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A charge-stabilizing, multimodular, ferrocene-bis(triphenylamine)-zinc- porphyrin-fullerene polyad
- A charge-stabilizing, multimodular, ferrocene-bis(triphenylamine)-zinc- porphyrin-fullerene polyad
- Wijesinghe C.A.; El-Khouly M.E.; Zandler M.E.; Fukuzumi S.; D'Souza F.
- Ewha Authors
- Shunichi Fukuzumi
- SCOPUS Author ID
- Shunichi Fukuzumi
- Issue Date
- Journal Title
- Chemistry - A European Journal
- vol. 19, no. 29, pp. 9629 - 9638
- SCI; SCIE; SCOPUS
- 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 8.5 μs 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. Step-by-step events: Occurrence of sequential energy and electron transfer leading to the generation of a long-lived charge-separated state is demonstrated in a novel multimodular donor-acceptor supramolecular system comprised of different photo and redox entities as a photosynthetic-antenna/reaction-center mimic (see figure; EnT=energy transfer, CS=charge separation, HS=hole shift, CR=charge recombination). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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