Characterizing the lone pair⋯π–hole interaction in complexes of ammonia with perfluorinated arenes

Literature Information

Publication Date 2021-03-23
DOI 10.1039/D1CP00451D
Impact Factor 3.676
Authors

Weixing Li, Imanol Usabiaga, Luca Evangelisti, Assimo Maris, Laura B. Favero, Sonia Melandri


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Abstract

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.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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