Abstract
The He(I) photoelectron spectra of the annelated thiophenes 1– 7 and the diarylsulfide 8 are reported. Based on MNDO calculations, the ionization potentials have been assigned to molecular orbitals. The electronic structure is discussed according to the molecules —in—molecules approach. The theory that the sulfur atom behaves like a carbon-carbon double bond is confirmed by the correlation of the π ionizations of 1– 4 with that of their carbocyclic counterparts. The conformational properties of 5 and 6 were investigated by MNDO calculations, indicating twisted conformations. In the photoelectron spectra no indications for conformational mixtures of 5 or 6 are present.
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