Structure and Energetics of Complexes of B₁₂N₁₂ with Hydrogen Halides—SAPT(DFT) and MP2 Study

Abstract

Molecular complexes of a fullerene analogue B12N12 with hydrogen halides (HCl, HBr, and HI) were studied with symmetry-adapted perturbation theory with density-functional theory applied for a description of monomers (SAPT(DFT)), Møller-Plesset theory to the second order (MP2), and its spin-component-scaled variant (SCS-MP2) in a limit of a complete basis set. For each halide five symmetry-distinct minimum structures of the complex have been found on the potential energy hypersurface, with interaction energies ranging from -6 to -18 kJ/mol. The natural bond orbital and the atom-in-molecules analysis of noncovalent bonds resulted in a division of these configurations into three categories: hydrogen-bonded, halogen-bonded, and those of a mixed type, involving simultaneously a hydrogen bonding and a π-hole bonding between halogen and boron atoms. A comparison of various approaches for the calculation of interaction energies shows that the SCS-MP2 supermolecular method gives results which are in a close agreement with SAPT(DFT), while the MP2 interaction energies are systematically more negative than the SAPT values. The ability of the B12N12 nanocage to bind hydrogen halides through several active sites on its surface puts under question the selectivity of the binding necessary in crystal engineering, especially for the hydrogen bromide and hydrogen iodide cases, which show small differences in stabilization energies for their minimum structures. The directionality of noncovalent bonds is explained on grounds of the anisotropy of some SAPT components, like electrostatics and induction, as well as by the σ-hole and π-hole models.

Metal‐Free Reduction of NO over a Fullerene‐like Boron Nitride Nanocluster: A Mechanistic Study by DFT Calculations

“…Two different B–N bonds are found in B 12 N 12 , one is shared between two six‐membered rings (1.44 Å), while the other is between the 4‐ and 6‐member ring (1.48 Å). These B−N bond lengths are found to be in excellent agreement with those reported in the previous studies . The energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the B 12 N 12 is 9.10 eV, which indicates the high stability of this system.…”

Mechanistic insight on (E)‐methyl 3‐(2‐aminophenyl)acrylate cyclization reaction by multicatalysis of solvent and substrate

“…In an effort to rationalize this vital free energy difference of 3Wa‐TS1 , 1A‐TS1 , and 1A1W‐TS1 , the weak interactions in these three RDS transition states are carefully analyzed by AIM and Multwfn . Sextuple, Quintuple, and quadruple HB interactions are found in 3Wa‐TS1 , 1A1W‐TS1 , and 1A‐TS1 (Supporting Information Table S1), respectively.…”

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