Andriichuk I. Crystal structure, redox reactions and sorption properties of metal-organic frameworks based on carboxylate azamacrocyclic nickel(II) and copper(II) complexes

The interaction of macrocyclic nickel(II) and copper(II) complexes with aromatic carboxylates depending on their basicity was shown to result in most cases in the formation of metal-organic frameworks (MOF) constructed from one- or two-dimensional coordination polymers. It is established that free space is present in the crystal lattices of some compounds which can be occupied be the adsorbates. The amount of the copper(II) ammine complex adsorbed by azamacrocyclic carboxylate MOFs during the heterophase interaction (solid - solution) depends on the crystal structure of the sorbent. The possibility of postsorption transformation of this adsorbate into nanosized copper(II) sulfide was demonstrated for the first time. It is shown that the transformation of the nickel(II) complexes in MOFs into the nickel(III) species can be considered as an approach to preparation of new redox active MOFs (RAMOFs). The structure of the nickel(III) ion and the chemical properties of the compounds formed (thermal stability, reactivity) depend essentially on the values of the potential of the Ni3+/2+ couple in macrocyclic environment. It is established that the redox interaction of crystalline macrocyclic nickel(II) carboxylates with silver(I), gold(III) and palladium(II) salts results in the formation of nanoclusters of corresponding metal. Based on the reactions with silver nitrate it was shown that the size of the nanoparticles is dependent on the crystal structure of MOF.