title: Chlorine Para-Substitution of 1-Phenylethanol: Resonant Photoionization Spectroscopy and Quantum Chemical Calculations of Hydrated and Diastereomeric Complexes.
abstract: 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 π system, and in turn the strength of OH···π and CH···π 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.
authors.affiliation: Dip.to di Chimica e Tecnologie del Farmaco, Università degli Studi di Roma La Sapienza , p.le Aldo Moro 5, 00185, Rome, Italy.
authors.forename: Flaminia
authors.initials: F
authors.lastname: Rondino
authors.affiliation: CNR-ISMN, c/o Dip.to di Chimica, Università degli Studi di Roma La Sapienza , p.le Aldo Moro 5, 00185, Rome, Italy.
authors.forename: Mauro
authors.initials: M
authors.lastname: Satta
authors.affiliation: Dip.to di Scienze e Tecnologie Chimiche, Università di Roma "Tor Vergata" , via della Ricerca Scientifica, 00133 Rome, Italy.
authors.forename: Susanna
authors.initials: S
authors.lastname: Piccirillo
authors.affiliation: Dip.to di Chimica e Tecnologie del Farmaco, Università degli Studi di Roma La Sapienza , p.le Aldo Moro 5, 00185, Rome, Italy.|Dip.to di Scienze e Tecnologie Chimiche, Università di Roma "Tor Vergata" , via della Ricerca Scientifica, 00133 Rome, Italy.
authors.forename: Alessandra
authors.initials: A
authors.lastname: Ciavardini
authors.affiliation: CNR-ISM , Area della Ricerca di Roma 1, via Salaria km 29.300, 00015 Monterotondo (RM), Italy.
authors.forename: Anna
authors.initials: A
authors.lastname: Giardini
authors.affiliation: Dip.to di Chimica e Tecnologie del Farmaco, Università degli Studi di Roma La Sapienza , p.le Aldo Moro 5, 00185, Rome, Italy.
authors.forename: Maurizio
authors.initials: M
authors.lastname: Speranza
authors.affiliation: CNR-ISM , Area della Ricerca di Roma 1, via Salaria km 29.300, 00015 Monterotondo (RM), Italy.
authors.forename: Lorenzo
authors.initials: L
authors.lastname: Avaldi
authors.affiliation: CNR-ISM , Area della Ricerca di Roma 1, via Salaria km 29.300, 00015 Monterotondo (RM), Italy.
authors.forename: Alessandra
authors.initials: A
authors.lastname: Paladini