A combined experimental and computational study on supramolecular assemblies in hetero-tetranuclear nickel(ii)–cadmium(ii) complexes with N2O4-donor compartmental Schiff bases

Abstract

Two new hetero-tetranuclear nickel(II)/cadmium(II) complexes, a cubane [(CH₃CO₂)₂Ni₂(L¹)₂Cd₂(NCS)₂] (1) and a linear tetramer [(DMSO)₂NiL²Cd(NCS)(μ_1,3-SCN)Ni(DMSO)L²Cd(NCS)₂] (2) {where H₂L¹ = N,N′-bis(3-methoxysalicylidene)propane-1,3-diamine and H₂L² = N,N′-bis(3-ethoxysalicylidene)propane-1,3-diamine are potential octadentate compartmental Schiff bases}, were synthesized and characterized. The structures of both complexes were confirmed by single crystal X-ray diffraction studies. Complex 1 contained a Ni₂Cd₂O₄ cubane core, whereas complex 2 featured an end-to-end thiocyanate-bridged tetranuclear moiety. Furthermore, complex 1 showed C–H⋯H–C interactions, whereas a unique S⋯π interaction was observed in complex 2. Theoretical studies were performed using several computational tools such as NBO and AIM analyses. Both complexes showed photoluminescence in DMSO medium at room temperature upon irradiation with ultraviolet light. The lifetimes of the excited states were ∼27 ns.