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1036643 
Journal Article 
Photophysical properties of Ru(II) bipyridyl complexes containing hemilabile phosphine-ether ligands 
Angell, SE; Zhang, Y; Rogers, CW; Wolf, MO; Jones, WE 
2005 
Yes 
Inorganic Chemistry
ISSN: 0020-1669
EISSN: 1520-510X 
44 
21 
7377-7384 
English 
Emission and absorbance spectra, along with low-temperature excited-state lifetimes, were obtained for the hemilabile complexes, [Ru(bpy)2L](PF6)2 [L = (2-methoxyphenyl)diphenylphosphine (RuPOMe) (1) and (2-ethoxyphenyl)diphenylphosphine (RuPOEt) (2)] in solid 4:1 ethanol/methanol solution. Spectral data were evaluated with ground-state reduction potentials using Lever parameters. Lifetime data for these complexes were collected from 77 to 160 K, and the rate constant for the combined radiative and nonradiative decay process, k, the thermally activated process prefactor, k'(0), the rate constant for the MLCT --> d-d transition, k', and the activation energy, DeltaE', were calculated from a plot of ln(1/tau) versus 1/T for both (1) and (2). The low-temperature luminescence lifetimes of (1) were observed to decrease with increases in water concentration. The photophysical and kinetic data of (1) and (2) are compared to literature data for [Ru(bpy)3](PF6)2. The emission maxima of (1) and (2) are blue-shifted relative to [Ru(bpy)3](PF6)2 due to the presence of the strong-field phosphine ligand, which enhances pi back-bonding to the bipyridyl ligands. The thermal activation energy, DeltaE', is significantly larger for [Ru(bpy)3](PF6)2 than for (1) and (2) resulting in a faster MLCT --> d-d transition for (1) and (2). These results are discussed in the context of radiationless decay through thermally activated ligand-field states on the metal complex. 
IRIS
• Methanol (Non-Cancer)
     Search 2012
          WOS
 
2,2'-Dipyridyl 
Chemistry, Physical 
Ethers 
Ligands 
Oxidation-Reduction 
Phosphines 
Photochemistry 
Physicochemical Phenomena 
Ruthenium 
Spectrophotometry 
 

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