Ning‐Hai Hu

The novel binuclear neutral nickel(II) complex [((2,6-iPr2C6H3)NCH)C6H3ONi(PPh3)Ph]2 (5), based on the 3,3‘-bisalicylaldimine ligand, has been synthesized in high yield, and its structure has been confirmed by X-ray crystallography, elemental analysis, and 1H NMR and 13C NMR spectra. Used in the polymerization of ethylene as an active single-component catalyst, the complex exhibited a high catalytic activity of up to 4.55 × 105 g of PE/((mol of Ni) h), and polyethylenes with a weight-average molecular weight (M̄w) of up to 487.7 kg/mol and relatively broad molecular weight distribution (M̄w/M̄n = 2.8−3.8) were produced.

In this paper, four novel silver(I) sulfonate coordination polymers containing neutral ligands, namely, [Ag2L1(biim)2]·2H2O (1), AgL2(biim) (2), [Ag(HL3)(Pic)2]·H2O (3), and [Ag3(L3)(HL3)(4,4‘-bipy)3(H2O)2]·4H2O (4), have been synthesized [L1 = 3-carboxy-4-hydroxybenzenesulfonate, L2 = p-aminobenzenesulfonate, H2L3 = p-hydroxybenzenesulfonic acid, biim = 1,1‘-(1,4-butanediyl)-bis(imidazole), Pic = β-picoline, 4,4‘-bipy = 4,4‘-bipyridine]. For compounds 1 and 2, Ag(I) cations are bridged by biim ligands to form a one-dimensional (1D) “zigzag” chain, and L1 and L2 sulfonate ligands are not coordinated to the silver cation. Compound 3 has a dimeric structure in which two silver cations are bridged by two HL3 ligands. For compound 4, L3 ligand coordinates to a silver cation as a monodentate ligand, and Ag(I) cations are bridged by 4,4‘-bipy ligands to form a 1D chain. Compound 1 contains water dimers, while compound 4 contains water trimers. Compounds 1−3 display room-temperature photoluminescence.

Three novel supramolecular assemblies constructed from polyoxometalate and crown ether building blocks, [(DB18C6)Na(H(2)O)(1.5)](2)Mo(6)O(19).CH(3)CN, 1, and [(Na(DB18C6)(H(2)O)(2))(3)(H(2)O)(2)]XMo(12)O(40).6DMF.CH(3)CN (X = P, 2, and As, 3; DB18C6 = dibenzo-18-crown-6; DMF = N,N-dimethylfomamide), have been synthesized and characterized by elemental analyses, IR, UV-vis, EPR, TG, and single crystal X-ray diffraction. Compound 1 crystallizes in the tetragonal space group P4/mbm with a = 16.9701(6) A, c = 14.2676(4) A, and Z = 2. Compound 2 crystallizes in the hexagonal space group P6(3)/m with a = 15.7435(17) A, c = 30.042(7) A, gamma = 120 degrees, and Z = 2. Compound 3 crystallizes in the hexagonal space group P6(3)/m with a = 15.6882(5) A, c = 29.9778(18) A, gamma = 120 degrees, and Z = 2. Compound 1 exhibits an unusual three-dimensional network with one-dimensional sandglasslike channels based on the extensive weak forces between the oxygen atoms on the [Mo(6)O(19)](2)(-) polyoxoanions and the CH(2) groups of crown ether molecules. Compounds 2 and 3 are isostructural, and both contain a novel semiopen cagelike trimeric cation [(Na(DB18C6)(H(2)O)(2))(3)(H(2)O)(2)](3+). In their packing arrangement, an interesting 2-D "honeycomblike" "host" network is formed, in which the [XMo(12)O(40)](3)(-) (X = As and P) polyoxoanion "guests" resided.

A new family of self-immobilized ethylene polymerization catalysts, derived from neutral, single-component salicylaldiminato phenyl nickel complexes, is described.