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A Combined Computational and Spectroelectrochemical Study of Platinum-Bridged Bis-Triarylamine Systems

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posted on 03.02.2014, 00:00 by Matthias Parthey, Kevin B. Vincent, Manuel Renz, Phil A. Schauer, Dmitry S. Yufit, Judith A. K. Howard, Martin Kaupp, Paul J. Low
The character of the electronic transitions in the ultraviolet–visible–near infrared (UV–vis–NIR) spectra of platinum-bis­(alkynyl) bridged, bis-triarylamine mixed-valence systems trans-[Pt­(CCC6H4NAr2)2 (PR3)2]n+ (R = ethyl, Ar = C6H4CH3-4 (1) or C6H4OCH3-4 (2); R = Ph, Ar = C6H4CH3-4 (3) or C6H4OCH3-4 (4), n = 0, 1, 2) has been determined from a combination of spectroscopic measurement and density functional theory calculations. The hybrid functional BLYP35 in combination with a suitable solvent model (i.e., conductor-like screening model (COSMO)) has been used to model the UV–vis–NIR and IR spectroscopic properties of [14]+, to confirm the description of [14]+ as examples of metal-bridged organic mixed-valence compounds, and to assign the principal features of the electronic spectra, including the triarylamine-based intervalence charge transfer transition located in the NIR region. The successful modeling of the charge distribution within the system demonstrates the utility of the BLYP35-COSMO protocol as a tool for use in the study of intramolecular charge transfer properties in mixed-valence complexes.