Synthesis, crystal structures and properties of five-coordinate Schiff-base Zn(II) complexes

Abstract

Five-coordinate Schiff-base Zn complexes (1,2-cyclohexanediamino-N,N′-bis(salicylidene)) zinc-pyridine 1 and (1,2-cyclohexanediamino-N,N′-bis(3,5-di-tert-butylsalicylidene)) zinc-pyridine 2 were synthesized and the structures of 1 and 2 have been determined by single-crystal X-ray analysis. All Zn atoms are five-coordinate in both structures. Both complexes exhibit interesting structures based on intermolecular π–π stacking and hydrogen bond interactions. Complex 1 has a one-dimensional molecular chain structure via π–π stacking interaction, while complex 2 has an interesting lattice structure (with cavities with dimensions 10.9 × 6.9 Å) formed through intermolecular π–π stacking and hydrogen bond interactions. 1 and 2 are compared and characterized by MS, elemental analysis, IR, UV-Vis and Photoluminescence (PL). Fluorescence spectra show that the maximal emission wavelength of 1 and 2 are 454 nm, and 480 nm, respectively, upon radiation by UV light. Cyclic voltammetry performed on 1 and 2 indicate a dependence of the cathodic potentials upon conformational and electronic effects. Electronic spectral properties of 1 and 2 were studied by TD-DFT methods. The fluorescent emission of these complexes originates from ligand-centred π–π∗ transitions. The Zn (II) centres play a key role in enhancing the fluorescent emission of the ligands.