Photoinduced electron transfer in α-cyclodextrin-based Supramolecular dyads: a free-energy-dependence study

Balan, Bijitha ; Gopidas, Karical R. (2006) Photoinduced electron transfer in α-cyclodextrin-based Supramolecular dyads: a free-energy-dependence study Chemistry - A European Journal, 12 (25). pp. 6701-6710. ISSN 0947-6539

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Official URL: http://onlinelibrary.wiley.com/doi/10.1002/chem.20...

Related URL: http://dx.doi.org/10.1002/chem.200501548

Abstract

Photoinduced electron transfer (PET) between α-cyclodextrin-appended pyrene (PYCD) and a few acceptor molecules was studied in aqueous solutions. The pyrene moiety in PYCD is located above the narrower rim of the α-CD and is fully exposed to water. The acceptors are monocyclic organic molecules and, upon dissolution in water in the presence of PYCD, a fraction of the donor-acceptor systems is present as supramolecular dyads and the remaining fraction as free molecules. Free-energy-dependence studies showed that electron transfer in the supramolecular dyads follows the Marcus equation. The donor-acceptor coupling and the reorganization energy were determined from fits of the data to the Marcus equation. The electronic coupling was found to be similar to those reported for hydrogen-bonded systems. It appears that the actual λout values are somewhat lower than values calculated with the continuum model. The experimental design has also allowed, for the first time, a visual demonstration of the inverted region on the basis of the raw fluorescence lifetime data.

Item Type:Article
Source:Copyright of this article belongs to John Wiley and Sons.
Keywords:Cyclodextrins; Donor-acceptor Systems; Electron Transfer; Fluorescence Quenching; Supramolecular Dyads
ID Code:62083
Deposited On:16 Sep 2011 04:08
Last Modified:16 Sep 2011 04:08

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