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Photoinduced electron transfer in multiporphyrinic interlocked structures: effect of copper(I) coordination within the central site (Articolo in rivista)
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- Photoinduced electron transfer in multiporphyrinic interlocked structures: effect of copper(I) coordination within the central site (Articolo in rivista) (literal)
- Anno
- 2004-01-01T00:00:00+01:00 (literal)
- Alternative label
L. Flamigni, A.M. Talarico, J.-C. Chambron, V. Heitz, M. Linke, N. Fujita, J.-P Sauvage (2004)
Photoinduced electron transfer in multiporphyrinic interlocked structures: effect of copper(I) coordination within the central site
in Chemistry (Weinh., Print)
(literal)
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- L. Flamigni, A.M. Talarico, J.-C. Chambron, V. Heitz, M. Linke, N. Fujita, J.-P Sauvage (literal)
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- ISI Web of Science (WOS) (literal)
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- Istituto per la Sintesi Organica e Fotoreattivita× (ISOF), CNR. Via P. Gobetti 101, 40129 Bologna (Italy)
Laboratoire de Chimie Organo-Minÿrale, UMR 7513 CNRS, Universitÿ Louis Pasteur, Institut Le Bel 4 rue Blaise Pascal, 67070 Strasbourg (France)
LIMSAG (UMR 5633 du CNRS)
Universitÿ de Bourgogne, Facultÿ des Sciences Gabriel, 6 boulevard Gabriel, 21000 Dijon (France)
Forschungszentrum Karlsruhe, Institute for Nanotechnology. Postfach 3640, 76021 Karlsruhe (Germany)
Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, 6-10-1 Hakazaki, Higashi-ku, Fukuoka 812-8581 (Japan) (literal)
- Titolo
- Photoinduced electron transfer in multiporphyrinic interlocked structures: effect of copper(I) coordination within the central site (literal)
- Abstract
- Photoinduced processes have been determined in a [2]catenane containing a zinc(II) porphyrin, a gold(m) porphyrin, and two free phenanthroline binding sites, Zn-Au+, and in the corresponding copper(I) phenanthroline complex, Zn-Cu+-Au+. In acetonitrile solution Zn-An(+) is present in two different conformations: an extended one, L, which accounts for 40 % of the total, and a compact one, S. In the L conformation, the electron transfer from the excited state of the Zn porphyrin to the gold-porphyrin unit (k = 1.3 x 10(9) s(-1)) is followed by a slow recombination (k = 8.3 x 10(7) s(-1)) to the ground state. The processes in the S conformation cannot be clearly resolved but a charge-separated (CS) state is rapidly formed and decays with a lifetime on the order of fifty picoseconds. In the catenate Zn-Cu+-Au+, the zinc-porphyrin excited state initially transfers energy to the Cu-1-phenantholine unit, producing a metal-to-ligand charge-transfer (MLCT) excited state localized on the copper complex with a rate k = 1.4 x 10(9) s(-1). From this excited state the transfer of an electron to the gold-porphyrin unit takes place, producing the CS state Zn-Cu2+-Au-., which decays with a lifetime of 10 us. The results are discussed in comparison with the closely related [2]rotaxane, in which a further charge shift from the copper center to the zinc-porphyrin unit leads to the fully CS state. Even in the absence of such full charge separation, it is shown that the lifetimes of the CS states are increased by a factor of about 2-2.5 over those of the corresponding rotaxanes. (literal)
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