Synthesis, crystal structures, and properties of inorganic-organic hybrid complexes constructed from copper(II) macrocyclic fragment

Reaction of a macrocyclic copper(II) complex [Cu(L)](ClO4)2 · 3H2O (I) (L = 1,3,10,12,16,19-hexaazatetracyclotetracosane) with a hexapod carboxylate ligand H6TTHA (H6TTHA = 1,3,5-triazine-2,4,6-triamine hexaacetic acid) and a tripod carboxylate ligand H3TATB (H3TATB = 4,4′,4″-S-triazine-2,4,6-triyl-tribenzoic acid) yielded two mononuclear copper(II) complexes [Cu(L)][H4TTHA] · 4H2O (II) and [Cu(L)][HTATB] · 4H2O (III). The complexes I–III have been structurally characterized. The crystal structures of complexes II and III show the copper(II) ion has a distorted pentacoordinate square-pyramidal geometry with two secondary and two tertiary amines from the macrocyclic complex [Cu(L)]2+ and one oxygen atom from the carboxylate ligand group at the axial position. The UV-Vis spectra are utilized to discuss the hydrolysis of the complex II.