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Substitution effects on the electronic structure of cyclohexane derivates and intermolecular interaction with He*(2³S) atom are discussed with the results of collision-energy-resolved Penning ionization electron spectroscopy. Interaction potentials are investigated with model potential calculations. Calculations of geometry optimization of two stable isomers (the equatorial isomer dominates) and many body Green function theory were used for assignments of photoelectron spectra.