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Photophysical effect of the coordination of water by ruthenium(II) bipyridyl complexes containing hemilabile phosphine-ether ligands

TitlePhotophysical effect of the coordination of water by ruthenium(II) bipyridyl complexes containing hemilabile phosphine-ether ligands
Publication TypeJournal Article
Year of Publication2002
AuthorsRogers, CW, Zhang, Y, Patrick, BO, Jones, WE, Wolf, MO
JournalINORGANIC CHEMISTRY
Volume41
Pagination1162-1169
Date PublishedMAR 11
ISSN0020-1669
Abstract

A substantial concentration-dependent red shift of the absorption and emission spectra (77 K) of {[}Ru(bpy)(2)(POMe-P,O)](2+) (1) (POMe = (2-methoxyphenyl)diphenylphosphine) is reported. NMR experiments show this shift to be due to equilibration of 1 with an aquo complex (1b) (K(eff) = (6 +/- 3) x 10(-3)) that forms upon displacement of the coordinated ether in the hemilabile POMe ligand. The excited-state lifetimes of 1 and 1b at 77 K in solid 2:1 ethanol/acetone solution are tau = 2.13 +/- 0.02 and 1.95 +/- 0.02 mus, respectively. The preparation and X-ray crystal structure of a related complex, {[}Ru(bPY)(2)(PO(i)Pr-P)(OH(2))](PF(6))(2) (2b) (PO(i)Pr-P = (2-(2-propoxy)phenyl)diphenylphosphine), is also reported. In solution, this species exists as an equilibrium mixture of complexes that cannot be readily separated. This species also has concentration-dependent absorption spectra in 2:1 ethanol/acetone solution, with a significant red shift (20 nm) at lower concentrations.

DOI10.1021/ic010827+