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Long-lived long-distance photochemically induced spin-polarized charge separation in β,β′-pyrrolic fused ferrocene-porphyrin-fullerene systems

Title
Long-lived long-distance photochemically induced spin-polarized charge separation in β,β′-pyrrolic fused ferrocene-porphyrin-fullerene systems
Authors
Lee S.-H.Larsen A.G.Ohkubo K.Cai Z.-L.Reimers J.R.Fukuzumi S.Crossley M.J.
Ewha Authors
Shunichi Fukuzumi
SCOPUS Author ID
Shunichi Fukuzumiscopus
Issue Date
2012
Journal Title
Chemical Science
ISSN
2041-6520JCR Link
Citation
vol. 3, no. 1, pp. 257 - 269
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
The exceptionally long lived charge separation previously observed in a β,β′-pyrrolic-fused ferrocene-porphyrin-fullerene triad (lifetime 630 μs) and related porphyrin-fullerene dyad (lifetime 260 μs) is attributed to the production of triplet charge-separated states. Such molecular excited-state spin polarization maintained over distances of up to 23 Å is unprecedented and offers many technological applications. Electronic absorption and emission spectra, femtosecond and nanosecond time-resolved transient absorption spectra, and cyclic voltammograms of two triads and four dyads are measured and analyzed to yield rate constants, donor-acceptor couplings, free-energy changes, and reorganization energies for charge-separation and charge-recombination processes. Production of long-lived intramolecular triplet states is confirmed by electron-paramagnetic resonance spectra at 77-223 K, as is retention of spin polarization in π-conjugated ferrocenium ions. The observed rate constants were either first predicted (singlet manifold) or later confirmed (triplet manifold) by a priori semiclassical kinetics calculations for all conceivable photochemical processes, parameterized using density-functional theory and complete-active-space self-consistent-field calculations. Identified are both a ps-timescale process attributed to singlet recombination and a μs-timescale process attributed to triplet recombination. © 2012 The Royal Society of Chemistry.
DOI
10.1039/c1sc00614b
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자연과학대학 > 화학·나노과학전공 > Journal papers
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