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Trapping of organophosphorus chemical nerve agents by pillar[5]arene: A DFT, AIM, NCI and EDA analysis

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Abstract

The encapsulation of organophosphorus (OP) nerve agents by pillar[5]arene (P5) molecule, shows that adsorption occurs with a larger structural reorganization of the host molecule. The computed binding energies shows that the complexes formed are more stable inside the cavity. Tabun was found to have the highest binding energy among the studied OPs. The computed Gibbs free energy is negative for Dimethyl methylphosphonate, sarin and tabun, and are positive for soman (GD) and ethyl-S-dimethylaminoethyl methylphosphonothiolate (VX). The inclusion complexes were found to have lower band gap. The quantum theory of Atoms-in-molecules analysis shows that ρ values were positive which implies the existence of noncovalent interactions. The Laplacian of the charge density ∇2ρ for bond critical points bonds are small and are negative which indicates the depletion of electronic charge along the bond paths and existence of an electrostatic nature of bonding between the guest and host molecule. The noncovalent interactions analysis clearly shows the existence of hydrogen bonding and van der Waals bonding in these inclusion complexes. The energy decomposition analysis shows that the, interaction between the P5 and the larger guest molecules VX and GD are mainly due to electrostatic interaction and for small guest, the interactions are mostly of van der Waals type.

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Acknowledgements

SA thank the SERB-DST, India for funding through a project with sanction No. SB/FT/CS-038/2013. NSV thank the Center for Computational Materials Science (CCMS), Tohoku university, Japan and its crew for the computational support though the SR-16000K super computer.

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  1. Department of Chemistry, School of Chemical and Biotechnology, SASTRA University, Thanjavur, 613 401, India

    Ambigapathy Suvitha & Natarajan Sathiyamoorthy Venkataramanan

  2. Center for Computational Chemistry and Materials Science (CCCMS), SASTRA University, Thanjavur, 613 401, India

    Natarajan Sathiyamoorthy Venkataramanan

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  1. Ambigapathy Suvitha
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Suvitha, A., Venkataramanan, N.S. Trapping of organophosphorus chemical nerve agents by pillar[5]arene: A DFT, AIM, NCI and EDA analysis. J Incl Phenom Macrocycl Chem 87, 207–218 (2017). https://doi.org/10.1007/s10847-017-0691-y

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