Conformers of saturated chains: Matrix isolation, structure, IR and UV spectra of n-Si(4)Me(10)

Artikel i vetenskaplig tidskrift, 1996

Infrared and ultraviolet spectra of the gauche and anti conformers of matrix-isolated permethyl-n-tetrasilane have been obtained separately by taking advantage of thermally induced gauche-to-anti conversion and of wavelength-selective photochemical destruction of either conformer. The resolved UV spectrum of the gauche conformer provides the first piece of experimental evidence in favor of the recently proposed reinterpretation of conformational effects on tetrasilane electronic states. According to this, it is not the energy but the intensity of the lowest singlet excitation that changes dramatically as the SiSiSiSi dihedral angle is varied, as a result of an avoided crossing between sigma sigma* and sigma pi* states. Implications for the general understanding of sigma conjugation in simple terms are discussed. Unconstrained MP2/6-31G* optimization predicts the existence of a third backbone conformer (ortho), with a dihedral angle of about 90 degrees. Its predicted (HF/3-21G*) mid-IR spectrum is indistinguishable from that of the gauche conformer, and the matrix-isolation spectra thus provide no evidence for or against its presence.