A combined computational and spectroelectrochemical study of platinum-bridged bis-triarylamine systems

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(Cî CC6H 4NAr2)2 (PR3)2] n+ (R = ethyl, Ar = C6H4CH3-4 (1) or C6H4OCH3-4 (2); R = Ph, Ar = C 6H4CH3-4 (3) or C6H 4OCH3-4 (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 [1-4]+, to confirm the description of [1-4]+ 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. © 2014 American Chemical Society.