2D coordination polymers and ionic complexes of the nickel(II) and zinc(II) cyclam cations with trigonal carboxylate linkers based on triazine core. Crystal structures, supramolecular catenation and spectral characterization

A series of complexes of tetraamine cations of the nickel(II) and zinc(II) and large trigonal aromatic carboxylates have been prepared and their structures have been determined by single crystal X-ray crystallography. All compounds obtained were also characterized by elemental analysis, thermogravimetric investigations, FTIR spectroscopy, diffuse reflectance spectra, as well as by powder X-ray diffraction measurements. It was shown that the coordination polymers {[(ZnL1)3(m-TATB)2]center dot 6H2O}(n), {[(NiL1)3(m-TATB)(2)]center dot 6 center dot.6H(2)O}(n) and {[(NiL1)3(p-TATB)2]center dot 4H2O}(n) (H3(m-TATB) - 3,3',3 ''-s-triazine-2,4,6-triyl-tribenzoic acid, H3(p-TATB) - 4,4',4 ''-s-triazine-2,4,6-triyl-tribenzoic acid, L1 - 1,4,8,11-tetraazacyclotetradecane) correspond to not-interwoven 2D coordination polymers forming 3D subnets which in complexes of m-TATB3-are supramolecularly catenated due to 7C-7C stacking interactions between the central triazine rings of the anions. The main prerequisite for the formation of ionic structure of complexes [ZnL1(H2O)2][H(p-TATB)]center dot 2 center dot.5H(2)O and [NiL2(H2O)(2)][H(p-TATB)]center dot H2O (L2 - 1,4,8,11-tetraazaundecane) is hydrogen bonding with participation of the coordinated water molecules and carboxylic groups resulting in the formation of two catenated 3D subnets. Luminescent properties of zinc compounds were also studied and compared with those of the acids.