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- W1994057596 abstract "[Ru(bpy)2(Mebpy-COOH)](PF6)2·3H2O (1), [Ru(phen)2(Mebpy-COOH)](ClO4)2·5H2O (2), [Ru(dppz)2(Mebpy-COOH)]Cl2·9H2O (3), and [Ru(bpy)(dppz)(Mebpy-COOH)](PF6)2·5H2O (4) (bpy = 2,2‘-bipyridine, Mebpy-COOH = 4‘-methyl-2,2‘-bipyridine-4-carboxylic acid, phen = 1,10-phenanthroline, dppz = dipyrido[3,2,-a;2‘,3-c]phenazine) have been synthesized and characterized spectroscopically and by microanalysis. The [Ru(Mebpy-COOH)(CO)2Cl2]·H2O intermediate was prepared by reaction of the monocarboxylic acid ligand, Mebpy-COOH, with [Ru(CO)2Cl2]n, and the product was then reacted with either bpy, phen, or dppz in the presence of an excess of trimethylamine-N-oxide (Me3NO), as the decarbonylation agent, to generate 1, 2, and 3, respectively. For compound 4, [Ru(bpy)(CO)Cl2]2 was reacted with Mebpy-COOH to yield [Ru(bpy)(Mebpy-COOH)(CO)Cl](PF6)·H2O as a mixture of two main geometric isomers. Chemical decarbonylation in the presence of dppz gave 4 also as a mixture of two isomers. Electrochemical and spectrophotometric studies indicated that complexes 1 and 2 were present as a mixture of protonated and deprotonated forms in acetonitrile solution because of water of solvation in the isolated solid products. The X-ray crystal structure determination on crystals of [Ru(bpy)2(MebpyCOO)][Ru(bpy)2(MebpyCOOH)]3(PF6)7, 1a, and [Ru(phen)2(MebpyCOO)](ClO4)·6H2O, 2a, obtained from solutions of 1 and 2, respectively, revealed that 1a consisted of a mixture of protonated and deprotonated forms of the complex in a 1:3 ratio and that 2a consisted of the deprotonated derivative of 2. A distorted octahedral geometry for the RuII centers was found for both complexes. Upon excitation at 450 nm, MeCN solutions of the protonated complexes 1−4 were found to exhibit emission bands in the 635-655 nm range, whereas the corresponding emission maxima of their deprotonated forms were observed at lower wavelengths. Protonation/deprotonation effects were also observed in the luminescence and electrochemical behavior of complexes 1−4. Comprehensive electrochemical studies in acetonitrile show that the ruthenium centers on 1, 2, 3, and 4 are oxidized from RuII to RuIII with reversible potentials at 917, 929, 1052, and 1005 mV vs Fc0/+ (Fc = ferrocene), respectively. Complexes 1 and 2 also exhibit an irreversible oxidation process in acetonitrile, and all compounds undergo ligand-based reduction processes." @default.
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- W1994057596 date "2007-09-20" @default.
- W1994057596 modified "2023-09-23" @default.
- W1994057596 title "Synthesis, Structure, Spectroscopic Properties, and Electrochemical Oxidation of Ruthenium(II) Complexes Incorporating Monocarboxylate Bipyridine Ligands" @default.
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- W1994057596 doi "https://doi.org/10.1021/ic700796m" @default.
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