Electronic Delocalization in the Radical Cations of Porphyrin Oligomer Molecular Wires.

ABSTRACT: The radical cations of a family of π-conjugated porphyrin arrays have been investigated: linear chains of N = 1-6 porphyrins, a 6-porphyrin nanoring and a 12-porphyrin nanotube. The radical cations were generated in solution by chemical and electrochemical oxidation, and probed by vis-NIR-IR and EPR spectroscopies. The cations exhibit strong NIR bands at ∼1000 nm and 2000-5000 nm, which shift to longer wavelength with increasing oligomer length. Analysis of the NIR and IR spectra indicates that the polaron is delocalized over 2-3 porphyrin units in the linear oligomers. Some of the IR vibrational bands are strongly intensified on oxidation, and Fano-type antiresonances are observed when activated vibrations overlap with electronic transitions. The solution-phase EPR spectra of the radical

SUBMITTER: Peeks MD 

PROVIDER: S-EPMC5543395 | biostudies-literature | 2017 Aug

REPOSITORIES: biostudies-literature