σ Bonds: Electronic structure, photophysics, and photochemistry of oligosilanes

Author:

Fogarty H. A.1,Casher D. L.1,Imhof Roman1,Schepers T.1,Rooklin D. W.1,Michl J.1

Affiliation:

1. 1Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309-0215, USA

Abstract

The making and breaking of σ bonds is an integral part of almost all photochemical reactions. Yet, the electronic states of σ electrons are not nearly as well understood as the states of π-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 σ 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.

Publisher

Walter de Gruyter GmbH

Subject

General Chemical Engineering,General Chemistry

Reference2 articles.

1. Csizmadia Kluwer Dordrecht and ( Theochem ( Theochem and Albinsson and Pure and σ BONDS In preparation HONDO based on HONDO;Venturini;Organometallics Mol Cryst Liq Cryst Am Chem Soc Mol Struct Mol Struct Chem Res Phys Chem Phys Chem A Phys Chem Chem Phys Applied Chemistry Phys Chem A Phys Chem A Phys Chem A Chem Phys Lett Phys Chem A Phys Chem A,1991

2. as critical for getting the best increments for fitting ab initio data Pure and Table Conformers of Si Me : Calculated relative ground - state energies ( kcal / mol ) and calculated and observed first transition energies ( cm;FOGARTY;Applied Chemistry,2003

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