Metal-to-Ligand Charge Transfer in the Gas-Phase Cluster Limit

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Abstract

The solvent dependence of metal-to-ligand charge transfer (MLCT) in the bis(2,2‘,2‘‘-terpyridyl)iron(II) complex, [Fe(terpy)2]2+, isolated in small gas-phase clusters with one or four molecules of the polar, organic solvents acetone, acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, methanol, and pyridazine is reported. The shift in the maximum of the MLCT band, Eop, for [Fe(terpy)2·(solvent)1]2+ clusters, measured using laser photofragmentation mass spectrometry, relative to the corresponding values in bulk solution ranges from +601 cm-1 for acetone to +764 cm-1 for pyridazine. The solvent dependence of the outer-sphere reorganization energy predicted by a dielectric continuum model provides a context for comparing Eop values determined for MLCT in [Fe(terpy)2·(solvent)n]2+ clusters (n = 1, 4) with those measured in solution. A model derived from Kirkwood's equation for the mutual electrostatic interaction energy of an ion and a polar medium predicts that the solvent reorganization energy associated with MLCT in [Fe(terpy)2]2+ is a linear function of (1 − Dop)/(2Dop+ 1), where Dop is the optical dielectric constant of the bulk solvent. A linear relationship between Eop and (1 − Dop)/(2Dop+ 1) is observed not only in the bulk solvents, as anticipated, but also in clusters containing as few as four solvent molecules.

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