Molecular structures of tetrabromothiophene and -selenophene as determined by gas-phase electron diffraction and high-level quantum chemical calculations

The molecular structures of tetrabromothiophene and tetrabromoselenophene were studied by gas-phase electron diffraction and quantum chemical calculations. Calculations at the DFT/B3LYP and MP2 levels of theory confirm that the molecules possess a planar structure in the gas phase. MD simulations were performed for both molecules. Definitive gas-phase molecular structures of tetrabromothiophene and tetrabromoselenophene are reported, based on refinements of electron diffraction data starting from different input geometries. The single-crystal structure of tetrabromoselenophene is also reported. Geometries of all tetrabromochalcogenophenes, C4Br4X (X = O, S, Se, Te), were calculated and trends in the geometrical parameters along the series are discussed.

Highlight► A combined GED/MS experiment was applied for molecular structures study of, C4Br4S and C4Br4Se, Planar structures of C2v equilibrium symmetry were found for these molecules. Calculations of DFT/B3LYP, MP2 and CCSD levels of theory and molecular dynamics simulations were performed.