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The conformational landscape of (S)-1-(4-chlorophenyl)ethanol, its monohydrated complex, and its diastereomeric adducts with R- and S-butan-2-ol, have been investigated by resonant two-photon ionization (R2PI) spectroscopy coupled with time-of-flight mass spectrometry. Theoretical calculations at the D-B3LYP/6-31++G** level of theory have been performed to assist in the interpretation of the spectra and in the assignment of the structures. The R2PI spectra and the predicted structures have been compared with those obtained on the analogous non-halogenated and fluorinated systems, i.e., (R)-1-phenylethanol and (S)-1-(4-fluorophenyl)ethanol, respectively. It appears that the presence of chlorine atom in the para position of the aromatic ring does not influence the overall geometry of bare molecule and its complexes with respect to the non-halogenated analogous systems. Anyway, it affects the electron density in the pi system, and in turn the strength of OH···pi and CH···pi interactions. A spectral chiral discrimination is evident from the R2PI spectra of the diastereomeric adducts of (S)-1-(4-chlorophenyl)ethanol with the two enantiomers of butan-2-ol.

Resonant Two Photon Ionization (R2PI) spectroscopy has been applied to the study of host-guest interactions in molecular clusters formed by supersonic exspansion. Here, the results of R2PI spectroscopy of the fluorinated organic molecules para and ortho-fluoro-sec-butylbenzene and their complexes with water and argon are reported and discussed. In particular, it is shown that the position of the fluorine atom on the aromatic ring influences the formation of different kind of complexes (sigma versus pi) with argon and water. Ab initio calculations were performed to get insight into the molecular shape and the structure of these clusters.