Delocalization in platinum-alkynyl systems: a metal-bridged organic mixed-valence compound.
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.
Jones
Simon C
SC
School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332, USA.
Coropceanu
Veaceslav
V
Barlow
Stephen
S
Kinnibrugh
Tiffany
T
Timofeeva
Tatiana
T
Brédas
Jean-Luc
JL
Marder
Seth R
SR