s Bonds: Electronic structure, photophysics,
and photochemistry of oligosilanes
H. A. Fogarty, D. L. Casher, R. Imhof, T. Schepers, D. W. Rooklin,
and J. Michl**
Department of Chemistry and Biochemistry, University
of Colorado, Boulder, CO 80309-0215, USA
Abstract: The making and breaking of s
bonds is an integral part of almost all photochemical reactions. Yet,
the electronic states of s electrons are
not nearly as well understood as the states of p-electron
systems. Efforts in our laboratory to enhance the current state of their
understanding are described, using the specific example of oligosilanes.
We address the intrinsically cyclic nature of s
delocalization and its dependence on chain length and conformation,
both in terms of theory and spectroscopic experiments, from the simplest
disilane chromophore to the spectral properties of the individual conformers
of permethylated heptasilane. We also describe a new low-energy luminescence
from certain conformers of permethylated oligosilanes.
* Lectures presented at the XIXth IUPAC Symposium on Photochemistry,
Budapest, Hungary, 14�19 July 2002. Other presentations are published
in this issue, pp.999�1090.
** Corresponding Author
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