Dataset Information

Exploiting the (-C-H···C-) Interaction to Design Cage-Functionalized Organic Superbases and Hyperbases: A Computational Study.

ABSTRACT: A set of carbon center-based P-ylidesubstituting bases have been exploited computationally with pentacyclo[5.4.0.0^2,6.0^3,10.0^5.9]undecane (PCU) and pentacyclo [6.4.0.0^2,7.0^3,11.0^6,10] dodecane (PCD) scaffolds using the B3LYP-D3/6-311+G(d,p) level of theory. The proton affinities calculated in the gas phase are in the range of superbases and hyperbases. The Atomsin-Molecules and Natural Bond Orbital calculations reveal that the -C-H···C- interaction plays a substantial role in improving the basicity, and tuning the -C-H···C- interaction can enhance the basicity of such systems. The free activation energy for proton exchange for PCD and PCU scaffolds substituted with P-ylide is substantially low. The computed results reveal the strength and nature of such - C-H···C- interactions compared to the -N-H···N- hydrogen bonds. The isodesmic reactions suggest that the superbasicity achieved using these frameworks arises from a combination of several factors, such as the ring strain of the bases in their unprotonated form, steric repulsion, and the intramolecular -C-H···C- interaction.

SUBMITTER: Saha A

PROVIDER: S-EPMC10586256 | biostudies-literature | 2023 Oct

REPOSITORIES: biostudies-literature

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Exploiting the (-C-H···C-) Interaction to Design Cage-Functionalized Organic Superbases and Hyperbases: A Computational Study.

Saha Anusuya A Ganguly Bishwajit B

ACS omega 20231002 41

A set of carbon center-based P-ylidesubstituting bases have been exploited computationally with pentacyclo[5.4.0.02,6.03,10.05.9]undecane (PCU) and pentacyclo [6.4.0.02,7.03,11.06,10] dodecane (PCD) scaffolds using the B3LYP-D3/6-311+G(d,p) level of theory. The proton affinities calculated in the gas phase are in the range of superbases and hyperbases. The Atomsin-Molecules and Natural Bond Orbital calculations reveal that the -C- ...[more]

PMID: 37867725

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Project description: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 [CCl4, CHCl3/CHCl3' (two orientations), CH2Cl2 , C2H4Cl2 , C2H4Br2 , and C2HCl3 ] and a few model chlorofluorocarbons (CFCs) (CClF3 , CCl2F2 , and CCl3F) 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 C2H4Br2 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.

Dataset Information

Exploiting the (-C-H···C-) Interaction to Design Cage-Functionalized Organic Superbases and Hyperbases: A Computational Study.

Publications

Exploiting the (-C-H···C-) Interaction to Design Cage-Functionalized Organic Superbases and Hyperbases: A Computational Study.

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