A fourfold interpenetrating three-dimensional cadmium(II) coordination polymer: synthesis, crystal structure and physical properties.

A novel three-dimensional CdII coordination framework, namely, poly[{µ-bis[4-(2-methylimidazol-1-yl)phenyl] ether-κ2N3:N3'}(µ-naphthalene-1,4-dicarboxylato-κ3O1:O4,O4')cadmium(II)], [Cd(C12H6O4)(C20H18N4O)]n or [Cd(1,4-NDC)(BMIOPE)]n, where 1,4-H2NDC is naphthalene-1,4-dicarboxylic acid and BMIOPE is bis[4-(2-methylimidazol-1-yl)phenyl] ether, has been prepared and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy and thermogravimetric analysis. The compound displays a novel fourfold interpenetrating diamond-like network. In addition, it not only shows a strong fluorescence emission in the solid state, but also exhibits excellent photocatalytic activity for the degradation of methylene blue (MB) at room temperature.

Acetic acid induced self-assembly of supramolecular compounds [Et4N]3[(WS4Cu2)2(mu-CN)3].2MeCN and [PPh4][WS4Cu3(mu-CN)2].MeCN from preformed clusters [A]2[WS4(CuCN)2] (A = Et4N, PPh4).

Reactions of two preformed trinuclear W/Cu/S clusters, [A](2)[WS(4)(CuCN)(2)] (1: A = Et(4)N; 2: A = PPh(4)), with different concentrations of acetic acid in MeCN generate two interesting 2D polymeric clusters [Et(4)N](3)[(WS(4)Cu(2))(2)(mu-CN)(3)].2MeCN (3), and [PPh(4)][WS(4)Cu(3)(mu-CN)(2)].MeCN (4), respectively. Compound 4 can also be readily obtained in a high yield from the reaction of 2 with equimolar [Cu(MeCN)(4)]PF(6) in MeCN. These compounds have been characterized by elemental analysis, IR spectra, thermal analysis, and single-crystal X-ray diffraction. An X-ray analysis reveals that compound 3 retains the WS(4)Cu(2) cluster core, which serves as a 3-connecting node to link equivalent nodes via single cyanide bridges, forming an anionic 2D (6,3) net. Compound 4 consists of a T-shaped WS(4)Cu(3) core, which also acts as a 3-connecting node, with links to 3 equivalent clusters either through single or double cyanide bridges, affording a different anionic 2D (6,3) network. The acetic acid induced aggregation of 3 and 4 from the two cluster precursors 1 and 2 suggests that this simple synthetic strategy is likely to be applicable to many related systems.

Bis(tetraphenylphosphonium) (micro-tetrathiotungstenio-kappa(4)S,S':S":S"')bis[(cyano-kappaC)cuprate](2-) acetonitrile solvate monohydrate.

The reaction of CuCN and KCN with (NH(4))(2)[WS(4)] followed by cation exchange with PPh(4)Br produced the title compound, (C(24)H(20)P)(2)[Cu(2)WS(4)(CN)(2)].CH(3)CN.H(2)O or (PPh(4))(2)[(NC)Cu(micro-S)(2)W(micro-S)(2)Cu(CN)].MeCN.H(2)O. In the structure of the dianion, [(NC)Cu(micro-S)(2)W(micro-S)(2)Cu(CN)](2-), the WS(4) moiety acts as a bidentate ligand that binds two CuCN groups, thus forming a slightly bent WCu(2) core with approximate D(2d) symmetry. The W-Cu distances are in the range 2.6463 (6)-2.6545 (6) A.