Intervalence Energy Effects Accompanying Double Crown Encapsulation of the Creutz-Taube Ion: An Interpretation Based on Three-Site Mixing
نویسندگان
چکیده
Recently we reported the profound effects of second-sphere crown ether binding upon the redox energetics and intervalence spectroscopy of selected mixed-valence (Crowd metal complex associatino is driven primarily by ether oxygen/ ammine hydrogen interactions, where the H-bond-donating capability of NH3 is greatly enhanced by coordination to a transition-metal cation.) For delocalized species such as the Creutz-Taube ion and its derivative^,^ asymmetric binding of a single crown (eq la) can significantly perturb the basic
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Intervalence excitation of the Creutz-Taube ion. Resonance Raman and time-dependent scattering studies of Franck-Condon effects
Franck-Condon effects associated with intervalence excitation of the Creutz-Taube ion (a prototypical delocalized mixed-valency system) have been evaluated via a time-dependent analysis of resonance Raman scattering intensities and the intervalence absorption lineshape. Quantitative studies in the extended near infrared (1320 nm excitation) revealed that at least eight, and possibly nine, vibra...
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