Computational Study on the Structure, Stability, and Electronic Feature Analyses of Trapped Halocarbons inside a Novel Bispyrazole Organic Molecular Cage

[Image: see text] Computational experiments on a novel crystal (Bharadwaj et al. Cryst. Growth Des.2019, 19, 369–375) having a series of seven host–guest complexes (HGCs) where the host species belong to the family of a novel bispyrazole organic cryptand (BPOC) and their structural, stability, and the electronic feature analyses have been reported using the quantum chemical calculation approach. This report systematically unravels an inclusive theory-based experiment on the well-known guest solvents (S) like halocarbon solvents [CCl(4), CHCl(3)/CHCl(3)’ (two orientations), CH(2)Cl(2), C(2)H(4)Cl(2), C(2)H(4)Br(2), and C(2)HCl(3)] and a few model chlorofluorocarbons (CFCs) (CClF(3), CCl(2)F(2), and CCl(3)F) trapped inside the host (BPOC) cryptand, which are the crux in forming the structures of biological and supramolecular systems. Using the implicitly dispersion-corrected DFT (M06-2X/6-31G*) approach, the BPOC molecular cage and its host–guest capabilities were evaluated for the encapsulation of the above said halocarbon solvents as well as the CFC models. The encapsulated C(2)H(4)Br(2) solvent inside the BPOC cage is found to be the most stable among all the HGCs; however, common in the solid phase, similar binary complexes have not been formerly examined in any gas/solvent-phase studies of the BPOC host species. Moreover, very interestingly, the stability pattern of the host–guest complexes enhances for the CFC models when the number of Cl atoms is increased. As the halogenated solvents through halogen and H-bonding are very decisive in understanding and controlling chemical reactions, the NCI-plots support the presence of the halogen bonding (C–Cl/Br···π) and H-bonding (C–H···π) interactions playing an imperative role in stabilizing the guests (solvents) inside the hydrophobic cavity. To get more insights, the HOMO–LUMO and MESP plots as well as natural population analyses have also been highlighted. This theoretical study portrays an inclusive information about the structural, stability, and electronic feature analyses of the host–guest assemblies consisting of the halogen and H-bonding interactions at the atomic level where the influences of such halocarbon solvents play crucial roles in comprehending and managing chemical reactions.