Search

The existence of unique ON⋯π pnicogen bonding in combination with C-H⋯π/C-H⋯O hydrogen bonding interactions has been experimentally affirmed in the heterodimers of nitromethane with aliphatic (acetylene; NMAc) and aromatic (benzene; NMBz) π-electron donors at low temperatures under isolated conditions. The potential energy surfaces of NMAc and NMBz dimers have been probed for stationary points using ab initio and DFT computational methods. Three unique geometries for NMAc dimers were optimized, which were stabilized through mixed ON⋯π pnicogen bonding and C-H⋯π/C-H⋯O hydrogen bonding interactions with varying strength. Within the Ar matrix at 12 K, only the C-H⋯π and C-H⋯O bound NMAc dimer was generated, while in N 2 , two geometries, one stabilized by pnicogen bonded ON⋯π and C-H⋯π interactions and the other by C-H⋯π and C-H⋯O interactions, were produced. The NMBz dimer has only one structure stabilized by both ON⋯π pnicogen and C-H⋯π hydrogen bonding interactions that appears to be generated preferentially. The binding energies of both the dimers have the greatest contribution from electrostatics in both classes of NMAc and NMBz dimers, which is closely followed by dispersion forces in the case of NMBz. The increased proton affinity of benzene over acetylene appears to enhance the strength of C-H⋯π hydrogen bonds in NMBz while the ON⋯π pnicogen bonds remain quite similar in strength in both NMBz and NMAc dimers.

The role of nitrogen, the first member of the pnicogen group, as an electron donor in hypervalent non-covalent interactions has been established long ago, while observation of its electron accepting capability is still elusive experimentally, and remains quite intriguing, conceptually. In the light of minimal computational exploration of this novel class of pnicogen bonding so far, the present work provides experimental proof with unprecedented clarity, for the existence of N(acceptor)N(donor) interaction using the model nitromethane (NM) molecule with ammonia (AM) as a Lewis base in NM-AM aggregates. The NM-AM dimer, in which the nitrogen atom of NM (as a unique pnicogen) accepts electrons from AM (the traditional electron donor), was synthesized at low temperatures under isolated conditions within inert gas matrixes and was characterized using infrared spectroscopy. The experimental generation of the NM-AM dimer stabilized via NN interaction has strong corroboration from ab initio calculations. Furthermore, confirmation regarding the directional prevalence of this NN interaction over C-HN and N-HO hydrogen bonding is elucidated quantitatively by quantum theory of atoms in molecules (QTAIM), electrostatic potential mapping (ESP), natural bond orbital (NBO), non-covalent interaction (NCI) and energy decomposition (ED) analyses. The present study also allows the extension of σ-hole/π-hole driven interactions to the atoms of the second period, in spite of their low polarizability.

The branching of a methyl group in a linear chain has a profound influence on the conformational morphology as it wields a strong control in reducing a large number of conformations. To unravel the effect of branching on the second non-hyperconjugative carbon atom on the conformational landscape, the conformations of tris(2-methylbutyl)phosphate (T2MBP) were studied using Density Functional Theory (DFT) computations and matrix isolation infrared spectroscopy. Experimentally, T2MBP along with N 2 /Ar/Kr/Xe gases was effusively expanded and deposited at a low temperature of 12 K, which was subsequently probed using infrared spectroscopy. The computations of all the conformations were accomplished using the B3LYP level of theory with the 6-311++G(d,p) basis set. A dimethyl(2-methylbutyl) phosphate (DM2MBP) prototype, a molecule containing a single 2-methylbutyl moiety, was examined for its conformations. Computations predicted 18 and 9 conformations each for the 'gauche' and 'trans' families, respectively, in which the third branched carbon completely influences the orientation of the fourth carbon, which simplifies the conformational problem of DM2MBP. Of the 18 and 9 bunches each in the 'gauche' and 'trans' families, only 7 and 3 conformations, respectively, became energetically important, which when extrapolated to T2MBP resulted in 343 and 147 conformational possibilities. The factor of degeneracy further reduced these numbers and a total of 168 conformations effectively contribute to the conformational composition of T2MBP in the gas phase. The role of stereo electronic and steric factors prevalent in the conformational clusters of T2MBP was unravelled respectively using natural bond orbital and non-covalent interaction analyses.

Albeit the first account of hypervalentπ interactions has been reported with halogenπ interactions, the feasibility of their extension to other hypervalent atoms as possible Lewis acids is still open. In this work, the role of phosphorus as an acceptor from the π electron cloud (Pπ pnicogen or phosphorus bonding) in PCl3-C2H2 and PCl3-C2H4 heterodimers is explored, by combining matrix isolation infrared spectroscopy with ab initio and DFT computational methodologies. The respective potential energy surfaces of the PCl3-C2H2 and PCl3-C2H4 heterodimers reveal unique minima stabilized by a concert of reasonably strong to weak interactions, of which Pπ phosphorus bonding was energetically dominant. Heterodimers, trimers and tetramers bound primarily by this unique phosphorus bond were generated at low temperatures. The dominance of phosphorus bonding in the PCl3-C2H2 and PCl3-C2H4 heterodimers over other interactions (such as Hπ, HCl, HP, Clπ and lone pair-π interactions) was confirmed and substantiated using extended quantum theory of atoms in molecules, natural bond orbital, electrostatic potential mapping and energy decomposition analyses. The following inferences in correlation with results from non-covalent-interaction analysis offer a complete understanding of the nature of the Pπ phosphorus bonding interactions. The significance of electrostatic forces kinetically favoring the formation of phosphorus bonded heterodimers, in addition to thermodynamic stabilization, is demonstrated experimentally.

Owing to the fact that σ stacking is as important as π stacking in determining the structural motifs of aliphatic saturated cyclic hydrocarbons, in this work we have provided the first unambiguous spectroscopic evidence for the existence of σ stacking interactions in cyclohexane dimers at low temperatures. Molecular beam experiments performed using effusive nozzle and supersonic jet sources on cyclohexane in an N2 matrix generated cyclohexane dimers stabilized through σ stacking and the dimers were characterized by infrared spectroscopy. The ab initio computations carried out on cyclohexane dimers identified eclipsed (face-to-face), parallel displaced and T-shaped structures, which are predominantly stabilized by σ stacking interactions. While natural bond orbital analysis substantiated a significant amount of σ → σ* interactions involved in the stabilization, the Atoms in Molecules analysis indicated that the stacking is induced by a plausible 'dihydrogen bonding' interaction. Energy decomposition analysis disclosed that a large measure of dispersion interactions effectively contributes for the overall stability of cyclohexane dimers.

The π electron systems are the conventional electron donors to the hydrogen acceptors in hydrogen bonding. Apart from the hydrogen atom, halogens, chalcogens, pnicogens and triel/tetrel atoms can also be envisaged as electron acceptors involving π clouds. Markedly, in pnicogenπ interactions, the bonding of the hypervalent (predominantly pentavalent) state of the phosphorus atom with π electron donors is elusive and can be thought of as an intuitive extension to trivalent phosphorusπ interactions. In this work, on the one hand, POCl 3 was taken as a prototypical molecule to explore these pentavalent phosphorus interactions and on the other hand, acetylene (C 2 H 2 ), ethylene (C 2 H 4 ) and benzene (C 6 H 6 ), in which phosphorusπ bonding can be expected to compete with hydrogen and halogen bonding interactions, were taken as π electron donors. All three POCl 3 -C 2 H 2 , POCl 3 -C 2 H 4 and POCl 3 -C 6 H 6 heterodimers were experimentally generated at low temperatures in Ar and N 2 matrices and were characterized by both infrared spectroscopy and state-of-the-art quantum chemical computations. Though hydrogen bonding dominates in POCl 3 -C 2 H 2 and POCl 3 -C 2 H 4 heterodimers, phosphorus bonding plays a definite and non-trivial role in their overall stabilization. An interesting paradigm transformation was noticed in the POCl 3 -C 6 H 6 system, where pentavalent phosphorusπ bonding was observed to completely influence the hydrogen bonding interaction. To further shed light on these Pπ systems, the interaction characteristics were analyzed with the help of electrostatic potential mapping, natural bond orbital and energy decomposition analyses.

Phosphorus, an important element among the pnicogen group, opens up avenues for experimental and computational explorations of its interaction in a variety of compounds. Although experimental proof of trivalent phosphorus bonding is limited and is growing with time, phosphorus bonding with pentavalent phosphorus has been a long sought after interaction both computationally and experimentally. In the present work, for the first time, we have provided unambiguous experimental evidence for the pentavalent phosphorus bonding interaction by exploiting a phosphoryl chloride (POCl3) prototype under isolated conditions at low temperatures. The POCl3 dimer and higher aggregates can be set as a unique example possessing pentavalent phosphorus bonding with a competing halogen bonding interaction. The POCl3-H2O heterodimer is another interesting system, stabilized through multiple phosphorus and hydrogen bonded interactions. Using matrix isolation infrared spectroscopy, the POCl3 homodimer and POCl3-H2O heterodimer were characterized and the structures were elucidated by employing ab initio and DFT methods. The multifaceted interactions in the POCl3 paradigm were investigated by using Natural Bond Orbital, Energy Decomposition and Electrostatic Potential Mapping analyses.

A phosphorous trichloride (PCl3)-benzene (C6H6) heterodimer was generated in a low temperature N2 matrix and was characterized using infrared spectroscopy. The structure of the heterodimer produced in the matrix isolation experiment was discerned through ab initio computations. Computations disclosed that the experimentally detected dimer is stabilized through strong non-covalent phosphorus bonded Pπ interaction, considered as a class of pnicogen bonding. This experimentally unmapped Pπ interaction so far has been reconnoitered using atoms in molecules and natural bond orbital and energy decomposition analyses. The influence of substitutions on both the PCl3 and C6H6 monomeric units of the heterodimer was subsequently examined to understand the strength of Pπ interaction as a result of these substitutions.