Fundamentals of Silicon Chemistry: Molecular States of Silicon‐Containing Compounds

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Abstract
Silicon and its compounds have made possible the design of new materials, which, from computers to space travel, have helped to shape the technology of our 20th century. Conversely, the demands of new technology have stimulated the fast development of silicon chemistry as part of the “renaissance” of inorganic chemistry. This article uses selected examples of predominantly organosilicon compounds to discuss in simplified terms the measurement and assignment of suitable spectroscopic “molecular fingerprints” as well as the resulting benefit for the preparative chemist. The comparison of “equivalent” states of “chemically related” molecules is emphasized, based on perturbation arguments and supporting quantum‐chemical models. Special attention is given to the relation between structure and energy, which allows us to understand and to predict the connectivity between and the spatial arrangement of silicon “building blocks”, the energy‐dependent electron distribution over the effective nuclear potentials of a molecular framework, and, especially, the partly considerable effects of “silicon substituents” on molecular properties. Future‐directed extensions and applications include polysilane band structures, Rydberg states of chromophores containing silicon centers, redox reactions and ion‐pair formation of silicon‐substituted π systems, and molecular dynamic phenomena in solution or on thermal fragmentation in the gas phase. The main objective is a set of clear and practical rules for interpreting measurements and planning experiments.