Metal–organic materials (MOMs) represent a developing class of compounds comprised of molecular building blocks, usually metal ions or metal clusters, which are linked by organic linkers. A successful strategy in building such crystalline solids is to employ appropriate bridging ligands that can bind metal ions in different modes and provide a possible way to achieve diverse dimensionalities, from discrete (e.g. nanoballs, metal–organic polyhedra) to polymeric threedimensional (3D) structures (e.g. porous coordination polymers, porous coordination networks, metal–organic frameworks MOFs). The rational design and synthesis of MOMs and MOFs, with potential use in the fields of gas/liquids storage/separation, catalysis, luminescence, sensors, and adsorption is continuing to be the focus of chemists and crystal engineers. The versatile coordination abilities of Zn(II) and Cd(II) allow a wide variety of architectures resulting from the self-assembly of these metals with organic ligands. A number of discrete compounds and one-, two- and three-dimensional (1D, 2D, 3D) coordination polymers (CPs) were fabricated using the combination: transition metal centers – auxiliary ligands – bidentate bridging ligand (bipyridine-type ligands, dicarboxylic acids). We used the mixed ligand ‘blend approach’ to decorate CPs by oxime ligands, and can conclude that bipyridine ligands and chosen dicarboxylates acted as multidentate linkers, while the bulky classic dioximes or pyridine-n-aldoxime (n = 2, 4) molecules act as auxiliary ligands whose coordination to the metal centers provides the loosely packed materials with the voids in the crystal lattice occupied (or might be potentially occupied) by small organic molecules. The increasing of CPs dimensionality has been achieved by substitution of starting monocarboxylates (such as formate or acetate salts) by polydentate sulfate, tetrafluoroborate or dicarboxylate ligands that afforded an access to the 2D and 3D CPs. All materials demonstrate blue-green emission in the solid state and the results suggest that these complexes may be good candidates for green and blue light emitting materials.