title: Binding energies and 19F nuclear magnetic deshielding in paramagnetic halogen-bonded complexes of TEMPO with haloperfluorocarbons.
abstract: 19F NMR measurements and theoretical calculations were performed to study paramagnetic complexes of iodoperfluorocarbons with stable nitroxide radicals. Contrary to what is usually measured for diamagnetic halogen-bonded complexes involving iodoperfluorocarbons, it was found that the formation of complexes with the 2,2,6,6-tetramethyl(piperidin-1-yloxyl) (TEMPO) radical determines downfield shifts in the 19F NMR spectra. The experimental finding was confirmed by calculating nuclear shielding using density functional theory and correcting the isotropic diamagnetic (19)F chemical shift with contact interactions evaluated from the hyperfine coupling tensor. The computational analysis of the interaction between CF3I and TEMPO, by using DFT and MP2 theories, showed that the occurrence of the halogen bond between the interacting partners is associated with a significant charge transfer to CF3I and that the measured downfield shift is due to the occurring spin transfer.
authors.affiliation: Dipartimento di Chimica, Materiali ed Ingegneria Chimica G. Natta, Politecnico di Milano, Via Mancinelli 7-20131 Milano, Italy. carlo.cavallotti@polimi.it
authors.forename: Carlo
authors.initials: C
authors.lastname: Cavallotti
authors.forename: Pierangelo
authors.initials: P
authors.lastname: Metrangolo
authors.forename: Franck
authors.initials: F
authors.lastname: Meyer
authors.forename: Francesco
authors.initials: F
authors.lastname: Recupero
authors.forename: Giuseppe
authors.initials: G
authors.lastname: Resnati