Recently some of us reported a series of one-dimensional compounds comprising square planar tetraazamacrocycle copper(II) building blocks forming Cu(II)–SCN–M–NCS–Cu(II) chains, where M = Mn, Co, Ni [5] and [6]. The thiocyanate ligand shows ambident ability with an end-on or an end-to-end coordination modes leading to compounds of various dimensionalities. In this kind of systems, the thiocyanate ligand may act as a mediator for the magnetic interactions between the paramagnetic copper(II) and metallic centers.