Ag(I)-mediated in situ dehydrogenative coupling of 3-amino-1,2,4-triazole into 3,3'-azobis(1,2,4-triazole) in Cd(II) coordination polymers.

Ag(I)-mediated in situ generation of 3,3'-azobis(1,2,4-triazole) (AzTAZ) from 3-amino-1,2,4-triazole (AmTAZ) through dehydrogenative coupling has been realized during the crystallization process of two Cd(II) coordination polymers with novel topological architectures: a (3, 4, 5)-connected (4 x 6(2))(2)(4 x 6(7) x 8(2))(2)(6(5) x 10) net for [Cd(2)(AmTAZ)(2)(AzTAZ)](n) (1) and a 4-connected (6(2) x 8(4))(6(4) x 8(2))(6(5) x 8)(2) net for [Cd(AzTAZ)(2)(H(2)O)](n) (2), whereas AmTAZ retains its original form in a heterometallic complex, [Ag(2)Cd(AmTAZ)(4)](n) (3).

Temperature-controlled syntheses of substituted 1,2,4-triazolelead(II) complexes: active lone pair and N-H...X (X = Cl, Br, I) hydrogen bonds.

Three isomorphous lead(II) complexes with a new {N(3)SX}-coordinated (X = Cl, Br, I) mode have been synthesized and characterized by X-ray diffraction. The structural analyses reveal that the coordination environment around the center metal is distinctly influenced by the stereochemical 6s(2) lone pair and N-H...X hydrogen bonds. Additionally, doubly deprotonated trzS(2-) (HtrzSH = 1,2,4-triazole-3-thiol) generated in situ via deamination and dehydrazination of ahtrzS(-) (ahtrzSH = 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole) was first observed in a semiconducting three-dimensional coordination network at higher reaction temperature.

Synthesis, structure, and luminescent properties of hybrid inorganic-organic framework materials formed by lead aromatic carboxylates: inorganic connectivity variation from 0D to 3D.

The hydro(solvo)thermal reactions of Pb(OAc)(2).3H(2)O with the aromatic carboxylic ligands 1,3,5-benzenetricarboxylic and 1,4-, 1,2-, and 1,3-benzenedicarboxylic acids (1,3,5-H(3)BTC; 1,4-, 1,2-, and 1,3-H(2)BDC) have yielded a family of inorganic-organic framework materials: [Pb(2)(1,3,5-BTC)(mu(3)-OH)(H(2)O)](n) (Iota), [NaPb(1,3,5-BTC)(H(2)O)](n) (IotaIota), [Pb(1,4-BDC)](n) (IotaIotaIota), [Pb(5)(1,2-BDC)(4)(OAc)(2)](n) (IV), and {[Pb(5)(1,3-BDC)(5)(H(2)O)(2)](2).H(2)O}(n) (V). These complexes have been characterized by means of single-crystal X-ray diffraction, X-ray powder diffraction, thermogravimetric analysis-mass spectrometry, and photoluminescence spectra. They are all three-dimensional structures except for two-dimensional IV. Topology analysis reveals that complexes I an V represent rare (4,8)-connected flu and (3,4)-connected zeolite-like nets, respectively. The five complexes exhibit diverse inorganic connectivity, including a 0D Pb(4)O(16) cluster for I, a 1D Pb-O-Pb chain for II, a 2D Pb-O-Pb network for III and IV, and an unprecedented 3D Pb-O-Pb framework for V. And the diversity in inorganic arrays leads to differences in luminescent properties of these complexes.

Controlled generation of acentric and homochiral coordination compounds from a versatile asymmetric ligand 4-(1H-1,2,4-triazol-3-yl)-4H-1,2,4-triazole.

Luminescent acentric and homochiral coordination compounds, which possess new topological networks, multiple helical structures and NLO properties, have been generated through the control of a versatile asymmetric ligand as well as inorganic anions, and this suggests a new protocol for preparing acentric and chiral materials.

Topology analysis and nonlinear-optical-active properties of luminescent metal-organic framework materials based on zinc/lead isophthalates.

Two 3D Zn(II) and Pb(II) isophthalates, [Zn(ip)]n (1) and [Pb4(mu4-O)(ip)3(H2O)]n (2) (H2ip = isophthalic acid), have been prepared under hydro(solvo)thermal conditions and characterized by single-crystal X-ray diffraction. The two complexes crystallize in different space groups (P4(3)2(1)2 for 1 and P2(1)/c for 2) and have different bridging modes of the ip ligand. The 3D framework of 1 is constructed by the interconnection of ZnO4 polyhedra via ip ligands, which represents a chiral net with PtS-type topology. In contrast, complex 2 is formed by the combination of Pb4O-cluster secondary building units and has a novel (3.4.5)(3(2).4(5).5(6).6(7).7(2)) topology, which is the first ever example of a (3,7)-connected net. Complex 1 displays a second harmonic generation efficiency of about 1.5 times that of KH2PO4. Optical properties and thermal stabilities of the two complexes have been studied. Additionally, the calculations of band structure and density of states of 1 have also been performed with the density functional theory method.

Synthesis, structure, and physical properties of a new anions-controlled Cd(II)-guanazole (3,5-diamino-1,2,4-triazole) hybrid family.

Nine members of a new anions-controlled Cd(II)-guanazole (3,5-diamino-1,2,4-triazole=Hdatrz) hybrid family, that is, [Cd3(datrz)6(H2O)2] (1), [Cd3(datrz)4F2] (2), [Cd5(datrz)4Cl4(OH)2] (3), [Cd5(datrz)4Br4(OH)2] (4), [Cd3(datrz)2(SO3)2].(H2O) (5), [Cd3(datrz)2(O2CMe)4] (6), [Cd(datrz)(O2CEt)] (7), [Cd(Hdatrz)(O2CtBu)2] (8), and [Cd(Hdatrz)2(H2Edta)] (9) have been synthesized by exploiting hydrothermal reactions of guanazole with suitable cadmium salts under appropriate reaction conditions. With effective control of inorganic or organic anions, the coordination diversity of the guanazole ligand in 1-9 manifests an unprecedented enrichment with five bridging modes varying from bidentate to quadridentate, two of which are first reported. Compound 1 is the first reported three-dimensional chiral complex constructed from the guanazole ligand which adopts a novel N1, N2, amino N-bridging mode. Halogen anions F-, Cl-, and Br- controlled compounds 2-4 are all three-dimensional, with their guanazole ligands possessing another novel quadridentate bridging mode. Sulfite anions controlled compound 5 displays a three-dimensional network with peculiar cage-like hexnuclear cadmium clusters. As for organic anions, low dimensional structures have been found for alkylcarboxylate anions MeCO2-, EtCO2-, and tBuCO2- controlled compounds 6, 7, and 8 (two-dimensional) and for H2Edta2- controlled compound 9 (zero-dimensional), and their guanazole ligands manifest low coordination numbers as well. These hybrid materials also present interesting structure-induced physical properties. The chiral compound 1 exhibits the second-order nonlinear optical properties at room temperature. Compounds 2-9 except 6 all exhibit photoluminescence of blue fluorescent emissions in the solid state at ambient temperature, which may be assigned to the intraligand pi-pi* transitions. Some structure related red or blue emission shifts have been investigated. Thermal studies show that most compounds of this study possess a high thermal stability.

New coordination motifs of melamine directed by N-H---X (X = Cl or Br) hydrogen bonds.

Unusual mu(2)- and mu(3)-coordination modes of melamine are found in two organic-inorganic hybrid copper halides, [Cu(2)Br(2)(MA)](n) (1) and [Cu(3)Cl(3)(MA)](n) (2) (MA = melamine), in which the MA ligand affords two N-heterocycle N atoms to link (Cu(2)Br(2))infinity stairs and serves as a novel mu(3) bridge to give a 3D framework, respectively.

A polar luminescent Zn polymer containing an unusual noninterpenetrated utp net.

A new Zn coordination polymer with the mixed ligands of 1,3,5-benzenetricarboxylate and 1,3-bis(4-pyridyl)propane has been hydrothermally synthesized, and an unusual distorted noninterpenetrated utp [or (10,3)-d] net has been defined.

A 3-D noninterpenetrating diamondoid network of a decanuclear copper(I) complex.

The solvothermal reaction of CuCl(2).2H(2)O with pyridine-4-thiol and ethanol yielded a novel photoluminescent 3-D polymeric complex with an interesting decorated diamondoid network that is constructed of decanuclear copper(I) cluster units and mu(4)-Cl ligands. The in situ generation of CuSO(4).5H(2)O implies the spontaneous occurrence of desulfurization and redox reactions in the present system.

4,4'-Thiodipyridinium tetrachlorocopper(II).

The title compound, (C(10)H(10)N(2)S)[CuCl(4)], was obtained by the reaction of cupric chloride with pyridine-4-thiol in a mixture of acetonitrile and tetrahydrofuran, suggesting that the desulfurization and coupling reactions of pyridine-4-thiol occurred in the presence of the Cu(2+) ion. X-ray diffraction analysis reveals the presence of one 4,4'-thiodipyridinium cation, H(2)bps(2+), and one [CuCl(4)](2-) anion. The cations interact with the anions via N-H...Cl hydrogen-bonding interactions to form a closed 'chair' conformation.

Poly[aquaneodymium(III)-mu5-2-oxido-5-sulfonatobenzoato].

The title compound, [Nd(C(7)H(3)O(6)S)(H(2)O)](n) or [Nd(SSA)(H(2)O)](n) (H(3)SSA is 5-sulfosalicylic acid), was synthesized by the hydrothermal reaction of Nd(2)O(3) with H(3)SSA in water. The compound forms a three-dimensional network in which the asymmetric unit contains one Nd(III) atom, one SSA ligand and one coordinated water molecule. The central Nd(III) ion is eight-coordinate, bonded to seven O atoms from five different SSA ligands [Nd-O = 2.405 (4)-2.612 (4) angstroms] and one aqua O atom [Nd-OW = 2.441 (4) angstroms].

Poly[[bis(pyridine-kappaN)copper(II)]-mu(3)-5-hydroxyisophthalato-kappa3O:O':O''].

In the title compound, [Cu(C(8)H(4)O(5))(C(5)H(5)N)(2)](n) or [Cu(OH-BDC)(py)(2)](n) (where OH-H(2)BDC is 5-hydroxyisophthalic acid and py is pyridine), the Cu atoms are coordinated by two N atoms from the pyridine ligands and by three O atoms from hydroxyisophthalate ligands in a highly distorted triangular bipyramidal environment, with Cu-O distances in the range 1.941 (4)-2.225 (5) A and Cu-N distances of 2.014 (6) and 2.046 (6) A. The [Cu(OH-BDC)](n) two-dimensional network is built up from interlocking 22-, 15- and eight-membered rings via sharing of Cu atoms and O-H...O hydrogen bonds. Consolidation of the packing structure is achieved by edge- or point-to-face C-H...pi interactions and offset or slipped pi-pi stacking interactions.

Hydrothermal syntheses, crystal structures, and properties of a novel class of 3,3',4,4'-benzophenone-tetracarboxylate (BPTC) polymers.

Three novel BPTC complexes, (H(2)BPTC)(4,4'-H(2)bpy)H(2)O (1), [Cd(2)Cu(HBPTC)(2)(mu(2)-4,4'-bpy)(2)(4,4'-bpy)(2)(H(2)O)(2)](n) (2), and [Co(3)(HBPTC)(2)(mu(2)-4,4'-bpy)(3)(H(2)O)(4)](n).2nH(2)O (3) (BPTC = 3,3',4,4'-benzophenone-tetracarboxylate and bpy = bipyridine), were hydrothermally synthesized. Complex 1, which is obtained as a coproduct during the syntheses of complexes 2 and 3, features a 2-D layered strong hydrogen bonding network with 2-fold interpenetration. Complex 2 has an unusual 2-D double-layered motif, which is linked together by Cu atoms in a face-to-face manner. It exhibits nanosized channels filled by 4,4'-bpy ligands. Three six-coordinated Co atoms in 3 are interlinked by HBPTC ligands to form a 2-D grid structure, which is further sustained by rigid 4,4'-bpy ligands into a 3-D open framework similar to CdSO(4) with the BPTC moieties situated in the tunnels. The thermal stabilities of complexes 1-3 were examined. The photoluminescence properties of complexes 1-2 and temperature-dependent magnetic susceptibility for 3 were also studied.

Poly[[[(1,10-phenanthroline-kappa2N,N')zinc(II)]-mu3-5-hydroxyisophthalato-kappa4O,O':O":O"'] monohydrate].

In the title compound, [[Zn(C8H4O5)(C12H8N2)].H2O]n or [[Zn(OH-BDC)(phen)].H2O]n (where OH-H2BDC is 5-hydroxyisophthalic acid and phen is 1,10-phenanthroline), the Zn atoms are coordinated by two N atoms from the phen ligands and by four O atoms from hydroxyisophthalate ligands in a highly distorted octahedral geometry, with Zn-O distances in the range 2.042 (4)-2.085 (5) A and Zn-N distances of 2.133 (5) and 2.137 (5) A. The [[Zn(OH-BDC)(phen)].H2O]n infinite zigzag polymer forms a helical chain of [Zn2(OH-BDC)2]n units. Face-to-face pi-pi interactions (3.60-3.75 A) occur between two phen rings belonging to the same helical chain. Consolidation of the packing structure is achieved by O-H...O hydrogen-bonding interactions between the carboxylate O atoms, the hydroxyl group and the water molecule, forming two-dimensional sheets.

Tetrakis(pyridinium-2-thiolato)zinc(II) dinitrate.

The crystal structure of the title compound, [Zn(C(5)H(5)NS)(4)](NO(3))(2), consists of a [Zn(C(5)H(5)NS)(4)](2+) (C(5)H(5)NS is pyridinium-2-thiolate) cation and two nitrate anions. The central Zn(II) atom lies at a site with imposed -4 symmetry and is surrounded by four S atoms [Zn-S = 2.3371 (5) A] from four symmetrical pyridinium-2-thiolate ligands in a distorted tetrahedral geometry. There are N-H.O hydrogen-bonding interactions between the pyridinium-2-thiolate ligands and nitrate O atoms. In addition, pi-pi interactions via aromatic N-containing ligands are discussed.

Polymeric (mu2-nitrato-kappa2O:O')(mu2-nitrato-kappa2O:O)(mu4-pyridinium-4-thiolato-kappa4S:S:S:S)disilver(I).

The title compound, [Ag(2)(NO(3))(2)(C(5)H(5)NS)](n), was obtained from the reaction of silver nitrate with bis(4-pyridyl) disufide (4-PDS) in a mixture of ethanol and water, which suggests that the disulfide bond of 4-PDS can be cleaved under mild conditions. The structure of the title compound is a two-dimensional infinite array in which the asymmetric unit contains two Ag atoms, a pyridinium-4-thiolate molecule and two nitrate groups. Each pyridinium-4-thiolate molecule acts as a mu(4) bridge, linking four Ag atoms, with Ag-S bond distances of 2.4870 (19), 2.5791 (19), 2.5992 (19) and 2.848 (2) A. The Ag.Ag distances lie in the range 2.889 (2)-3.049 (1) A.

A simultaneous redox, alkylation, self-assembly reaction under solvothermal conditions afforded a luminescent copper(I) chain polymer constructed of Cu3I4- and EtS-4-C5H4N+Et components (Et = CH3CH2).

A simultaneous redox, alkylation, self-assembly reaction under solvothermal conditions afforded a novel copper(I) chain polymer constructed of luminescent Cu3I4- and unprecedented EtS-4-C5H4N+Et components (Et = CH3CH2).

A novel ligand-unsupported 3D framework polymer of trimeric copper(I) and its NLO property.

A novel 3-D coordination polymer with trimeric copper (I) unit, [Cu(3)(CN)(IN)(2)](n)(IN = isonicotinate), was hydrothermally synthesized by the reaction of Cu(NO(3))(2).3H(2)O with isonicotinic and terephthalic acids. The structure was characterized to be a twofold interpenetrated 3-D coordination network polymer with two-coordinated copper(I). It has a powder SHG efficiency about that of KDP.

Catena-poly[[dichlorozinc(II)]-micro-1,3-di-4-pyridylpropane-kappa(2)N:N'].

The title compound, [ZnCl(2)(bpp)](n) (where bpp is 1,3-di-4-pyridylpropane, C(13)H(14)N(2)), has been prepared by the hydrothermal reaction of ZnCl(2) and bpp at 433 K. The Zn, Cl and central propyl C atom lie on the mirrors of the P2(1)/m space group. The molecular structure shows a weave-like polymeric chain. Each Zn atom is coordinated by two N atoms and two Cl atoms in a distorted tetrahedral geometry, with the Zn-N distance being 2.055 (5) A and the Zn-Cl distances being 2.239 (3) and 2.247 (2) A.