Microwave, infrared and Raman spectra, r0 structural parameters, ab initio calculations and vibrational assignment of 1-fluoro-1-silacyclopentanea)

The microwave spectrum (6500–18 500 MHz) of 1-fluoro-1-silacyclopentane, c-C4H8SiHF has been recorded and 87 transitions for the 28Si, 29Si, 30Si, and 13C isotopomers have been assigned for a single conformer. Infrared spectra (3050-350 cm−1) of the gas and solid and Raman spectrum (3100-40 cm−1) of the liquid have also been recorded. The vibrational data indicate the presence of a single conformer with no symmetry which is consistent with the twist form. Ab initio calculations with a variety of basis sets up to MP2(full)/aug-cc-pVTZ predict the envelope-axial and envelope-equatorial conformers to be saddle points with nearly the same energies but much lower energy than the planar conformer. By utilizing the microwaverotational constants for seven isotopomers (28Si, 29Si, 30Si, and four 13C) combined with the structural parameters predicted from the MP2(full)/6–311+G(d,p) calculations, adjusted r0 structural parameters have been obtained for the twist conformer. The heavy atom distances in Å are: r0(SiC2) = 1.875(3); r0(SiC3) = 1.872(3); r0(C2C4) = 1.549(3); r0(C3C5) = 1.547(3); r0(C4C5) = 1.542(3); r0(SiF) = 1.598(3) and the angles in degrees are: ∠CSiC = 96.7(5); ∠SiC2C4 = 103.6(5); ∠SiC3C5 = 102.9(5); ∠C2C4C5 = 108.4(5); ∠C3C5C4 = 108.1(5); ∠F6Si1C2 = 110.7(5); ∠F6Si1C3 = 111.6(5). The heavy atom ring parameters are compared to the corresponding rs parameters. Normal coordinate calculations with scaled force constants from MP2(full)/6–31G(d) calculations were carried out to predict the fundamental vibrational frequencies, infrared intensities, Raman activities, depolarization values, and infrared band contours. These experimental and theoretical results are compared to the corresponding quantities of some other five-membered rings

pπ-Molecular Orbitals of Conjugated Linear Polyene Molecules as Molecular Orbital Functional Groups in the Design of Near-infrared Dyes

While reviewing molecular orbital models for the pπ-electronic sys-tem of conjugated polyene molecules new examples on embedding of higher linear polyenes will be presented. It is shown that embedding (Hali subgraphs) and right-hand mirror-plane (McClelland subgraphs) fragments are MO functional groups of importance in molecular modeling of near IR absorbing pigments. The major new result reported in this paper is the recognition that the HOMO/LUMO gap for perylene-3,4:9,10-bis(carboximide) and poly(peri-naphthalene) related materials is determined by the embedding fragment which circumvents the need to do a full molecule calculation