Nitropyridine-1-Oxides as Excellent 7t-Hole Donors: Interplay between o-Hole (Halogen, Hydrogen, Triel, and Coordination Bonds) and π-Hole Interactions

In this manuscript, we use the primary source of geometrical information, i.e., Cambridge Structural Database (CSD), combined with density functional theory (DFT) calculations (PBEO-D3/def2-TZVP level of theory) to demonstrate the relevance of 7r-hole interactions in para-nitro substituted pyridine-1-oxides. More importantly, we show that the molecular electrostatic potential (MEP) value above and below the pi-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-0- coordinated to a transition metal). The CSD search discloses that p-nitro-pyridine-1-oxide derivatives have a strong propensity to participate in 7r-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 7r-hole and HB/XB/TrB/CB interactions (6-bonding). The synergistic effects between 7r-hole and or-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).