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- W2002875235 abstract "Steady-state optical absorption and nanosecond transient absorption spectromcopy have been employed to examine ligand photolysis and recombination of (dimethylsulfoxide)2Fe(II)protoporphyrinIX ((DMSO)2Fe(II)PPIX), (DMSO)2tetrakis-4-(sulfonatophenyl)-Fe(II)porphyrin. ((DMSO)2Fe(II)4ASP) and (DMSO)2Fe(II)uroporphyrin ((DMSO)2Fe(II)URO) complexes in neat DMSO. The steady-state optical absorption data indicate that all three complexes are six-coordinate and low-spin. The corresponding nanosecond transient absorption data demonstrate that photo excitation of the (DMSO)2Fe(II)PPIX and (DMSO)2Fe(II)URO complexes results in formation of a transient species with an absorption maximum and minimum at ≈434 and ≈424 nm, respectively. These transient specientdecay exponentially with rate constants of ≈2 x 106s1. Excitation of the ((DMSO)2Fe(II)4SP, on the other hand, produces a trassient species with a broad absorption maximum centered at ≈438 nm with a minima at ≈424 nm in kinetic difference spectrum. The initially formed transient decays exponentially with rate constants of ≈1.5 x 105s1. Examination of the temperature dependence of the rate constants for ligand recombination reveals that the activation enthalpy is higer for ligand recombination to the (DMSO)Fe(II)4SP complex than either the (DMSO)Fe(II)PPIX or (DMSO)Fe(II)URO complexes (8,8.6.1 and 6.8 kcal mol1 for Fe(II)4SP, Fe(II)PPIX and Fe(II)URO, respontively). These results allow for the interpretation of the activation energy for ligand recombination in terms of electrostatic, steric and solvent interactions." @default.
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- W2002875235 date "1998-04-01" @default.
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- W2002875235 title "Ligand photolysis and recombination of (dimethylsulfoxide)2Fe(II)porphyrin complexes" @default.
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- W2002875235 doi "https://doi.org/10.1016/s0020-1693(97)05920-3" @default.
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