title: Electron spin dynamics in photoexcited diamagnetic and paramagnetic corroles.
abstract: Three corroles, which differ by their cavity's core, namely, diamagnetic free-base tris(pentafluorophenyl)corrole and its gallium(III) complex and the paramagnetic oxo-chromium(V) complex, were studied by steady-state and time-resolved electron paramagnetic resonance (EPR) spectroscopy. The magnetic and orientational parameters of the corroles, oriented in a nematic liquid crystal, were determined and interpreted in terms of their structure, geometry, and excited states spin dynamics. It was shown that both diamagnetic corroles, photoexcited to their triplet states, exhibit similar EPR line shapes, which is characterized by a negative zero-field splitting parameter, D, whose origin is due to molecular "stretching". Photoexcited Cr(V)O-corrole exhibits polarized ground-state EPR spectrum in emission mode. This polarization stems from the sequence of photophysical and photochemical reactions, involving the formation of the trip-quartet/trip-doublet composite states and their selective quenching via a charge transfer state.
authors.affiliation: Department of Physical Chemistry and The Farkas Center for Light-Induced Processes, The Hebrew University of Jerusalem, Jerusalem 91904, Israel.
authors.forename: Eli
authors.initials: E
authors.lastname: Stavitski
authors.forename: Alexander
authors.initials: A
authors.lastname: Berg
authors.forename: Tapan
authors.initials: T
authors.lastname: Ganguly
authors.forename: Atif
authors.initials: A
authors.lastname: Mahammed
authors.forename: Zeev
authors.initials: Z
authors.lastname: Gross
authors.forename: Haim
authors.initials: H
authors.lastname: Levanon