On the Significant Importance of Hg···Cl Spodium Bonding/�/�-Hole/Noncovalent Interactions and Nanoelectronic/Conductivity Applications in Mercury Complexes: Insights from DFT Spectrum

Hazra, S and Majumdar, D and Frontera, A and Roy, S and Gassoumi, B and Ghalla, H and Dalai, S (2024) On the Significant Importance of Hg···Cl Spodium Bonding/�/�-Hole/Noncovalent Interactions and Nanoelectronic/Conductivity Applications in Mercury Complexes: Insights from DFT Spectrum. In: Crystal Growth and Design, 24 (17). 7246 -7261.

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Abstract

This work synthesized two Hg complexes (1-2) using a LO-rich ligand (LO-rich = LO-VAN/LET-VAN) in CH3OH and CH3OH/DCM media. Complex 1 is discrete (HgCl2)3LO-VAN, while 2 is the coordination polymer (CP) HgCl2LET-VANn. The complexes were characterized using spectroscopy, SCXRD, HRMS, PXRD, SEM-EDX, and XPS study. The X-ray structure revealed that 1 crystallizes in the monoclinic space group P21/c and is built from isolated trinuclear units of (HgCl2)3LO-VAN. Similarly, 2 crystallizes in the monoclinic space group P21/n, having polynuclear units of HgCl2LET-VANn. The Hg(II) center has favorable stereochemical features and is five-coordinated, creating trigonal (1) and square bipyramidal geometries (2). DFT-D3 at the B3LYP/LanL2DZ level of theory using Gaussian 09 was used to explore the FMO/MEP/NBO and ELF-LOL plot of Hg complexes. Hirshfeld surface and 2D fingerprint plots were used to analyze the H···H, H···O/O···H, and H···Cl/Cl···H contacts. The FMO energy gap explains the complex�s conductivity and nanoelectronic applications. The transfer of electronic charge on the surface has been explained through NBO. ELF-LOL profile demonstrates exceptional complex stability. The existence of spodium bonding (SpBs)/�-/�-holes and noncovalent interactions was investigated by DFT. The nature and strength of the Hg···Cl SpBs were analyzed by QTAIM and an NCI plot. The findings revealed that SpBs exhibit weak noncovalent interactions characterized by bond critical points (BCPs), bond paths, and reduced density gradient (RDG) iso-surfaces. The MEP surface demonstrated the presence of �-/�-holes at the Hg atoms, facilitating directional SpB formation. Herein, the nature of the interaction energies is influenced by SpBs and the concurrent formation of additional noncovalent interactions such as �-stacking and CH···�, O contacts. Primarily, the research emphasizes the importance of �-/�-hole interactions in forming mercury complexes through self-assembly. © 2024 American Chemical Society.

Item Type:	Journal Article
Publication:	Crystal Growth and Design
Publisher:	American Chemical Society
Additional Information:	The copyright for this article belongs to publisher.
Keywords:	Atomic emission spectroscopy; Chelation; Chlorine compounds; Electron spin resonance spectroscopy; Gallium compounds; Ligands; Light modulators; Mercury amalgams; Modems; Molecular dynamics; Molecular orbitals; Operational amplifiers; Photodetectors; Pulse amplifiers; Solvent extraction; Spectroscopic analysis; Stereocenters; Variable frequency oscillators; Variable gain amplifiers; X ray absorption spectroscopy; X ray diffraction analysis; X ray photoelectron spectroscopy, Complex 1; Coordination Polymers; Coordination-polymers; Hg complexes; Hole interactions; Mercury complex; Monoclinic space groups; Non-covalent interaction; Spectra's; Synthesised, Mercury compounds
Department/Centre:	Division of Chemical Sciences > Solid State & Structural Chemistry Unit
Date Deposited:	17 Sep 2024 11:25
Last Modified:	17 Sep 2024 11:25
URI:	http://eprints.iisc.ac.in/id/eprint/86166

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