Preparation and Structural Features of Cu(I)Cu(II) Coordination Polymers Obtained by Using Tripodal Complexes as Bridging Ligands

A tripodal complex [CuCl(tpmtm)] (tpmtm: tris(2-pyrimidylthio)methanide) is used to synthesize coordination polymers. The tripodal complex unit worked as bidentate, tridentate, or tetradentate bridging ligands for [CunClm] units via coordination of three outer nitrogen atoms of the tpmtm ligand and also an axial chloro ligand. X-ray crystallography exhibited that obtained coordination polymers contained novel structures of [CunClm] moieties such as chloride-bridged linear CuICuIICuI and CuICuIICuIICuI and cage-shaped CuICuIICuIICuI mixed-valence copper cluster units. The relationship between the numbers of the outer coordination sites on the tripodal complex and structures of the coordination polymers is observed showing that participation in the coordination of two, three, or four outer coordination sites on the tripodal complex afforded the one-dimensional chain, two-dimensional sheet, or three-dimensional structures, respectively.