Five-coordinate Schiff-base Zn complexes (1,2-cyclohexanediamino-N,N 0 -bis(salicylidene)) zinc-pyridine 1 and (1,2-cyclohexanediamino-N,N 0 -bis(3,5-di-tert-butylsalicylidene)) zincpyridine 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 -stacking and hydrogen bond interactions. Complex 1 has a one-dimensional molecular chain structure via -stacking interaction, while complex 2 has an interesting lattice structure (with cavities with dimensions 10.9 Â 6.9 Å ) formed through intermolecular -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 -* transitions. The Zn (II) centres play a key role in enhancing the fluorescent emission of the ligands.