Coordination Behavior of the Tellurium Incorporated Mercuraazametallamacrocycle and Investigation of d10⋅⋅⋅d10 Interactions between Closed Shell (Ag+ Hg2+) Metal Ions

Abstract

AbstractHerein, a new tellurium and mercury containing mercuraazametallamacrocycle has been prepared via (2+2) condensation of bis(o‐aminophenyl)telluride and bis(o‐formylphenyl)mercury(II). The isolated bright yellow solid of mercuraazametallamacrocycle has adopted unsymmetrical figure‐of‐eight conformation in the crystal structure. To study the metallophilic interactions between closed shell metal ions, the macrocyclic ligand has been treated with two equiv. of AgOTf (OTf=trifluoromethansulfonate) and AgBF4, which afforded greenish‐yellow bimetallic silver complexes. The isolated silver complexes displayed intramolecular Hg⋅⋅⋅Ag, Te⋅⋅⋅Ag interactions as well as intermolecular Hg⋅⋅⋅Hg interactions and formed an extended 1D molecular chain by directing six atoms to interact as TeII⋅⋅⋅AgI⋅⋅⋅HgII⋅⋅⋅HgII⋅⋅⋅AgI⋅⋅⋅TeII in a non linear fashion. The Hg⋅⋅⋅Ag, Te⋅⋅⋅Ag interactions have also been studied in solution by 199Hg, 125Te NMR spectroscopy, absorption, and emission spectroscopy. In DFT calculations, the Atom in Molecule (AIM) analysis, non‐covalent interactions (NCI), natural bonding orbital (NBO) analysis strongly supported for experimental evidences and revealed that the intermolecular Hg⋅⋅⋅Hg interaction is stronger than the intramolecular Hg⋅⋅⋅Ag interactions.