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Nitropyridine-1-Oxides as Excellent π-Hole Donors: Interplay between σ-Hole (Halogen, Hydrogen, Triel, and Coordination Bonds) and π-Hole Interactions

Department of Chemistry, Universitat de les Illes Balears, Crta de Valldemossa km 7.5, 07122 Palma de Mallorca (Baleares), Spain
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Int. J. Mol. Sci. 2019, 20(14), 3440; https://doi.org/10.3390/ijms20143440
Received: 29 June 2019 / Revised: 9 July 2019 / Accepted: 11 July 2019 / Published: 12 July 2019
(This article belongs to the Special Issue Host-Guest Complexes)
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Abstract

In this manuscript, we use the primary source of geometrical information, i.e., Cambridge Structural Database (CSD), combined with density functional theory (DFT) calculations (PBE0-D3/def2-TZVP level of theory) to demonstrate the relevance of π-hole interactions in para-nitro substituted pyridine-1-oxides. More importantly, we show that the molecular electrostatic potential (MEP) value above and below the π–hole of the nitro group is largely influenced by the participation of the N-oxide group in several interactions like hydrogen-bonding (HB) halogen-bonding (XB), triel bonding (TrB), and finally, coordination-bonding (CB) (N+–O coordinated to a transition metal). The CSD search discloses that p-nitro-pyridine-1-oxide derivatives have a strong propensity to participate in π-hole interactions via the nitro group and, concurrently, N-oxide group participates in a series of interactions as electron donor. Remarkably, the DFT calculations show from strong to moderate cooperativity effects between π–hole and HB/XB/TrB/CB interactions (σ-bonding). The synergistic effects between π-hole and σ-hole bonding interactions are studied in terms of cooperativity energies, using MEP surface analysis and the Bader’s quantum theory of atoms in molecules (QTAIM). View Full-Text
Keywords: CSD analysis; π-hole interactions; σ-hole interactions; supramolecular chemistry; cooperativity CSD analysis; π-hole interactions; σ-hole interactions; supramolecular chemistry; cooperativity
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Galmés, B.; Franconetti, A.; Frontera, A. Nitropyridine-1-Oxides as Excellent π-Hole Donors: Interplay between σ-Hole (Halogen, Hydrogen, Triel, and Coordination Bonds) and π-Hole Interactions. Int. J. Mol. Sci. 2019, 20, 3440.

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