Please use this identifier to cite or link to this item: https://une.intersearch.com.au/unejspui/handle/1959.11/596
Title: Photoinduced electron transfer between the interlocked components of porphyrin catenanes: effect of the presence of nonequivalent reduction sites on the charge recombination rate
Contributor(s): Flamigni, L (author); Talarico, AM (author); Serroni, S (author); Puntoriero, F (author); Gunter, MJ (author); Johnston, M (author); Jeynes, T (author)
Publication Date: 2003
DOI: 10.1002/chem.200204502
Handle Link: https://hdl.handle.net/1959.11/596
Abstract: Catenanes made up of several polyether-strapped porphyrin macrocycles interlinked with the cyclic electron acceptor cyclobis(paraquat-p-phenylene) were spectroscopically, photophysically, and electrochemically characterized. The catenanes exhibit very rich redox behavior due to the presence of several different and interacting electro-active subunits. The redox patterns represent useful fingerprints that provide detailed information on the electronic interactions and the chemical environments that the electroactive subunits experience in the supramolecular arrays. A photoinduced electron transfer from the porphyrin excited state (charge separation CS) occurs with ґ=20 ps in the catenanes with a larger strap and faster than 20 ps (instrumental resolution) in the catenanes with a shorter strap. The resulting charge-separated state recombines to the ground state (charge recombination CR) with lifetimes similar in all cases, 41±4 ps. Comparison of the electron transfer rates CS and CR in the host-guest complexes of the same porphyrins with the noncyclic electron acceptor paraquat, indicate slower reactions in the [2]catenanes. This behavior is assigned to the different separation between reacting partners determined by the type of bond (weak interaction or mechanical) and to a two-step consecutive electron transfer to different sites of the macrocyclic electron acceptor in the catenanes which retards charge recombination.
Publication Type: Journal Article
Source of Publication: Chemistry: A European Journal, 9(11), p. 2649-2659
Publisher: Wiley-VCH Verlag GmbH & Co KGaA
Place of Publication: Weinheim, Germany
ISSN: 0947-6539
Field of Research (FOR): 030302 Nanochemistry and Supramolecular Chemistry
Peer Reviewed: Yes
HERDC Category Description: C1 Refereed Article in a Scholarly Journal
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