Anion interactions with (polypyridyl)ruthenium complexes, and their importance in the cation-exchange chromatographic separation of stereoisomers of dinuclear species

Fletcher, Nicholas C., and Keene, F. Richard (1999) Anion interactions with (polypyridyl)ruthenium complexes, and their importance in the cation-exchange chromatographic separation of stereoisomers of dinuclear species. Dalton Transactions (5). pp. 683-689.

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Abstract

The separation of the ligand-bridged dinuclear complex cation [{(Me₂bpy)₂Ru}₂(µ-bpm)]⁴⁺ (Me₂bpy = 4,4'-dimethyl-2,2'-bipyridine; bpm = 2,2'-bipyrimidine) into its two diastereoisomeric forms, meso and rac, by cation-exchange chromatography has been investigated, using a wide range of organic counter anions (aromatic and aliphatic) in the aqueous eluents. ¹H NMR titration studies not only confirm association between the complex cation and the counter anions in solution, but also reveal differential associations with the two diastereoisomers of [{(Me₂bpy)₂Ru}₂(µ-bpm)]⁴⁺. Analogous interactions are also evident with mononuclear species, [Ru(pp)₃]²⁺ , where pp is a bidentate ligand such as Me₂bpy, 1,10-phenanthroline (phen) or 2,2'-bipyridine (bpy): from ¹H NMR titration studies, the first association with a number of organic anions has a stability constant in the order of 100 dm³ mol⁻¹ in aqueous solution. This association also affects the emission from the MLCT excited state of the monomers, with up to a 10% enhancement in the luminescence.

Item ID: 22771
Item Type: Article (Refereed Research - C1)
Keywords: photoinduced charge separation; bipyridyl receptor molecules; metal-complexes; electron-transfer; ruthenium(II) photosensitizers; acceptor groups; binding; modes; nucleic-acids; ligand; donor
ISSN: 1477-9234
Date Deposited: 09 Aug 2012 02:05
FoR Codes: 03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030207 Transition Metal Chemistry @ 70%
03 CHEMICAL SCIENCES > 0301 Analytical Chemistry > 030108 Separation Science @ 30%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%
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