Experimental proof for σ and π-hole driven dual pnicogen bonding in phosphoryl chloride-nitromethane heterodimers: A combined matrix isolation infrared and ab initio computational studies

Mahapatra, Nandalal; Chandra, Swaroop; Ramanathan, N.; Sundararajan, K.

doi:10.1016/j.molstruc.2021.132045

Cited by 8 publications

(12 citation statements)

References 63 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This anisotropy in the ESP, a π-hole, is known to facilitate ON...X pnicogen bonds involving nitromethane as the Lewis acid due to nitrogen. Spectroscopic evidence for pnicogen bonding hosted by nitrogen has been reported by our group, previously, within heterodimers of nitromethane with ammonia and phosphoryl chloride. , …”

Section: Introductionsupporting

confidence: 70%

“…These are also visible in the full-color image, as encircled in Figure . The access of these π-holes for the formation of ON...O pnicogen bonds is known to cause the disappearance of the respective critical point on the ESP projection on the van der Waals isosurface of the submolecule. , Such a disappearance cements the electrostatic origins of the corresponding pnicogen bonding interaction. It also conveys the proximity of the nucleophilic donor (oxygen, here) to the electron-accepting nitrogen.…”

Section: Resultsmentioning

confidence: 99%

“…Spectroscopic evidence for pnicogen bonding hosted by nitrogen has been reported by our group, previously, within heterodimers of nitromethane with ammonia and phosphoryl chloride. 12,13 The emergence of pnicogen bonding as an interaction in which nitromethane could participate inspires a revisit to the structure of dimers of nitromethane. Also, the absence of hydrogen bonding in liquid nitromethane raises a question as to what other interactions, other than van der Waals forces, could be prevalent among the nitromethane molecules.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Unique O═N...O Pnicogen Interactions in Nitromethane Dimers: Evidence Using Matrix Isolation Infrared Spectroscopy and Computational Methodology

et al. 2022

Self Cite

View full text Add to dashboard Cite

Geometries of nitromethane homodimers have been revisited using ab initio and density functional methodologies, following their formation within cryogenic matrices, confirmed using infrared spectroscopy. In contrast to the claim that the intermolecular interactions are due to dispersion forces or very weak hydrogen bonds, in the present work, concrete evidence for the prevalence of O N...O pnicogen bonding has been presented. The pnicogen bonds have been found to be primarily responsible for the characteristic geometry of a homodimer. The formation of a nitromethane dimer with pnicogen bonding stabilization is evidenced using matrix isolation infrared spectroscopy with Ne and Ar matrices and computations. The interactions within homodimers have been characterized using quantum theory of atoms in molecules, natural bond orbital, energy decomposition, electrostatic potential mapping, and noncovalent interaction analyses. The larger intermolecular separations in liquid nitromethane indicated by previous molecular dynamics-based studies alongside the supposed invariance of infrared spectra in the gas phase and liquid phase could have led to the assumption of a lack of intermolecular interactions. However, the prevalence of hydrogen and pnicogen bonds across these larger than usual separations is affirmed by the geometries presented here.

show abstract

Section: Introductionsupporting

confidence: 70%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Unique O═N...O Pnicogen Interactions in Nitromethane Dimers: Evidence Using Matrix Isolation Infrared Spectroscopy and Computational Methodology

et al. 2022

Self Cite

View full text Add to dashboard Cite

show abstract

“…However, some of the first experimental and computational pieces of evidence for nitrogen-hostedpnicogen bonding have begun appearing since 2018. [90][91][92][93] Non-covalent interactions involving p-electron clouds are quite significant owing to their ubiquity in biological systems. [94][95][96][97][98] This has been explained by Bauza et al in their work wherein the pnicogen-p interaction is energetically more favourable than either the halogen or the chalcogen-p interaction.…”

Section: Introductionmentioning

confidence: 99%

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

Mahapatra

Chandra

Ramanathan

et al. 2022

Phys. Chem. Chem. Phys.

Self Cite

View full text Add to dashboard Cite

show abstract

“…The holes of group IV–VII element-containing molecules can interact with Lewis bases, forming tetrel, − pnicogen, − chalcogen, − and halogen ,− bonds, respectively. Among hole-bonding complexes, the interactions of pnicogen-containing molecules with Lewis bases have found sustained attention of a variety of theoretical − and experimental studies − by dint of their significant importance in chemical reactions − and biological systems …”

Section: Introductionmentioning

confidence: 99%

σ-Hole and LP-Hole Interactions of Pnicogen···Pnicogen Homodimers under the External Electric Field Effect: A Quantum Mechanical Study

et al. 2022

View full text Add to dashboard Cite

σ-Hole and lone-pair (lp)-hole interactions within σ-hole···σ-hole, σ-hole···lp-hole, and lp-hole···lp-hole configurations were comparatively investigated on the pnicogen···pnicogen homodimers (PCl 3 ) 2 , for the first time, under field-free conditions and the influence of the external electric field (EEF). The electrostatic potential calculations emphasized the impressive versatility of the examined PCl 3 monomers to participate in σ-hole and lp-hole pnicogen interactions. Crucially, the sizes of σ-hole and lp-hole were enlarged under the influence of the positively directed EEF and decreased in the case of reverse direction. Interestingly, the energetic quantities unveiled more favorability of the σ-hole···lp-hole configuration of the pnicogen···pnicogen homodimers, with significant negative interaction energies, than σ-hole···σ-hole and lp-hole···lp-hole configurations. Quantum theory of atoms in molecules and noncovalent interaction index analyses were adopted to elucidate the nature and origin of the considered interactions, ensuring their closed shell nature and the occurrence of attractive forces within the studied homodimers. Symmetry-adapted perturbation theory-based energy decomposition analysis alluded to the dispersion force as the main physical component beyond the occurrence of the examined interactions. The obtained findings would be considered as a fundamental underpinning for forthcoming studies pertinent to chemistry, materials science, and crystal engineering.

show abstract

Experimental proof for σ and π-hole driven dual pnicogen bonding in phosphoryl chloride-nitromethane heterodimers: A combined matrix isolation infrared and ab initio computational studies

Cited by 8 publications

References 63 publications

Unique O═N...O Pnicogen Interactions in Nitromethane Dimers: Evidence Using Matrix Isolation Infrared Spectroscopy and Computational Methodology

Unique O═N...O Pnicogen Interactions in Nitromethane Dimers: Evidence Using Matrix Isolation Infrared Spectroscopy and Computational Methodology

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

σ-Hole and LP-Hole Interactions of Pnicogen···Pnicogen Homodimers under the External Electric Field Effect: A Quantum Mechanical Study

Contact Info

Product

Resources

About