A charge-stabilizing, multimodular, ferrocene-bis(triphenylamine)-zinc-porphyrin-fullerene polyad

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Authors
Wijesinghe, Channa A.
El-Khouly, Mohamed E.
Zandler, Melvin E.
Fukuzumi, Shunichi
D'Souza, Francis
Advisors
Issue Date
2013-07-15
Type
Article
Keywords
Artificial photosynthesis , Electron transfer , Ferrocene , Fullerene , Porphyrinoid , Zinc
Research Projects
Organizational Units
Journal Issue
Citation
Wijesinghe, C. A., El-Khouly, M. E., Zandler, M. E., Fukuzumi, S. and D'Souza, F. (2013), A Charge-Stabilizing, Multimodular, Ferrocene–Bis(triphenylamine)–Zinc-porphyrin–Fullerene Polyad. Chem. Eur. J., v.19:no.29:pp.9629–9638
Abstract

A novel multimodular donor-acceptor polyad featuring zinc porphyrin, fullerene, ferrocene, and triphenylamine entities was designed, synthesized, and studied as a charge-stabilizing, photosynthetic-antenna/reaction-center mimic. The ferrocene and fullerene entities, covalently linked to the porphyrin ring, were distantly separated to accomplish the charge-separation/hole-migration events leading to the creation of a long-lived charge-separated state. The geometry and electronic structures of the newly synthesized compound was deduced by B3LYP/3-21G(*) optimization, while the energy levels for different photochemical events was established using data from the optical absorption and emission, and electrochemical studies. Excitation of the triphenylamine entities revealed singlet-singlet energy transfer to the appended zinc porphyrin. As predicted from the energy levels, photoinduced electron transfer from both the singlet and triplet excited states of the zinc porphyrin to fullerene followed by subsequent hole migration involving ferrocene was witnessed from the transient absorption studies. The charge-separated state persisted for about 8.5s and was governed by the distance between the final charge-transfer product, that is, a species involving a ferrocenium cation and a fullerene radical anion, with additional influence from the charge-stabilizing triphenylamine entities located on the zinc-porphyrin macrocycle.

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Publisher
WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Journal
Book Title
Series
Chemistry - A European Journal;v.19:no.29
PubMed ID
DOI
ISSN
0947-6539
EISSN