, the yield is (1398.5 g * 13.19%) / (500 g * 37.24%) × 100% = 99.1%.

[0048] Example 2

[0049] (1) Add 500 g of ruthenium(III) chloride trihydrate (ruthenium mass content is 37.45%) and 3500 mL of ethylene glycol dimethyl ether to a reaction vessel, stir and heat to 80 °C to obtain a ruthenium(III) chloride solution.

[0050] (2) Dissolve 1660 g of 1,10 - phenanthroline in 4980 mL of ethanol to obtain a 1,10 - phenanthroline solution.

[0051] (3) Under an argon atmosphere, add all of the 1,10-phenanthroline solution prepared in (2) to the ruthenium(III) chloride solution prepared in (1) at a rate of 40 mL / min. After the addition of the 1,10-phenanthroline solution is complete, carry out a redox-coordination reaction for 5 h while maintaining the reflux state of the resulting mixed system. After the reaction is complete, rotary evaporate to remove approximately 90% of the solvent from the resulting reaction stock solution, filter, wash the resulting solid product twice with diethyl ether at 1 °C, and then dry at 50 °C for 5 h to obtain 1399.6 g of a red solid, which is dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate with a purity of 99.2%. It is determined that the mass percentage content of ruthenium in the obtained dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate is 13.19%. Calculated based on ruthenium, the yield is (1399.6 g * 13.19%) / (500 g * 37.45%) × 100% = 98.6%.

[0052] Example 3

[0053] (1) Add 500 g of ruthenium(III) chloride trihydrate (ruthenium mass content is 37.75%) and 2500 mL of ethylene glycol dimethyl ether to a reaction vessel, stir and heat to 85 °C to obtain a ruthenium(III) chloride solution.

[0054] (2) Dissolve 2019 g of 1,10-phenanthroline in 12115 mL of ethanol to obtain a 1,10-phenanthroline solution.

[0055] (3) Under an argon atmosphere, add all of the 1,10-phenanthroline solution prepared in (2) to the ruthenium(III) chloride solution prepared in (1) at a rate of 50 mL / min. After the addition of the 1,10-phenanthroline solution is complete, carry out a redox-coordination reaction for 6 h while maintaining the reflux state of the resulting mixed system. After the reaction is complete, rotary evaporate to remove approximately 90% of the solvent from the resulting reaction stock solution, filter, wash the resulting solid product twice with diethyl ether at 2 °C, and then dry at 60 °C for 4 h to obtain 1405.6 g of a red solid, which is dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate with a purity of 99.1%. It is determined that the mass percentage content of ruthenium in the obtained dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate is 13.20%. Calculated based on ruthenium, the yield is (1405.6 g * 13.20%) / (500 g * 37.75%) × 100% = 98.3%.

[0056] Example 4

[0057] (1) Add 1000 g of ruthenium(III) chloride trihydrate (ruthenium mass content is 37.24%) and 5000 mL of ethylene glycol dimethyl ether to a reaction vessel, stir and heat to 90 °C to obtain a ruthenium(III) chloride solution.

[0058] (2) Dissolve 2656 g of 1,10 - phenanthroline in 2656 mL of ethanol to obtain a 1,10 - phenanthroline solution.

[0059] (3) Under an argon atmosphere for the entire reaction system, add all of the 1,10 - phenanthroline solution prepared in (2) to the ruthenium(III) chloride solution prepared in (1) at a rate of 50 mL / min. After the addition of the 1,10 - phenanthroline solution is complete, carry out a redox - coordination reaction for 6 h while maintaining the reflux state of the resulting mixed system. After the reaction is completed, rotary evaporate to remove approximately 90% of the solvent in the resulting reaction material solution, filter, wash the resulting solid product twice with diethyl ether at 2 °C, and then dry at 60 °C for 6 h to obtain 2782.6 g of a red solid, which is dichlorotris(1,10 - phenanthroline)ruthenium(II) hydrate with a purity of 99.1%; upon determination, the mass percentage content of ruthenium in the obtained dichlorotris(1,10 - phenanthroline)ruthenium(II) hydrate is 13.20%. Based on ruthenium, the yield is (2782.6 g * 13.20%) / (1000 g * 37.24%) × 100% = 98.6%.

[0060] Example 5

[0061] The difference from Example 1 is that in step (2), ethanol is replaced with methanol, and other operations are the same as in Example 1.

[0062] The result is: 1390.9 g of a red solid is obtained, which is dichlorotris(1,10 - phenanthroline)ruthenium(II) hydrate with a purity of 99.2%; upon determination, the mass percentage content of ruthenium in the obtained dichlorotris(1,10 - phenanthroline)ruthenium(II) hydrate is 13.20%. Based on ruthenium, the yield is (1390.9 g * 13.20%) / (500 g * 37.24%) × 100% = 98.6%.

[0063] Example 6

[0064] The difference from Example 1 is that in step (2), ethanol is replaced with propanol, and other operations are the same as in Example 1.

[0065] The result is: 1395.1 g of a red solid is obtained, which is dichlorotris(1,10 - phenanthroline)ruthenium(II) hydrate with a purity of 99.1%; upon determination, the mass percentage content of ruthenium in the obtained dichlorotris(1,10 - phenanthroline)ruthenium(II) hydrate is 13.20%. Based on ruthenium, the yield is (1395.1 * 13.20%) / (500 g * 37.24%) × 100% = 98.9%.

[0066] Comparative Example 1

[0067] Dissolve 1328 g of 1,10-phenanthroline in 2500 mL of N,N-dimethylformamide, and then add 500 g (1.91 mol) of ruthenium(III) chloride (ruthenium mass content is 37.24%); after the addition of ruthenium(III) chloride is complete, stir and react under a nitrogen atmosphere, control the temperature at 85 °C, and the time is 5 h; after the reaction is completed, cool the reaction solution to room temperature, add 200 g of sodium hydroxide and 150 g of ammonium hydroxide, filter to obtain 962.0 g of a red solid, namely dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate. After determination, the mass percentage of ruthenium in the obtained dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate is 13.20%. Calculated based on ruthenium, the yield is (962.0 * 13.20%) / (500 g * 37.24%) × 100% = 68.2%.

[0068] Comparative Example 2

[0069] The difference from Example 1 is that in step (1), ethylene glycol dimethyl ether is replaced by ethanol, and other operations are the same as in Example 1.

[0070] The result is: 1103.9 g of a red solid is obtained, which is dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate, and the purity is 96.5%; after determination, the mass percentage of ruthenium in the obtained dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate is 13.19%. Calculated based on ruthenium, the yield is (1103.9 * 13.19%) / (500 g * 37.24%) × 100% = 78.2%.

[0071] Test Example

[0072] Characterize the dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate obtained in Example 1. The obtained hydrogen spectrum is as Figure 1 shown, the carbon spectrum is as Figure 2 shown, and the mass spectrum is as Figure 3 shown.

[0073] It can be seen from Figure 1 that the hydrogen spectrum ( 1 HNMR, 500 MHz, DMSO), chemical shift (ppm): 8.80 - 8.78 (d, 6H), 8.40 (d, 6H), 8.08 (dd, 6H), 7.78 - 7.76 (d, 6H).

[0074] It can be seen from Figure 2 that the carbon spectrum ( 13 C NMR, 500 MHz, DMSO), chemical shift (ppm): 152.78, 147.25, 136.89, 130.48, 128.09, 126.36.

[0075] It can be seen fromFigure 3 It can be seen that for the mass spectrum (ESI(+)): [C 36 H 24 ClN6Ru] + the molecular weight is 677, and in the figure, m / z = 677 is the strongest proton peak, which is consistent with the actual [M-Cl] + molecular weight.

[0076] The detection results of the hydrogen spectrum, carbon spectrum and mass spectrum indicate that the product obtained in Example 1 is consistent with the target compound of dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate.

[0077] From the above examples, it can be known that the preparation method provided by the present invention is a simple, high-yield, low-cost and efficient synthesis method of dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate, which is suitable for batch industrial production.

[0078] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A method for preparing dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate, characterized in that, The steps include: Adding a monohydric alcohol solution of 1,10-phenanthroline to a 1,2-dimethoxyethane solution of ruthenium(III) chloride, and subjecting the obtained mixed system to a redox-coordination reaction under reflux conditions to obtain the dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate; The monohydric alcohol has 1 to 3 carbon atoms.

2. The preparation method according to claim 1, characterized in that, The concentration of the 1,2-dimethoxyethane solution of ruthenium(III) chloride is 0.1 to 0.2 g / mL, and the ruthenium(III) chloride is ruthenium(III) chloride hydrate.

3. The preparation method according to claim 1 or 2, characterized in that, The preparation temperature of the 1,2-dimethoxyethane solution of ruthenium(III) chloride is 75 to 90 °C.

4. The preparation method according to claim 1, characterized in that, The monohydric alcohol includes one or more of methanol, ethanol, and propanol.

5. The preparation method according to claim 1 or 4, characterized in that, The concentration of the monohydric alcohol solution of 1,10-phenanthroline is 0.1 to 1 g / mL.

6. The preparation method according to claim 5, wherein The adding rate of the monohydric alcohol solution of 1,10-phenanthroline is 30 to 50 mL / min.

7. The preparation method according to claim 1, characterized in that, In the mixed system, the molar ratio of ruthenium(III) chloride to 1,10-phenanthroline is 1:3 to 6.

8. The preparation method according to claim 1 or 7, characterized in that, The time of the redox-coordination reaction is 3 to 6 h, and the redox-coordination reaction is carried out under a protective atmosphere.

9. The preparation method according to claim 1, characterized in that, After the redox-coordination reaction, it further includes: sequentially concentrating, washing, and drying the obtained reaction liquor to obtain the dichlorotris(1,10-phenanthroline)ruthenium(II) hydrate.

10. The preparation method according to claim 9, characterized in that, The concentration is to remove the solvent in the reaction liquor; the washing reagent is ice-cold diethyl ether, and the temperature of the ice-cold diethyl ether is 0 to 2 °C; the drying temperature is 40 to 60 °C, and the time is 4 to 6 h.

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