Syntheses, crystal structures and photo physical aspects of azido-bridged tetranuclear cadmium (II) complexes: DFT/TD-DFT, thermal, antibacterial and anti-biofilm properties

Abstract

In this work we have reported two novel tetranuclear Cd(II) complexes viz. [Cd4 (LOMe)2 (μ1,1-N3)3 (μ1,3-N3)]n (1) and [Cd4 (LOEt)2 (μ1,1-N3)3(OAc)]2 (2) where (H2LOMe) and (H2LOEt) are two important less explored salen-type Schiff base ligands. Both of the complexes have been characterized by using routine spectroscopic techniques, elemental analyses (C, H and N), X-ray powder diffraction pattern (PXRD) and thermal analysis by TGA along with single x-ray crystallography. The complete structural study discloses that in both cases the fully deprotonated ligand [LOMe]2- or [LOEt]2- utilized all potential coordination sites to accommodate four Cd(II) ions. Complex 1 is a one-dimensional polymer with azide (N3) linkage having both (μ1,1 end on) and (μ1,3 end-to-end) azido bridging but complex 2 is a discrete octanuclear ensamble where two [Cd4(O)4(N)2]2+ units bridged to each other showing μ1,1 end on end on azide bridging. Exploration of photo physical properties in DMSO solvent reveals that Cd(II) complexes enhance appreciably the fluorescence behavior over free Schiff base ligands (H2LOMe) and (H2LOEt). DFT calculations performed at B3LYP/def2-TZVP level of theory reveal both the energetics and composition of FMOs in these complexes and also show electrophilic and nucleophilic areas via molecular electrostatic maps [ESP] concept. The antibacterial, membrane damage assay and anti-biofilm properties of complexes 1 and 2 were investigated very carefully against some important Gram-positive and Gram-negative bacterial strains.