article · Crystal Growth & Design
Two mercury complexes have been synthesised using oxygen-rich ligands, producing a discrete trinuclear complex and a polynuclear coordination polymer. Detailed structural characterisation using single-crystal X-ray diffraction confirmed that the mercury centres adopt five-coordinated geometries, forming trigonal and square bipyramidal arrangements within monoclinic crystal systems. Computational investigations using density functional theory were employed to study the electronic behaviour, stability, and noncovalent interactions of the compounds. Calculations based on frontier molecular orbitals examine the electronic energy gaps, explaining conductivity characteristics relevant to nanoelectronic contexts. Furthermore, theoretical topological analyses verified the presence of weak, directional spodium bonds mediated by sigma- and pi-holes on the mercury atoms. These interactions, alongside pi-stacking and related noncovalent contacts, play a central role in guiding the self-assembly and overall architecture of the complexes.
Understanding noncovalent forces, such as spodium bonding and sigma-hole interactions, helps scientists control how metal complexes assemble into functional architectures. By linking these subtle atomic interactions to fundamental electronic properties such as conductivity, this research contributes to the rational design of stable metal-organic structures tailored for chemical physics investigations and molecular-level electronic systems.
The findings are relevant to nanoelectronics and conductive materials, based on theoretical calculations of frontier molecular orbital energy gaps. However, this research represents very early-stage fundamental chemistry and computational modelling. Because the abstract does not report functional device testing, electrical measurements, or pilot synthesis, significant experimental validation and applied research would be required before identifying an immediate commercial pathway or industry end user.
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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-VAN]n. 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-VAN]n. 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)/σ-/π-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 σ-/π-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 π-stacking and CH···π, O contacts. Primarily, the research emphasizes the importance of σ-/π-hole interactions in forming mercury complexes through self-assembly.
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DOI: 10.1021/acs.cgd.4c00893
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