title: Electronic transitions in conformationally controlled tetrasilanes with a wide range of SiSiSiSi dihedral angles.
abstract: Unlike π-electron chromophores, the peralkylated n-tetrasilane σ-electron chromophore resembles a chameleon in that its electronic spectrum changes dramatically as its silicon backbone is twisted almost effortlessly from the syn to the anti conformation (changing the SiSiSiSi dihedral angle ω from 0 to 180°). A combination of UV absorption, magnetic circular dichroism (MCD), and linear dichroism (LD) spectroscopy on conformationally controlled tetrasilanes 1-9, which cover fairly evenly the full range of angles ω, permitted a construction of an experimental correlation diagram for three to four lowest valence electronic states. The free chain tetrasilane n-Si4 Me10 (10), normally present as a mixture of three enantiomeric conformer pairs of widely different angles ω, has also been included in our study. The spectral trends are interpreted in terms of avoided crossings of 1B with 2B and 2A with 3A states, in agreement with SAC-CI calculations on the excited states of 1-7 and conformers of 10.
authors.affiliation: International Research Center for Elements Science (IRCELS), Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011 (Japan); Present address: Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku,Tokyo 113-0033 (Japan).
authors.forename: Hayato
authors.initials: H
authors.lastname: Tsuji
authors.forename: Heather A
authors.initials: HA
authors.lastname: Fogarty
authors.forename: Masahiro
authors.initials: M
authors.lastname: Ehara
authors.forename: Ryoichi
authors.initials: R
authors.lastname: Fukuda
authors.forename: Deborah L
authors.initials: DL
authors.lastname: Casher
authors.forename: Kohei
authors.initials: K
authors.lastname: Tamao
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Nakatsuji
authors.forename: Josef
authors.initials: J
authors.lastname: Michl
keywords: SAC-CI calculations; UV/Vis spectroscopy; conformational effects; electronic spectra; silicon