naa a22 4500 510774628 CHVBK 20180411083226.0 cr unu---uuuuu 180411e20130901xx s 000 0 eng 10.1007/s12210-013-0241-5 doi (NATIONALLICENCE)springer-10.1007/s12210-013-0241-5 Ultraviolet and infrared spectroscopy of neutral and ionic non-covalent diastereomeric complexes in the gas phase [Elektronische Daten] [Flaminia Rondino, Alessandra Ciavardini, Mauro Satta, Alessandra Paladini, Caterina Fraschetti, Antonello Filippi, Bruno Botta, Andrea Calcaterra, Maurizio Speranza, Anna Giardini, Susanna Piccirillo] Non-covalent intermolecular interactions responsible for chiral discrimination have been investigated in the gas phase both in neutral and ionic complexes. Mass-selected resonant two-photon ionization (R2PI) as well as infrared depleted R2PI (IR-R2PI) techniques have been applied to investigate the role of fluorine substitution in the chiral recognition process between (R)-1-phenyl 1-ethanol (ER), (S)-1-(4-fluorophenyl)-ethanol (pFES), (R)-1-phenyl-2,2,2-trifluoroethanol (FER) and the two enantiomers of butan-2-ol (BR/S), generated in a supersonic molecular beam. The results have been interpreted with the aid of theoretical predictions at the D-B3LYP/6-31G** level of theory. The diastereomeric complexes of ER and pFES with R- and S-butan-2-ol are structurally similar, and dispersive interactions between the aliphatic chain of the alcohol and the π system of the chromophore as well repulsive interactions are mainly responsible for chiral recognition. FER forms, predominantly with S-butan-2-ol, also stable complexes in which the alcohol is oriented away from the aromatic ring. The ionic complexes between pure enantiomers of the bis (diamido)-bridged basket resorcin[4]arene and cytarabine are generated in the gas phase by electrospray ionization and investigated by IRMPD. The proton-bound diastereomers show clearly different IRMPD spectra which, in light of ONIOM (B3LYP/6-31(d):UFF) calculations, are consistent with the occurrence of several isomeric structures, in which the N(3)-protonated guest is either accommodated inside the host cavity or outside it. The spectral differences are attributed to the effects of the intramolecular hydrogen bonding between the C(2′)_OH group and the aglycone oxygen atom of the nucleosidic guest upon repulsive interactions between the same oxygen atom and the aromatic rings of the host. Accademia Nazionale dei Lincei, 2013 Chirality nationallicence Non-covalent interactions nationallicence IRMPD spectroscopy nationallicence R2PI spectroscopy nationallicence Fluorine nationallicence Nucleosides nationallicence Resorcinarenes nationallicence Rondino Flaminia C.R. ENEA Frascati, Via E. Fermi 45, Frascati, 00044, Rome, Italy aut Ciavardini Alessandra Dip. di Scienze e Tecnologie Chimiche, Università di Roma "Tor Vergata”, via della Ricerca Scientifica, 00133, Rome, Italy aut Satta Mauro CNR-ISMN, Rome, Italy aut Paladini Alessandra CNR-IMIP, Tito Scalo, Potenza, Italy aut Fraschetti Caterina Dip.di Chimica e Tecnologie del Farmaco, Università di Roma "La Sapienza”, Rome, Italy aut Filippi Antonello Dip.di Chimica e Tecnologie del Farmaco, Università di Roma "La Sapienza”, Rome, Italy aut Botta Bruno Dip.di Chimica e Tecnologie del Farmaco, Università di Roma "La Sapienza”, Rome, Italy aut Calcaterra Andrea Dip.di Chimica e Tecnologie del Farmaco, Università di Roma "La Sapienza”, Rome, Italy aut Speranza Maurizio Dip.di Chimica e Tecnologie del Farmaco, Università di Roma "La Sapienza”, Rome, Italy aut Giardini Anna CNR-IMIP, Tito Scalo, Potenza, Italy aut Piccirillo Susanna Dip. di Scienze e Tecnologie Chimiche, Università di Roma "Tor Vergata”, via della Ricerca Scientifica, 00133, Rome, Italy aut Rendiconti Lincei Springer Milan 24/3(2013-09-01), 259-267 2037-4631 24:3<259 2013 24 12210 https://doi.org/10.1007/s12210-013-0241-5 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/s12210-013-0241-5 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Rondino Flaminia C.R. ENEA Frascati, Via E. Fermi 45, Frascati, 00044, Rome, Italy aut NATIONALLICENCE 700 1- Ciavardini Alessandra Dip. di Scienze e Tecnologie Chimiche, Università di Roma "Tor Vergata”, via della Ricerca Scientifica, 00133, Rome, Italy aut NATIONALLICENCE 700 1- Satta Mauro CNR-ISMN, Rome, Italy aut NATIONALLICENCE 700 1- Paladini Alessandra CNR-IMIP, Tito Scalo, Potenza, Italy aut NATIONALLICENCE 700 1- Fraschetti Caterina Dip.di Chimica e Tecnologie del Farmaco, Università di Roma "La Sapienza”, Rome, Italy aut NATIONALLICENCE 700 1- Filippi Antonello Dip.di Chimica e Tecnologie del Farmaco, Università di Roma "La Sapienza”, Rome, Italy aut NATIONALLICENCE 700 1- Botta Bruno Dip.di Chimica e Tecnologie del Farmaco, Università di Roma "La Sapienza”, Rome, Italy aut NATIONALLICENCE 700 1- Calcaterra Andrea Dip.di Chimica e Tecnologie del Farmaco, Università di Roma "La Sapienza”, Rome, Italy aut NATIONALLICENCE 700 1- Speranza Maurizio Dip.di Chimica e Tecnologie del Farmaco, Università di Roma "La Sapienza”, Rome, Italy aut NATIONALLICENCE 700 1- Giardini Anna CNR-IMIP, Tito Scalo, Potenza, Italy aut NATIONALLICENCE 700 1- Piccirillo Susanna Dip. di Scienze e Tecnologie Chimiche, Università di Roma "Tor Vergata”, via della Ricerca Scientifica, 00133, Rome, Italy aut NATIONALLICENCE 773 0- Rendiconti Lincei Springer Milan 24/3(2013-09-01), 259-267 2037-4631 24:3<259 2013 24 12210 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer