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Submillisecond-lived photoinduced charge separation in inclusion complexes composed of Li+@C60 and cyclic porphyrin dimers

Title
Submillisecond-lived photoinduced charge separation in inclusion complexes composed of Li+@C60 and cyclic porphyrin dimers
Authors
Kamimura T.Ohkubo K.Kawashima Y.Nobukuni H.Naruta Y.Tani F.Fukuzumi S.
Ewha Authors
Shunichi Fukuzumi
SCOPUS Author ID
Shunichi Fukuzumiscopus
Issue Date
2013
Journal Title
Chemical Science
ISSN
2041-6520JCR Link
Citation
vol. 4, no. 4, pp. 1451 - 1461
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
Lithium ion encapsulated [60]fullerene (Li+@C60) is included within a free base and nickel complex of a cyclic porphyrin dimer (M-CPDPy, M = H4 and Ni2) to afford supramolecules (Li+@C60⊂M-CPDPy) in a polar solvent (benzonitrile) with the association constants of 2.6 × 10 5 M-1 and 3.5 × 105 M-1, respectively. From the electrochemical analysis, the energies of the charge-separated (CS) states are estimated to be 1.07 eV for Li +@C60⊂H4-CPDPy and 1.20 eV for Li+@C60⊂Ni2-CPDPy. Both values are lower than the triplet excited energies of the fullerene and porphyrin. Upon the photoexcitation at the Q-band of the porphyrin chromophore of Li +@C60⊂H4-CPDPy, electron transfer from the triplet excited state of the free base porphyrin to Li +@C60 occurs to produce the CS state. Li +@C60⊂Ni2-CPDPy also undergoes photoinduced electron transfer to produce the CS state. The lifetimes of the resulting CS states are 0.50 ms for Li+@C60⊂H 4-CPDPy and 0.67 ms for Li+@C 60⊂Ni2-CPDPy. These remarkably long CS lifetimes are the best values ever reported for non-covalent porphyrin-fullerene supramolecules in solution and are attributable to the lower CS energies than the triplet energy of each chromophore. This journal is © The Royal Society of Chemistry 2013.
DOI
10.1039/c3sc22065f
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자연과학대학 > 화학·나노과학전공 > Journal papers
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