Magnetic Coupling between Copper(II) Ions Mediated by Hydrogen-Bonded (Neutral) Water Molecules

A new hydrogen-bonded dinuclear copper(II) coordination compound has been synthesized from the Schiff-base ligand 6-(pyridine-2-ylhydrazonomethyl)phenol (Hphp). The molecular structure of [Cu-2(php)(2)(H2O2)(2)(ClO4)](ClO4)- (H2O) (1), determined by single-crystal X-ray diffraction, reveals the presence of two copper(II) centers held together by means of two strong hydrogen bonds, with O center dot O contacts of only 2.60-2.68 angstrom. Temperature-dependent magnetic susceptibility measurements down to 3 K show that the two metal ions are antiferromagnetically coupled (J = -19.8(2) cm(-1)). This exchange is most likely through two hydrogen-bonding pathways, where a coordinated water on the first Cu, donates a H bond to the O atoms of the coordinated php at the other Cu. This strong O center dot H (water) bonding interaction has been clearly evidenced by theoretical calculations. In the relatively few related cases from the literature, this exchange path, mediated by a (neutral) coordinated water molecule, was not recognized.

Diacetatobis[2-(2-furyl)-1H-imidazo[4,5-f]-[1,10]phenanthroline]cadmium(II)

In the title complex, [Cd(C2H3O2)(2)(C17H10N4O)(2)], the central Cd-II ion (site symmetry 2) shows an uncommon eight-coordinate CdN4O4 coordination geometry arising from two N,N-chelating 2-(2-furyl)-1H-imidazo[4,5-f]-1,10-phenanthro-line molecules and two O, O-bidentate acetate anions.

PH-Dependent syntheses and structures of two Copper(II)/Phenanthroline/p-Sulfonatocalix[4]arene supramolecular compounds with 1D water-filled channels

Two copper-organic framework supramolecular assemblies of p-sulfonatocalix[4]arene and 1,10-phenanthroline Cu-2[C12H8N2][C28H20S4O16][H2O](23.5) (1) and Cu-3[C12H8N2](3)[C28H19S4O16]Cl[H2O](17.6) (2) were obtained by pH-dependent synthesis at room temperature. Both structures show ID water-filled channels (rectangular shape in I and triangular in 2) with the solvent-accessible volume occupying 30.8% (1) and 24.2% (2) of the unit-cell volume, respectively. The calixarene molecules in both structures assume analogous cone shapes of C-2 nu symmetry instead of the conventional C-4 nu symmetry. Their connecting to different amounts of copper/phenanthroline cations leads to the formation of different structures.

Self-assembly of a water chain with tetrameric and decameric clusters in the channel of a mixed-valence (CuCuII)-Cu-I complex

The reaction of Cu(BF4)(2) with pyridine-2,6-dicarboxylic acid (H(2)pydc) and trans-1,2-bis(4-pyridyl)ethylene (bpe) under hydrothermal conditions afforded a porous mixed-valence (CuCuII)-Cu-I coordination polymer. Coexistence of tetrameric and decameric water clusters within the channels of the complex leads to a novel water chain. The metal-organic framework provides both hydrophilic and hydrophobic environments for stabilizing the clusters and retains its integrity upon dehydration and rehydration.

Syntheses and crystal structures of [Mn(H2O)(4)(bpy)]L center dot 4H(2)O, [Mn(H2O)(4)(bpy)]L ' center dot 4H(2)O (H2L = SUCCINIC ACID, H2L ' = FUMARIC ACID)

Reactions of freshly prepared M(OH)(2-2x)(CO3)(x) (.) yH(2)O (M = Mn, Zn) and 4,4'-bipyridine (bpy) with succinic acid (H2L) or famaric acid (H2L') in CH3OH-H2O afforded [Mn(H2O)(4)(bpy)]L (.) 4H(2)O, 1, [Mn(H2O)(4)(bpy)]L' (.) 4H(2)O, 2 and [Zn(H2O)(4)(bpy)]L (.) 4H(2)O, 3. The three coordination polymers are isostructural and consist of (1)(infinity)[M(H2O)(4)(bpy)(2/2)](2+) cationic chains, crystal H2O molecules and dicarboxylate anions (succinate or fumarate anions). Within the chains, the metal atoms are each octahedrally coordinated by four aqua oxygen atoms and two pyridyl nitrogen atoms from two 4,4'-bipyridine ligands. The crystal H2O molecules are hydrogen bonded to dicarboxylate anions to form ribbon-like anionic chains. The cationic and anionic chains are interconnected via hyqrogen bonds to generate a 3D network. Crystal data: 1 triclinic, P (1) over bar, a = 7.235(1), b = 7.749(2), c = 10.020(2) Angstrom, alpha = 79.95(3), beta = 88.79(3), gamma = 71.39(3)degrees, V = 523.9(2) Angstrom(3) and D-cal = 1.494 g cm(-3) for Z = 1; 2 triclinic, P (1) over bar, a = 7.127(1), b = 7.800(2), c = 9.945(2) Angstrom, alpha = 80.26(3), beta = 87.86(3), gamma = 72.69(3)degrees, V = 520.2(2) Angstrom(3) and D-cal = 1.498 g cm(-3) for Z = 1; 3 triclinic, P (1) over bar, a = 7.189(1), b = 7.764(2), c = 9.843(2) Angstrom, alpha = 79.16(3), beta = 87.80(3), gamma = 71.29(3)degrees, V = 510.9(2) Angstrom(3) and D-cal = 1.559 g cm(-3) for Z = 1.

微孔配位聚合物的合成与表征

微孔配位聚合物是近年来被广泛研究的领域之一，这类材料在储气材料等领域的应用前景逐步被开发出来。作为良好的储气材料，配位聚合物必须具有规则的孔道结构和良好的稳定性。本论文以合成多维孔道新化合物为目标，成功合成并解析出13个微孔配位聚合物。对化合物的元素分析、红外和TGA等进行了表征，同时对部分化合物的紫外和荧光性质进行了测定。 首先，对微孔配位聚合物的最新研究动态进行了简要介绍，并对一些代表性化合物的结构类型、性能以及应用等进行了归纳总结。然后介绍了合成配位聚合物晶体的实验原理，化合物的表征方法。 本论文在水热条件下，成功合成了13个新化合物分别为：(C19H15N4)2(NO3)2∙3H2O (3-3)，(C19H15N4)2[CdCl4] (3-4)，2Ag(tta)∙AgNO3 (3-5)，Cu8(tta)15(H2O)Cl (3-6)，[Zn(5-CH3-tta)2(isoH)2] (BDC) (3-7)，Pb[(PO3)2C(OH) CH3]•H2O (4-1)，Ni(C5H4NCOO)2∙4H2O (5-2)，Co(C5H4NCOO)2(H2O)2∙2H2O (5-3)，[CdCl2(C13H12N2O)2] (5-4)，{C6H4(COOH)S}2 (5-5)，(Deta)(ClO4)NO3 (5-6)，(NH4)2[-Mo8O26] (6-1) 和 (NH4)2[Mo4O13] (6-2)。其中化合物3-5，3-6和3-7是由四氮唑和金属构筑的纳米孔道三维化合物；化合物3-3，3-4，5-2，5-3，5-4，5-5和5-6均具有超分子网络结构；4-1是有机膦酸为配体的二维层状化合物，是首例(5,5)连接的(47•63) (48•62)拓扑网络。化合物6-1是一维无限链骨架的钼酸盐，6-2是二维层状的钼酸盐，显示了不寻常的(32•4)(32•53•8)(3•42•54•6•82)(34•43•54•64) 拓扑网络。最后对论文进行概括总结，并展望了下一阶段的工作安排。

Constructing porous frameworks from one-dimensional cobalt-oxygen clusters and pyridinedicarboxylate ligands adopting two rare coordination modes

A porous material with cobalt-oxygen cluster framework has been synthesized hydrothermally, which possesses large and rigid channels and manifests strong antiferromagnetic interactions, and the pyridinedicarboxylate ligand exhibits two types of rare coordination modes.

A one-dimensional network from the self-assembly of gold nanoparticles by a necklace-like polyelectrolyte template mediated by metallic ion coordination

A new approach to one-dimensional organization of gold nanoparticles (2-4 nm) is described, using poly(4-vinylpyridine) (P4VP) molecular chain as a template with the mediation of free Cu2+ ion coordination. The assembly was conducted on freshly prepared mica surfaces and in aqueous solution, respectively. The surface assembly was characterized by tapping mode atomic force microscopy (AFM), observing the physisorbed molecules in their chain-like conformation with an average height of 0.4 nm.

Coordination-Induced Formation of One-Dimensional Nanostructures of Europium Benzene-1,3,5-tricarboxylate and Its Solid-State Thermal Transformation

Novel one-dimensional europium benzene-1,3,5-tricarboxylate compressed nanorods have been synthesized oil it large scale through direct precipitation in solution phase under moderate conditions without the assistance of any surfactant, catalyst, or template. The obtained nanorods have widths of about 50-100 not, thicknesses of 10-20 nm, and lengths ranging from a few hundred nanometers to several micrometers. X-ray powder diffraction. elemental analysis, Fourier transform infrared Studies, and thermogravimetric and differential thermal analysis show that the nanorods have the structural formula of Eu(1,3,5-BTC)center dot 6H(2)O. Upon UV excitation, these nanorods exhibit a highly efficient luminescence. which comes from the Eu3+ ions. Moreover, Eu2O3 nanorods Could also be obtained via a thermal decomposition method using the corresponding complex as a precursor. This synthetic route is promising for the preparation of other one-dimensional crystalline nanomaterials because of its simplicity and the low cost of the starting reagents.

High-dimensional assembly depending on polyoxoanion templates, metal ion coordination geometries, and a flexible bis(imidazole) ligand

By introducing the flexible 1,1'-(1,4-butanediyl)bis(imidazole) (bbi) ligand into the polyoxovanadate system, five novel polyoxoanion-templated architectures based on [As8V14O42](4-) and [V16O38Cl](6-) building blocks were obtained: [M(bbi)(2)](2)[As8V14O42(H2O)] [M = Co (1), Ni (2), and Zn (3)], [Cu(bbi)](4)[As8V14O42(H2O)] (4), and [Cu(bbi)](6)[V16O38Cl] (5). Compounds 1-3 are isostructural, and they exhibit a binodal (4,6)-connected 2D structure with Schlafli symbol (3(4)center dot 4(2))(3(4)center dot 4(4)center dot 5(4)center dot 6(3))(2), in which the polyoxoanion induces a closed four-membered circuit of M-4(bbi)(4). Compound 4 exhibits an interesting 3D framework constructed from tetradentate [As8V14O42](4-) cluster anions and cationic ladderlike double chains. There exists a bigger M-8(bbi)(6)O-2 circuit in 4. The 3D extended structure of 5 is composed of heptadentate [V16O38Cl](6-) anions and flexural cationic chains; the latter consists of six Cu(bbi) segments arranged alternately. It presents the largest 24-membered circuit of M-24(bbi)(24) so far observed made of bbi molecules and transition-metal cations. Investigation of their structural relations shows the important template role of the polyoxoanions and the synergetic interactions among the polyoxoanions, transition-metal ions, and flexible ligand in the assembly process.

A two-dimensional molybdenum (V) phosphate with covalently bonded transition metal coordination complexes: hydrothermal synthesis and structure characterization of Na-2[{Mn(phen)(2)(H2O)}{Mn(phen)(2)}(3){Mn (Mo12O24)-O-V (HPO4)(6)(PO4)(2)(OH)(6)}] center dot 4H(2)O (phen=1,10-phenanthroline)

An organic-inorganic hybrid molybdenum phosphate, Na-2[{Mn(phen)(2)(H2O)} {Mn(phen)(2)}(3){(MnMo12O24)-O-v (HPO4)(6)(PO4)(2) (OH)(6)}] . 4H(2)O (phen=1,10-phenanthroline), involving molybdenum present in V oxidation state and covalently bonded transition metal coordination complexes, has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Deep brown-red crystals are formed in the triclinic system, space group P (1) over bar, a=16.581(l)Angstrom, b=18.354(1)Angstrom, c=24.485(2)Angstrom, alpha=80.589(l)degrees, beta=71.279(1)degrees, gamma=67.084(1)degrees, V=6493.8(8)Angstrom(3), Z=2, lambda(MoKalpha)=0.71073Angstrom (R(F)=0.0686 for 29,053 reflections). Data were collected on a Bruker Smart Apex CCD diffractometer at 293 K in the range of 1.76 < theta < 28.06degrees using omega-2theta scans technique. The structure of the title compound may be considered to be based on {Mo6O12(HPO4)(3)(PO4)(OH)(3)} units bonded together with {Mn(phen)(2)} subunits into a two-dimensional network. Two types of tunnels are observed in the solid of the title compound.

Lattice Boltzmann study of hydrodynamic effects in lamellar ordering process of two-dimensional quenched block copolymers

By incorporating self-consistent field theory with lattice Boltzmann method, a model for polymer melts is proposed. Compared with models based on Ginzburg-Landau free energy, our model does not employ phenomenological free energies to describe systems and can consider the chain topological details of polymers. We use this model to study the effects of hydrodynamic interactions on the dynamics of microphase separation for block copolymers. In the early stage of phase separation, an exponential growth predicted by Cahn-Hilliard treatment is found. Simulation results also show that the effect of hydrodynamic interactions can be neglected in the early stage.

Synthesis and structure of new low dimensional polymeric haloplumbate(II) complexes [Pb4Br12(C40H40N8)] and [Pb4Cl12(C40H40N8)]center dot H2O

New low dimensional polymeric haloplumbate(II) complexes of the dication of (4,4'-bis(imidazolyl-ylmethyl)biphenyl) were synthesised and their crystal structures determined. Complex 1, [Pb4Br12(C40H40N8)], has cis-edge-shared, octahedral, lead bromide double chains. In compound 2 [Pb4Cl12(C40H40N8)]center dot H2O, the inorganic chains are corner-shared, square pyramidal chains of lead chloride. In both compounds the organic ammoniums form regular layers that alternate with the inorganic chains.

A copper/p-sulfonatocalix[6]arene/phenanthroline supramolecular compound with 1D [Cu-2-calixarene](n) coordination chains

A supramolecular complex [Cu(phen)(2)H2O]{[Cu(phen)(H2O)](2)[C6AS]}center dot 2.5H(2)O (phen = 1,10'-phenanthroline and C6AS = p-sulfonatocalix[6]arene) has been synthesized under hydrothermal condition, and characterized by IR spectroscopy, TG analysis and single crystal X-ray diffraction. In the structure, unprecedented 1D ({[Cu(phen)(H2O)](2)[C(6)AS]}(2-))(n) coordination chains (exactly being belts) are stacked into some 2D layers by the pi center dot center dot center dot pi stacking interactions, which are further interconnected into a 3D extended structure by hydrogen bonding.

A three-dimensional metal-organic framework based on a triazine derivative: syntheses, structure analysis, and sorption studies

A novel metal-organic framework [Cu-3(m-TATB)(2)Py(CH3OH)(2)] (1) constructed of a triazine-based trigonal-planar ligand, 3,3',3 ''-s-triazine-2,4,6- triyltribenzoate (m-H(3)TATB), has been synthesized and structurally characterized. Compound 1 features three-dimensional (3D) channels and cavities together, and exhibits high carbon dioxide sorption at normal pressure.