title: Metal Linkage Effects on Ultrafast Energy Transfer.
abstract: We report the preparation of several new porphyrin homodimers bridged by a platinum(II) ion in which very intense electronic communication through the coordination link occurs. Moreover, the synthesis of a new porphyrin dyad and its photophysical properties are reported. This dyad exhibits the fastest singlet energy transfer ever reported for synthetic systems between a zinc(II) porphyrin and a porphyrin free base. This extremely fast transfer (∼100 femtoseconds) is in the same range as the fastest one measured in natural systems. This feature is due to the platinum(II) linker, which allows for strong MO couplings between the two porphyrin units as experimentally supported by electrochemistry and corroborated by DFT computations.
authors.affiliation: Institut de Chimie, UMR CNRS 7177, Université de Strasbourg, 4 rue Blaise Pascal, 67000, Strasbourg, France.
authors.forename: Hervé
authors.initials: H
authors.lastname: Dekkiche
authors.affiliation: Département de Chimie, Université de Sherbrooke, Sherbrooke, PQ, J1K 2R1, Canada.
authors.forename: Antoine
authors.initials: A
authors.lastname: Buisson
authors.affiliation: Département de Chimie, Université de Sherbrooke, Sherbrooke, PQ, J1K 2R1, Canada.
authors.forename: Adam
authors.initials: A
authors.lastname: Langlois
authors.affiliation: Département de Chimie, Université de Sherbrooke, Sherbrooke, PQ, J1K 2R1, Canada.
authors.forename: Paul-Ludovic
authors.initials: PL
authors.lastname: Karsenti
authors.affiliation: Institut de Chimie, UMR CNRS 7177, Université de Strasbourg, 4 rue Blaise Pascal, 67000, Strasbourg, France.
authors.forename: Laurent
authors.initials: L
authors.lastname: Ruhlmann
authors.affiliation: Institut de Chimie, UMR CNRS 7177, Université de Strasbourg, 4 rue Blaise Pascal, 67000, Strasbourg, France. rruppert@unistra.fr.
authors.forename: Romain
authors.identifier: http://orcid.org/0000-0002-1513-1949
authors.initials: R
authors.lastname: Ruppert
authors.affiliation: Département de Chimie, Université de Sherbrooke, Sherbrooke, PQ, J1K 2R1, Canada. Pierre.Harvey@USherbrooke.ca.
authors.forename: Pierre
authors.initials: P
authors.lastname: Harvey
keywords: Förster and Dexter mechanisms; platinum; porphyrinoids; singlet energy transfer