Copper-organic coordination polymers with porous structures

Three copper coordination polymers containing organosulfur ligands ({[Cu-2(1)(bpsb)(3)(CIO4)](CIO4)}(n) (1), {[Cu-2(1)(bpsb)(3)CI](CIO4)}(n) (2), and {[Cu-Pi(bpb)(2)Br](CIO4).3dmf.MeCN}(n) (3) (bpsb 1,2-bis[(2-pyrimidinyl)sulfanylmethy-yl]benzene, bpb = 1,2-bis [(4-pyridyl) sulfanylmethyl]benzene, dmf = N, N-dimethylformamide)) were synthesized and characterized by X-ray structural analysis. Complexes 1 and 2 have similar structures. In both, each bpsb molecule exhibits an exo-bidentate coordination fashion and bridges 3-coordinated copper(I) and 4-coordinated copper(I) through pyrimidinyl rings. Thus, six copper(I) centers, three 3-coordinated and three 4-coordinated located at two different planes alternatively, are linked by six bpsb molecules forming a crown-like nanocavity; such nanocavities make up a 2-D lamellar structure. In complex 3, each copper(II) center adopts a distorted square pyramidal coordination mode; each bpb molecule acts as an exo-bidentate ligand through coordinating to copper(II) atoms in two different directions to form a square unit with solvent molecule guests. Such square units share copper atoms and generate a single-stranded infinite 1-D chain structure.