Pentavalent P…π phosphorus bonding with associated Cl…π halogen bonding in influencing the geometry of POCl3-Phenylacetylene heterodimers: Evidence from matrix isolation infrared spectroscopy and ab initio computations

Unique Dispersion-Induced Tetrel Bond with Co-operative σ-hole-Induced Pnicogen Bond in the POCl3-Acetone Heterodimer: Experimental Confirmation at Low Temperatures

“…Phosphorus is known to exist at two stable oxidation states: trivalent (+3) and pentavalent (+5). Phosphorus bonding at both these states has been observed quite recurrently in experiments performed at our laboratory − and also in the extensive computational forays by several groups around the world, over the past decade. Phosphoryl chloride (POCl 3 ), a well-known precursor in the synthesis of organic phosphates, has proven to be an efficient prototype for the study of pentavalent phosphorus bonding.…”

Interplay of unique N⋯π pnicogen and H⋯π/H⋯O hydrogen bonding interactions in the heterodimers of nitromethane with acetylene and benzene as π-electron donors: experimental characterization at low temperatures under isolated conditions with computational corroboration

“…Arsenic (As) is proven to participate in the As⋯π interaction in the XRD results published by Vickaryous and co-workers. 99 Evidence supporting the presence of H⋯π (C–H⋯π, N–H⋯π and O–H⋯π) and P⋯π interactions 19,69,100 using computational and matrix-isolated infrared spectroscopy has been obtained in our laboratory. As mentioned before nitrogen forms the smallest of pnicogens making its π-hole feeble.…”

“…69 Numerous instances of phosphorus (pentavalent and trivalent) hosting pnicogen bonds have been isolated, experimentally. 19,70–80…”

π‐hole driven N⋅⋅⋅O/N⋅⋅⋅π Pnicogen and C⋅⋅⋅O Tetrel Bonding inNitromethane‐Carbonyl Dimers: Comprehensive Study using Matrix Isolation Infrared Spectroscopy and Quantum Chemical Computations

“…[26][27][28][29] One of the techniques, which applies this strategy is matrix-isolation infrared spectroscopy. [30][31][32][33][34][35][36][37] The non-covalent interactions mentioned here are consequences of localised anisotropy in the molecular electrostatic potential (MESP), surrounding an atom within a molecule, of positive polarity. These occur along the extension of a σ-bond/ over the π-electron cloud and are termed a σ-hole/ π-hole respectively.…”

“…This shift in frequency could be captured by vibrational spectroscopy which, along with the support of quantum chemical calculations enables structure elucidation and hence characterising the interaction [26–29] . One of the techniques, which applies this strategy is matrix‐isolation infrared spectroscopy [30–37] …”