title: Delocalization in platinum-alkynyl systems: a metal-bridged organic mixed-valence compound.
abstract: A complex featuring two triarylamine redox centers bridged by Pt, trans-bis(triethylphosphine)-bis{4-[bis(4-methoxyphenyl)amino]phenylethynyl} platinum(II), has been synthesized as a model system for pi-conjugated Pt-containing polymers. Analysis of the intervalence charge-transfer band displayed by its mixed-valence monocation affords a quantitative assessment of electronic delocalization through the Pt bridge; this is found to be only slightly smaller than that determined for a benzene-bridged analogue. These results are supported by density functional theory calculations, which show that the active orbitals involved in the electron-transfer process in both cases have similar delocalization through the bridging unit.
authors.affiliation: School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332, USA.
authors.forename: Simon C
authors.initials: SC
authors.lastname: Jones
authors.forename: Veaceslav
authors.initials: V
authors.lastname: Coropceanu
authors.forename: Stephen
authors.initials: S
authors.lastname: Barlow
authors.forename: Tiffany
authors.initials: T
authors.lastname: Kinnibrugh
authors.forename: Tatiana
authors.initials: T
authors.lastname: Timofeeva
authors.forename: Jean-Luc
authors.initials: JL
authors.lastname: Brédas
authors.forename: Seth R
authors.initials: SR
authors.lastname: Marder