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ABSTRACT: In this Article, self-assembly of AgX (X = NO3(-) and ClO4(-)) salts and four flexible unsymmetrical bis(pyridyl) ligands, namely, N-(pyridin-2-ylmethyl)pyridin-3-amine (L1), N-(pyridin-3-ylmethyl)pyridin-2-amine (L2), N-(pyridin-4-ylmethyl)pyridin-2-amine (L3), and N-(pyridin-4-ylmethyl)pyridin-3-amine (L4), results in the formation of eight helical silver(I) coordination polymers, [Ag(L)(NO3)]n [L = L1 (1), L2 (2), L3 (3), L4 (4)] and [Ag(L)(ClO4)]n [L = L1 (5), L2 (6), L3 (7), L4 (8)], which have been characterized by elemental analysis, IR, TG, PL, and powder and single-crystal X-ray diffraction. The alternating one-dimensional (1-D) left- and right-handed helical chains are included in achiral complexes 1-3 and 5-8. By contrast, the ligand L4 only alternately bridges Ag(I) cation to form the 1-D right-handed helical chain in complex 4. The pitches of these helical chains locate in the range 5.694(5)-17.016(6) Å. Meanwhile, the present four unsymmetrical bis(pyridyl) ligands in the eight complexes present diverse cis-trans and trans-trans conformation and facilitate the construction of helical structures. Moreover, the solid-state luminescent emission intensities of the perchlorate-containing complexes are stronger than those of nitrate-containing complexes at room temperature.
Inorganic Chemistry 05/2013; · 4.60 Impact Factor
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ABSTRACT: Nucleobase tautomers and their metal complexes have attracted considerable attention due to their fascinating architectures along with wide applications. In this paper, 4,6-dihydroxypyrimidine (H(2)DHP), an analogue of uracil and thymine, was employed to react with the vital elements of alkaline earth metals in an aqueous solution and lead to the formation of four novel complexes, [Mg(HDHP)(2) (H(2)O)(4)] (1), [Ca(HDHP)(2)(H(2)O)(3)](n)·nH(2)O (2), [Sr(HDHP)(2)(H(2)O)(3)](n)·nH(2)O (3), and [Ba(HDHP)(2)(H(2)O)(2)](n)·nH(2)O (4), which have been characterized by elemental analysis, IR, TG, UV-Vis, PL, powder and single-crystal X-ray diffraction and progressively evolve from zero-dimensional (0D) mononuclear, one-dimensional (1D) zig-zag double chain, two-dimensional (2D) double layer, to a three-dimensional (3D) porous network along with the increase of cation radii. This tendency in dimensionality follows salient crystal engineering principles and can be explained by considering factors such as hard-soft acid-base principles and cation radii. The deprotonated H(2)DHP ligand exhibits four new coordination modes, namely, O-monodentate (complex 1), N,O-chelating (complexes 2 and 3), O,O-bridging (complexes 2 and 3), and κ(1)O:κ(2)O-bridging mode (complex 4). Interestingly, the structural investigation indicates that the HDHP(-) monoanion shows three unusual types of tautomers, which are essential for the diagnosis of disease and investigation of medicine. Furthermore, the four complexes exhibit strong blue emission compared to free H(2)DHP ligand at room temperature and may be potential candidates for blue fluorescent biological materials used in organisms.
Dalton Transactions 05/2012; 41(27):8354-60. · 3.84 Impact Factor
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ABSTRACT: Self-assembly of silver(I) salts and three ortho-hydroxyl and carboxyl groups decorated arenesulfonic acids affords the formation of nine silver(I)-sulfonates, (NH(4))·[Ag(HL1)(NH(3))(H(2)O)] (1), {(NH(4))·[Ag(3)(HL1)(2)(NH(3))(H(2)O)]}(n) (2), [Ag(2)(HL1)(H(2)O)(2)](n) (3), [Ag(2)(HL2)(NH(3))(2)]·H(2)O (4), [Ag(H(2)L2)(H(2)O)](n) (5), [Ag(2)(HL2)](n) (6), [Ag(3)(L3)(NH(3))(3)](n) (7), [Ag(2)(HL3)](n) (8), and [Ag(6)(L3)(2)(H(2)O)(3)](n) (9) (H(3)L1 = 2-hydroxyl-3-carboxyl-5-bromobenzenesulfonic acid, H(3)L2 = 2-hydroxyl-4-carboxylbenzenesulfonic acid, H(3)L3 = 2-hydroxyl-5-carboxylbenzenesulfonic acid), which are characterized by elemental analysis, IR, TGA, PL, and single-crystal X-ray diffraction. Complex 1 is 3-D supramolecular network extended by [Ag(HL1)(NH(3))(H(2)O)](-) anions and NH(4)(+) cations. Complex 2 exhibits 3-D host-guest framework which encapsulates ammonium cations as guests. Complex 3 presents 2-D layer structure constructed from 1-D tape of sulfonate-bridged Ag1 dimers linked by [(Ag2)(2)(COO)(2)] binuclear units. Complex 4 exhibits 3-D hydrogen-bonding host-guest network which encapsulates water molecules as guests. Complex 5 shows 3-D hybrid framework constructed from organic linker bridged 1-D Ag-O-S chains while complex 6 is 3-D pillared layered framework with the inorganic substructure constructing from the Ag2 polyhedral chains interlinked by Ag1 dimers and sulfonate tetrahedra. The hybrid 3-D framework of complex 7 is formed by L3(-) trianions bridging short trisilver(I) sticks and silver(I) chains. Complex 8 also presents 3-D pillared layered framework, and the inorganic layer substructure is formed by the sulfonate tetrahedrons bridging [(Ag1O(4))(2)(Ag2O(5))(2)](∞) motifs. Complex 9 represents the first silver-based metal-polyhedral framework containing four kinds of coordination spheres with low coordination numbers. The structural diversities and evolutions can be attributed to the synthetic methods, different ligands and coordination modes of the three functional groups, that is, sulfonate, hydroxyl and carboxyl groups. The luminescent properties of the nine complexes have also been investigated at room temperature, especially, complex 1 presents excellent blue luminescence and can sensitize Tb(III) ion to exhibit characteristic green emission.
Inorganic Chemistry 11/2011; 50(24):12562-74. · 4.60 Impact Factor
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ABSTRACT: Eight novel silver(I) complexes constructed from ortho-hydroxyl arenesulfonic acids, [Ag(NH3)2]·(HL1) (1), [Ag2(L1)]n (2), [Ag2(HL2)(H2O)3]n (3), [Ag(HL3)(MeCN)2]n (4), [Ag2(HL3)2]n (5), [Ag2(HL4)(H2O)3]n (6), {(NH4)2·[Ag(NH3)2]2}·2(H2L5)·5H2O (7), and [Ag(H2L5)0.5]n (8) (H2L1 = 2-hydroxyl-5-methyl-benzenesulfonic acid; H3L2 = 2-hydroxyl-5-methyl-1,3-benzenedisulfonic acid; H2L3 = 2-hydroxyl-5-bromo-benzenesulfonic acid; H3L4 = 2-hydroxyl-5-bromo-1,3-benzenedisulfonic acid; H4L5 = 2,4-dihydroxyl-1,5-benzenedisulfonic acid), have been synthesized and characterized by elemental analysis, infrared, thermogravimetric analysis, UV–vis, photoluminescence (PL), powder and single-crystal X-ray diffraction. Complex 1 has a three-dimensional (3-D) supramolecular framework containing right-handed helical channels through the hydrogen-bonding interactions. Complex 2 exhibits a wavelike “inorgano-organic” layer structure, in which the inorganic substructures consist of Ag1 polyhedral chains linked through Ag2 dimers by sharing two vertexes and two edges. Complex 3 presents the 3-D pillared layered structure, and the inorganic layer substructures are formed by sulfonate tetrahedra bridging Ag–O chains through two vertexes. The sulfonate group in complex 4 bridges adjacent Ag(I) ions to generate a one-dimensional chain structure. Complex 5 exhibits a planar “inorgano-organic” layer structure, in which the inorganic substructures consist of chains of vertex-sharing Ag1 polyhedra and edge-sharing Ag2 polyhedra interlinked by sharing edges. Complex 6 shows a similar 3-D pillared layered structure with complex 3. In complex 7, the free water molecules, ammonium cations, and sulfonate groups form a 3-D hydrogen-bonding host network which encapsulates the [Ag(NH3)2]+ cations as guests. Complex 8 also displays a 3-D pillared layered structure with a two-dimensional (2-D) inorganic substructure formed by Ag(I) polyhedral chains interlinked by sharing edges. The structural diversities and evolutions can be attributed to the different ligands and the coordination modes of the sulfonate groups which are influenced by the hydroxyl groups. The solid-state luminescent properties have also been investigated at room temperature.
05/2011;
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ABSTRACT: The first metal-organic framework containing an unprecedented in situ-generated C-substituted hexamethylenetetramine ligand has been successfully prepared by the reaction of silver nitrate, 4-formylbenzoic acid and hexamethylenetetramine under traditional solution conditions, which holds the unusual (3,4)-connected topological network.
Dalton Transactions 02/2011; 40(6):1224-6. · 3.84 Impact Factor
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ABSTRACT: Self-assembly of four bis(pyridyl) ligands with longer flexible spacer: 1,4-bis(3-pyridylaminomethyl)benzene (L1), 1,4-bis(2-pyridylaminomethyl)benzene (L2), 1,3-bis(3-pyridylaminomethyl)benzene (L3) and 1,3-bis(2-pyridylaminomethyl)benzene (L4), and CuX (X = Br and I) leads to the formation of eight [Cu(n)X(n)]-based (X = Br and I; n = 1, 2, and 4) complexes, [Cu(2)I(2)L1(PPh(3))(4)] (1), [Cu(4)Cl(2)Br(2)(L4)(2)(PPh(3))(6)]·(CH(3)CN)(2) (2), [Cu(2)I(2)(L3)(2)] (3), {[Cu(2)Br(2)L2(PPh(3))(2)]·(CH(2)Cl(2))(2)}(n) (4), [CuIL1](n)·nCH(2)Cl(2) (5), [CuIL1](n) (6), [CuIL4](n) (7) and [Cu(2)I(2)L4](n) (8), which have been synthesized and characterized by elemental analysis, IR, TG, powder and single-crystal X-ray diffraction. Structural analyses show that the eight complexes possess an increasing dimensionality from 0D (1-3) to 1D (4) to 2D (5-8), in which 1 and 2 contain a CuX unit, 2-7 contain a Cu(2)X(2) unit and 8 contains a Cu(4)X(4) unit. Such evolvement indicates that the conformation of flexible bis(pyridyl) ligands and the participation of triphenylphosphine (PPh(3)) as a second ligand take an essential role in the framework formation of the Cu(i) complexes. Moreover, a pair of symmetry-related L3 ligands in complex 3 coordinate to the rhomboid Cu(2)I(2) dimer to form "handcuff-shaped" dinuclear structures, which are further joined together through intermolecular N-HI hydrogen bonds to furnish a 2D (4,4) layer. Although complexes 5 and 6 exhibit a similar 2D (4,4) layer constructed from L1 ligand bridging [Cu(2)I(2)](n) units, the different packing fashion of the layers leads to the formation of 3D porous frameworks of 5 and dense 3D frameworks of 6. The "twisted-boat" conformation of the Cu(4)I(4) tetramer unit in complex 8 has not been reported so far.
Dalton Transactions 10/2010; 39(42):10038-50. · 3.84 Impact Factor
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ABSTRACT: The first example of rare-earth organic frameworks with 3-aminopyrazine-2-carboxylic acid (Hapca) was synthesized under hydrothermal conditions and characterized by elemental analysis, IR, PL, TG, powder and single-crystal X-ray diffraction. These ten complexes exhibit three different structure types with decreasing lanthanide radii: [La(apca)(3)](n) () for type I, {[Ln(apca)(ox)(H(2)O)(2)].H(2)O}(n) (Ln = Pr (2), Nd (3), ox = oxalate) for type II, and [Ln(2)(apca)(4)(OH)(2)(H(2)O)(2)](n) (Ln = Sm (4), Eu (5), Gd (6), Tb (7), Dy (8), Er (9), Y (10)) for type III. The structure of type I consists of 1D "snowflake" chains along a-axis, which are further interconnected by hydrogen bonds to produce a 3D sra net topology containing infinite (-C-O-La-)(n) rod-shaped SBU. Type II has 2D Ln-apca-ox 4(4)-net, in which a planar udud water tetramers (H(2)O)(4) are formed by coordinated and free water molecules. Type III also comprises of 2D 4(4)-layer network constructed from Ln-apca-OH. The structure diversity is mainly caused by the variation of coordinated ligand and lanthanide contraction effect. Remarkably, the oxalate in type II was in situ synthesized from 3-aminopyrazine-2-carboxylic acid through an oxidation-hydrolysis reaction. The luminescent investigations reveal that complex exhibits strong blue emission and complex exhibits characteristic luminescence of Eu(3+).
Dalton Transactions 07/2010; 39(27):6276-84. · 3.84 Impact Factor
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ABSTRACT: A series of silver(I) pyridone-sulfonates, namely [Ag5(HL1)3(NO3)2(H2O)]n (1) [Ag2(HL1)2]n.2nH2O (2), [Ag2(HL1)(NO3)]n (3), and [Ag3(HL2)2(NO3)(H2O)]n (4) (HL1 = 4(1H)-pyridone-3-sulfonate monoanion, HL2 = 2(1H)-pyridone-5-sulfonate monoanion), have been synthesized and characterized by elemental analyses, IR, TG, PL and X-ray analyses. Complex 1, which exhibits a novel continuous silver polyhedral framework containing four kinds of coordination spheres, has been recently reported. Complex 2 presents the first one-dimensional (1-D) "butterfly" array composed of SO3-bridged columns of Ag(I) ions and symmetric pendant organic groups in silver(I) sulfonates, while complex 3 possesses a two-dimensional (2-D) layer structure in which the inorganic network substructure consists of helical chains of edge-sharing Ag1 distorted octahedra linked through dimers of edge-sharing Ag2 distorted anti-trigonal prisms by sharing two corners and two edges. Replacing H2L1 by H2L2 leads to the formation of complex 4, a three-dimensional (3-D) pillared layered framework, which is also extended by the rare mu4 nitrate anion. In complexes 1-4, all the inorganic parts can be considered as being built up from versatile polyhedra of silver(I) centers by sharing corners, edges or faces. The sulfonic group shows some novel coordination modes, which is first reported here. Solid-state fluorescence quenching and thermal stability are discussed for all of these complexes.
Dalton Transactions 10/2009; · 3.84 Impact Factor
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ABSTRACT: The first continuous silver polyhedra framework containing four kinds of coordination spheres has been successfully prepared by the reaction of silver(I) nitrate and 4(1H)-pyridone-3-sulfonic acid. This polyhedra framework is constructed from four kinds of silver(I) polyhedra by sharing corners, edges and faces.
Dalton Transactions 03/2009; · 3.84 Impact Factor
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ABSTRACT: The Co(II) atom in the title complex, [CoCl(2)(C(4)H(5)N(3))(4)], exists in an all-trans Cl(2)N(4)Co octa-hedral geometry. The Co(II) atom lies on a special position of 2 site symmetry. Adjacent mol-ecules are linked by N-H⋯N and N-H⋯Cl hydrogen bonds into a three-dimensional network.
Acta Crystallographica Section E Structure Reports Online 01/2009; 65(Pt 12):m1502. · 0.35 Impact Factor
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ABSTRACT: The reaction of cobalt(II) sulfate and 2-amino-pyrazine affords the title salt, [Co(H(2)O)(6)][Co(C(4)H(5)N(3))(2)(H(2)O)(4)](SO(4))(2)·2H(2)O. The metal atoms in the tetra-aqua-coordinated and hexa-aqua-coordinated complex cations lie on centers of inversion in slightly distorted octa-hedral geometries. The cations, anions and solvent water mol-ecules are linked by O-H⋯O, O-H⋯N and N-H⋯O hydrogen bonds into a three-dimensional network.
Acta Crystallographica Section E Structure Reports Online 01/2009; 65(Pt 12):m1503. · 0.35 Impact Factor
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ABSTRACT: The reaction of manganese(II) sulfate and 2-amino-pyrazine affords the title salt, [Mn(H(2)O)(6)][Mn(C(4)H(5)N(3))(2)(H(2)O)(4)](SO(4))(2)·2H(2)O. The metal atoms in the tetra-aqua-coordinated and hexa-aqua-coordinated cations lie on centers of inversion in octa-hedral geometries. The cations, anions and solvent water mol-ecules are linked by O-H⋯O, N-H⋯O and O-H⋯N hydrogen bonds into a three-dimensional network.
Acta Crystallographica Section E Structure Reports Online 01/2009; 65(Pt 12):m1504. · 0.35 Impact Factor
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ABSTRACT: In the C(2)-symmetric dinuclear title complex, [Zn(2)(C(18)H(13)N(4)O(2))(2)(C(2)H(3)O(2))(2)] x 4 H(2)O, each Zn(II) ion is five-coordinated in a distorted trigonal bipyramidal fashion by one carboxylate O atom from one benzoate ligand, one imine N atom and two pyridyl N atoms from a second benzoate ligand, and one O atom from an acetate anion. The two Zn atoms are bridged by the two benzoate ligands, forming a dinuclear structure with a 14-membered macrocycle. Adjacent dinuclear units are further connected by extensive hydrogen bonds involving the solvent water molecules, giving a three-dimensional hydrogen-bonded framework. The framework can be regarded as an example of the four-connected node network of the PtS topology.
Acta crystallographica. Section C, Crystal structure communications 05/2008; 64(Pt 4):m182-4. · 0.78 Impact Factor
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ABSTRACT: The first two-dimensional lanthanum(III) coordination polymer, [La(1,5-NDS)1.5(H2O)5]n(1) (1,5-NDS2− = 1,5-naphthalenedisulfonate), was synthesized and structurally characterized by single-crystal X-ray diffraction analysis. The disulfonate ligands act in the η1:η1:μ2 and η1:η1:η1:μ3 binding modes to link the LaO9 tricapped trigonal prisms into a lamellar structure. It exhibits strong purple emission in the solid state.
Zeitschrift für anorganische Chemie 01/2008; 634(3):593 - 596.
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ABSTRACT: Three three-dimensional polymers, namely, [Zn(bpea)(H2O)]n (1), [Cd(bpea)(H2O)]n (2), and [Ni(bpea)(4,4′-bipyridine)(pyridine)]n (3) have been synthesized by the hydrothermal reaction of ZnII, CdII, or NiII salts with biphenylethene-4,4′-dicarboxylic acid. Complexes 1 and 2 have a 2-fold interpenetrating three-dimensional (3D) structure with Pts topology, and complex 1 exhibits strong fluorescent emission bands at 435 and 459 nm in the solid state at room temperature. Complex 3 is a 3D structure with an unprecedented 9-fold interpenetrated Ths topology.
01/2008;
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ABSTRACT: The Zn atom in the title compound, [Zn(C(7)H(5)O(3))(2)(C(12)H(8)N(2))(H(2)O)]·H(2)O, exists in a distorted cis-ZnN(2)O(4) octa-hedral coordination geometry. One of the 4-hydroxy-benzoate anions chelates in a bidentate manner whereas the other is monodentate. The complex mol-ecules are linked through the uncoordinated water mol-ecules into a hydrogen-bonded sheet structure.
Acta Crystallographica Section E Structure Reports Online 01/2008; 64(Pt 2):m422. · 0.35 Impact Factor
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ABSTRACT: The Zn atom in the title salt, [ZnCl(C(12)H(8)N(2))(2)(H(2)O)]Cl·C(3)H(7)NO, is chelated by two phenanthroline mol-ecules and is bonded to one chloride ion and one water mol-ecule, resulting in a ZnN(4)ClO octa-hedral coordination environment with the Cl and O atoms in a cis conformation. The cations and anions are linked by O-H⋯Cl hydrogen bonds across a center of inversion, forming a hydrogen-bonded dimeric association. The dimethyl-formamide solvent mol-ecule is disordered over two orientations in a 0.56 (1):0.44 (1) ratio.
Acta Crystallographica Section E Structure Reports Online 01/2008; 64(Pt 2):m423. · 0.35 Impact Factor
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ABSTRACT: The Co(II) atom in the title compound, [Co(C(8)H(5)O(3))(2)(H(2)O)(4)]·4H(2)O, which exists in an all-trans octa-hedral coordination geometry, lies on a center of inversion. The coordinated and uncoordinated water mol-ecules engage in extensive hydrogen-bonding inter-actions, forming a three-dimensional hydrogen-bonded network.
Acta Crystallographica Section E Structure Reports Online 01/2008; 64(Pt 3):m446. · 0.35 Impact Factor
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ABSTRACT: The Zn(II) atom in the title compound, [Zn(C(8)H(5)O(3))(2)(H(2)O)(2)], which lies on a twofold rotation axis, is coordinated by two monodentate carboxyl-ate groups and two water mol-ecules in a tetra-hedral geometry; the geometry is distorted towards octa-hedral owing to two long Zn⋯O(carbon-yl) contacts [2.512 (2) Å]. Hydrogen-bonding inter-actions give rise to a three-dimensional network. The formyl group is disordered approximately equally over two positions.
Acta Crystallographica Section E Structure Reports Online 01/2008; 64(Pt 3):m447. · 0.35 Impact Factor
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ABSTRACT: In the title complex, [Mn(SO4)(C(3)H(7)NO)(H2O)2]n, each Mn(II) ion has a distorted octahedral geometry formed by three O atoms of three different sulfate groups, one O atom of a dimethylformamide ligand and two water molecules. The sulfate groups act as tridentate bridging ligands connecting the Mn(II) ions into a two-dimensional layer structure which can be regraded as a 4.8(2) network.
Acta Crystallographica Section C Crystal Structure Communications 06/2007; 63(Pt 5):m225-7. · 0.52 Impact Factor
