Assembly of trinuclear and tetranuclear building units of Cu2+ towards two 1D magnetic systems: synthesis and magneto-structural correlations.

Two new 1D coordination polymers, [Cu(3)(μ(3)-OH)(ppk)(3)(μ-N(CN)(2))(OAc)](n) (1) and {[Cu(4)(pdmH)(2)(pdm)(2)(μ(2)-OH)(H(2)O)]·ClO(4)}(n) (2) based on two different blocking ligands phenyl-2-pyridylketoxime (ppk) and pyridine-2,6-dimethanol (pdmH(2)) have been synthesized and were characterized by X-ray single crystal structural analysis. In compound 1, the hydroxido-bridged trinuclear core, {Cu(3)(μ(3)-OH)(ppk)(3)(OAc)}, acts as secondary building units and are connected by the N(CN)(2)(-) anions resulting in a one dimensional (1D) coordination polymer. The 1D coordination chains undergo π-π interactions giving rise to a 3D supramolecular framework. In compound 2, tetrameric [Cu(4)(pdmH)(2)(pdm)(2)(H(2)O)](2+) cores are linked via hydroxido groups forming a zigzag 1D coordination chain where non-coordinated ClO(4)(-) ions are intercalated between the chains. Variable temperature magnetic susceptibility study of suggests that Cu(II) ions in the trinuclear Cu(3)(μ(3)-OH) cores are antiferromagnetically coupled with J = -459.7 cm(-1) and g = 2.11 and the trinuclear cores are further weakly coupled antiferromagnetically (zj' = -5.25 cm(-1)) through the N(CN)(2)(-) bridging ligand. Investigation of the magnetic properties of reveals that Cu(II) ions are coupled antiferromagnetically in the tetranuclear core with J = -27.1 cm(-1) and g = 2.17; the Cu(II)(4) building units are further coupled antiferromagnetically with zj' = -9.65 cm(-1). The experimental magnetic behaviours of 1 and 2 are correlated by first principle DFT calculations which provide a qualitative understanding of the origin of antiferromagnetic interactions in both cases.