Molecular triads composed of ferrocene, C60, and nitroaromatic entities: electrochemical, computational, and photochemical investigations

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Authors
Zandler, Melvin E.
Smith, Phillip M.
Fujitsuka, Mamoru
Ito, Osamu
D'Souza, Francis
Advisors
Issue Date
2002-12-27
Type
Article
Keywords
Comparative Study , Research Support, Non-U.S. Gov't , Research Support, U.S. Gov't, Non-P.H.S. , Research Support, U.S. Gov't, P.H.S.
Research Projects
Organizational Units
Journal Issue
Citation
The Journal of organic chemistry. 2002 Dec 27; 67(26): 9122-9.
Abstract

Synthesis and physicochemical characterization of a series of molecular triads composed of ferrocene, C(60), and nitroaromatic entities are reported. Electrochemical studies revealed multiple redox processes involving all three redox active ferrocene, C(60), and nitrobenzene entities. Up to eight redox couples within the accessible potential window of o-dichlorobenzene containing 0.1 M (TBA)ClO(4) are observed. A comparison between the measured redox potentials with those of the starting compounds revealed absence of any significant electronic interactions between the different redox entities. The geometric and electronic structure of the triads are elucidated by using ab initio B3LYP/3-21G methods. In the energy-optimized structures, as predicted by electrochemical studies, the first HOMO orbitals are found to be located on the ferrocene entity, while the first LUMO orbitals are mainly on the C(60) entity. The coefficients of the subsequent LUMO orbitals track the observed site of electrochemical reductions of the triads. The photochemical events of the triads are probed by both steady-state and time-resolved techniques. The steady-state emission intensities of the triads and the starting dyad, 2-(ferrocenyl)fulleropyrrolidine, are found to be completely quenched compared to fulleropyrrolidine bearing no redox active substituents. The subpicosecond and nanosecond transient absorption spectral studies revealed efficient charge separation (and rapid charge recombination) in the triads, and this has been attributed to the close spacing of the redox entities of the triad to one another.

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Full text of this article is not available in SOAR.
Publisher
John Wiley and Sons
Journal
Book Title
Series
The Journal of organic chemistry
J. Org. Chem.
PubMed ID
DOI
ISSN
0022-3263
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