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

Herein, 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 center dot center dot center dot Ag, Te center dot center dot center dot Ag interactions as well as intermolecular Hg center dot center dot center dot Hg interactions and formed an extended 1D molecular chain by directing six atoms to interact as Te-II center dot center dot center dot Ag-I center dot center dot center dot Hg-II center dot center dot center dot Hg-II center dot center dot center dot Ag-I center dot center dot center dot Te-II in a non linear fashion. The Hg center dot center dot center dot Ag, Te center dot center dot center dot Ag interactions have also been studied in solution by Hg-199, Te-125 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 center dot center dot center dot Hg interaction is stronger than the intramolecular Hg center dot center dot center dot Ag interactions.