Gurtovyi R. Structure, luminescent and electrophysical properties of carboxylate coordination polymer, based on azamacrocyclic complexes of nickel(II), copper(II) and zinc(II) and their composites.

The structures of 34 ionic compounds and coordination polymers (CP) based on tetra-, penta- and hexaazamacrocyclic cations of nickel(II), copper(II) and zinc(II) and aromatic carboxylates and sulfonates were determined by the method of X-ray crystallography. It is shown that independently on their nature (ionic compound, electro-neutral, anionic 1D or 2D CPs) the potential vacant space occupied be crystal solvent molecules is present in the crystal lattices of the majority of compounds. Luminescent properties of synthesized complexes were studied. It is shown that ligand-centered luminescence inherent in the zinc (II) complexes is due to the electronic transition in aromatic systems of carboxylates. A number of composites was obtained based on zinc-containing CPs and luminescent organic dyes. It was shown that in the case of overlapping of dye absorption band with emission bands of CPs the bimodal emission of composites is obseerved. Nitrocompounds were shown to quench the luminescence of [Zn(L1)(DPhDC)]n and his composite with acridine orange. Processes of iodine sorption was studied using a set of three pairs of isostructural CP. It is shown that the amount of iodine adsorbed by complexes formed by redox-active nickel(II) is higher than that captured by redox-inert zinc(II)-containing analogue under the same conditions. The formation of nickel(III) ions as a result of nickel(II) oxidation is confirmed by EPR spectroscopy. In the majority of cases iodine-containing composites unlike individual CPs display electronic conductivity. The possibility to utilize such CP and composites thereupon as sensibilizing coating of photo-anode in iodine-iodide photoelectrochemical cell was demonstrated.