研究目的
To design and synthesize ruthenium tris-diimine photosensitizers functionalized with four methylphosphonate anchoring groups for stable grafting onto transparent conductive oxides and covalent coupling with water-splitting catalysts in dye-sensitized photoelectrochemical cells for solar fuel production.
研究成果
Novel ruthenium tris-diimine photosensitizers with four methylphosphonate anchors were successfully synthesized and characterized. The organometallic route has limitations in scope, while the traditional approach offers wider versatility. The alkyne-functionalized complex RuP4OEt-EPIP provides opportunities for immobilizing dye-catalyst assemblies. Electronic properties are not significantly altered by the anchors due to the methylene spacer, which is beneficial for DS-PEC applications. Future work should focus on improving yields and exploring applications in solar fuel production.
研究不足
Synthetic limitations include low yields for some complexes (e.g., 10-20% for cis-Ru(4,4′-(CH2PO3Et2)2-bpy)2Cl2 in traditional approach, 20% for RuP4OEt-TMS-EPIP), insolubility of [(η6-arene)Ru(dppz)Cl](PF6) preventing synthesis by organometallic route, formation of side-products with hydrolyzed phosphonate groups, and challenges in preparing triflate precursors for certain ligands (TMS-EPIP, phendione). Optimization of yields and purification methods is needed.
1：Experimental Design and Method Selection:
Two synthetic routes (traditional and organometallic) were evaluated for synthesizing heteroleptic ruthenium tris-diimine complexes. The organometallic route used half-sandwich η6-arene ruthenium complexes as intermediates, with thermal and microwave activation methods compared. The traditional approach involved preparing cis-Ru(4,4′-(CH2PO3Et2)2-bpy)2Cl2 intermediates.
2：Sample Selection and Data Sources:
Various diimine N^N ligands (bpy, phen, phenamine, dppz, phendione, TMS-EPIP, EPIP) were selected. Ligands were synthesized or purchased from Sigma Aldrich or Strem, with custom synthesis by Oribase Pharma for 4,4′-(CH2PO3Et2)2-bpy.
3：List of Experimental Equipment and Materials:
Equipment included Bruker Avance 300 MHz NMR spectrometer, Shimadzu UV-1800 or Agilent Cary 60 UV/Vis spectrometer, Thermoquest Finnigan LCQ ESI-MS spectrometer, and microwave reactor. Materials included ruthenium precursors (RuCl3·3H2O, Ru(DMSO)4Cl2), ligands, solvents (methanol, ethanol, 2-methoxyethanol, acetonitrile, dichloromethane), and reagents (KPF6, triflic acid).
4：Experimental Procedures and Operational Workflow:
For organometallic route: Synthesis of [(η6-arene)Ru(N^N)Cl](PF6) and [(η6-arene)Ru(N^N)(OTf)](OTf) precursors, followed by reaction with 4,4′-(CH2PO3Et2)2-bpy under thermal (reflux in solvent mixtures) or microwave (150°C, 20 min in ethanol) conditions. Purification by chromatography on silica gel. For traditional approach: Synthesis of cis-Ru(4,4′-(CH2PO3Et2)2-bpy)2Cl2 from Ru(DMSO)4Cl2, then reaction with N^N ligands in water/ethanol mixture, purification as above.
5：Data Analysis Methods:
UV/Vis spectroscopy for monitoring reactions and characterizing complexes, cyclic and square wave voltammetry for redox properties in acetonitrile with nBu4NBF4 electrolyte, NMR and ESI-MS for structural confirmation.
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