RT info:eu-repo/semantics/article
T1 Characterizing the lone pair⋯π–hole interaction in complexes of ammonia with perfluorinated arenes
A1 Li, Weixing
A1 Usabiaga, Imanol
A1 Calabrese, Camilla
A1 Evangelisti, Luca
A1 Maris, Assimo
A1 Favero, Laura B.
A1 Melandri, Sonia
AB When hydrogen is completely replaced by fluorine, arenes become prone to forming a lone pair⋯π–hole non-covalent bond with ligands presenting electron rich regions. Such a species is ammonia, which confirms this behavior engaging its lone pair as the electron donor counterpart in the 1 : 1 adducts with hexafluorobenzene and pentafluoropyridine. In this work, the geometrical parameters of the interaction have been unambiguously identified through the detection, by means of Fourier transform microwave spectroscopy, of the rotational spectra of both normal species and their 15NH3 isotopologues. An accurate analysis of the experimental data, including internal dynamics effects, endorsed by quantum chemical calculations, both with topological analysis and energy decomposition method, extended to the hydrogenated arenes and their water complexes, proved the ability of ammonia to create a stronger and more flexible lone pair⋯π–hole interaction than water. Interestingly, the higher binding energies of the ammonia lone pair⋯π–hole interactions correspond to larger intermolecular distances.
SN 1463-9076
YR 2021
FD 2021
LK https://uvadoc.uva.es/handle/10324/74593
UL https://uvadoc.uva.es/handle/10324/74593
LA eng
NO Phys.Chem.Chem.Phys., 2021, 23, 9121-9129
DS UVaDOC
RD 04-abr-2025