RESUMEN
Five new organic-inorganic hybrid compounds based on [P2W18O62]6- (abbreviated as {P2W18}) and several types of transition metal complexes (TMCs) have been synthesized and characterized by IR, UV-Vis, XRD, cyclic voltammetry measurements and single crystal X-ray diffraction analysis. [Cu(phen)2][Cu(phen)(H2O)3][Cu(phen)2(H2O)][P2W18O62]·8H2O (1) (phen = 1,10-phenanthroline) is a {P2W18} bi-supported complex of phen, while [Cu(2,2'-bpy)(H2O)2]2[Cu(2,2'-bpy)2][P2W18O62]·3.5H2O (2) (2,2'-bpy = 2,2'-bipyridine) is a 1-D chain structure formed by {P2W18} and copper complexes of 2,2'-bpy. [Ag(2,2'-bpy)2]5[HP2W18O62]·H2O (3), [Ag(2,2'-bpy)(H2O)]2[Ag(2,2'-bpy)]2[Ag2(2,2'-bpy)3][P2W18O62] (4), and [Ag(2,2'-bpy)(H2O)]3[Ag2(2,2'-bpy)3][Ag(2,2'-bpy)][P2W18O62]·H2O (5) are constructed from {P2W18} and silver complexes of 2,2'-bpy. Compounds 4 and 5 are novel dimers of {P2W18} joined by silver complexes, while compound 3 contains two different kinds of silver complexes, forming a novel supramolecular structure. Each of the five compounds is formed by {P2W18} and more than one type of TMC. The formation mechanism of these compounds has been carefully discussed. In addition, we also synthesized two supramolecular structures based on {P2W18} and organic moieties: [H6P2W18O62](phen)5.5 (6) and [H6P2W18O62](phen)3·43H2O (7). The catalytic properties of these compounds were also tested.
RESUMEN
The title complex, [Ni2(C9H4O6)2(C13H8N4)2(H2O)4]·2H2O, bis-(µ-5-carb-oxy-benzene-1,3-di-carboxyl-ato-κ(2) O (1):O (1'))bis-[di-aqua(1H-imidazo[4,5-f][1,10]phenanthroline-κ(2) N (7),N (8))nickel(II)] di-hydrate, was obtained under solvothermal conditions by the reaction of benzene-1,3,5-tricarboxylic acid (H3BTC) with Ni(NO3)2 in the presence of 1H-imidazo[4,5-f][1,10]phenanthroline (IP). The crystal has triclinic (P-1) symmetry with a centrosymmetric binuclear nickel(II) cluster. The Ni(II) atom is coordinated by two N atoms from a chelating 1H-imidazo[4,5-f][1,10]phenanthroline ligand, two carboxyl-ate O atoms from two 5-carb-oxy-benzene-1,3-di-carboxyl-ate ligands and two water mol-ecules in a slightly distorted octa-hedral geometry. Two carboxyl-ate groups bridge two Ni(II) cations, forming the binuclear complex. Extensive N-Hâ¯O, O-Hâ¯O and O-Hâ¯N hydrogen bonding is present in the crystal structure, forming a three-dimensional supermolecular framework. Weak π-π stacking is observed between parallel HBTC(2-) and IP ring systems, the face-to-face separation being 3.695â (2)â Å.
RESUMEN
Two unprecedented 3D porous anionic metal-organic frameworks, [Me2NH2]2[Cd2(bpdc)3].4dma 1 and [Me2NH2]2[Cd2(NH2bdc)3].4dma 2 (dma = N,N'-dimethylacetamide, bpdc = 4,4'-biphenyldicarboxylate, NH(2)bdc = 2-amino-1,4-benzenedicarboxylate) have been solvothermally synthesized with a dimethylammonium cations template. Both 1 and 2 are constructed from low-symmetry SBUs. 1 has a chiral framework with helical nanotube-like channels, and 2 has a MOF-5-like motif. The fluorescence, N2 adsorption and ion-exchange properties for 1 have been examined.
Asunto(s)
Compuestos Organometálicos/química , Compuestos de Amonio Cuaternario/química , Aniones/química , Cadmio/química , Cristalografía por Rayos X , Modelos Moleculares , Estructura Molecular , Compuestos Organometálicos/síntesis química , Porosidad , Propiedades de SuperficieRESUMEN
Two POM-pillared 3D porous compounds, [Cu(I)Cu(II)(Cu(II)fcz)(2)(H(2)O)(5)(PMo(VI)(10)Mo(V)(2)O(40))].6H(2)O () and [Cu(I)(2)(Cu(II)fcz)(2)(H(2)O)(2)(PMo(VI)(8)V(V)(3)V(IV)(3)O(42))].6H(2)O () (Hfcz = fluconazole, (1-(2,4-difluorophenyl)-1,1-bis[(1H-1,2,4-triazol-1-yl)methyl]benzyl alcohol) have been constructed based on different polyanions, (Cufcz)(2)(2+) macrocations and copper cations by the hydrothermal method. The (Cufcz)(2)(2+) macrocations link Cu cations to generate a 2D wavelike cationic sheet. Then the POM anions act as pillars to the cationic sheet to form different POM-pillared 3D frameworks. In compound 2 , the polyanion exhibits a rare coordination mode and acts as a penta-dentate ligand, which acts as to pillars to the cationic sheet to form an unprecedented 3D (3,4,5,6)-connected open framework with (3.6.7)(3(2).6.7(3))(3(3).4.6(2).7(3).8)(3(4).4(2).6(2).7(6).8)(3(2).6(2).7(6).8(4).10) topology. In compound , polyanions covalently link cationic sheets to extend to an unusual 3D (3,4,6)-connected framework with the (5(2).6)(5(2).6(2).7.9)(5(4).6(4).7(4).9(3)) topology. To the best of our knowledge, it is the first time that POM-pillared 3D metal-organic frameworks have been realized by combining POMs with deliberately designed macrocations and transition-metal ions, using a rational approach for synthesis of POM-based open metal-organic frameworks. In addition, the electrochemical behaviors of compounds 1 and 2 have been investigated.
RESUMEN
A 3D chiral nanoporous coordination framework consisting of homochiral nanotubes assembled from octuple helices with a 19.4 A by 22.4 A aperture is formed by the parallel alignment of eight infinite helical chains.
RESUMEN
A novel cadmium(II) coordination polymer, poly[[[bis(4,4'-bipyridine)cadmium(II)]-mu(3)-4,4'-dicarboxybiphenyl-3,3'-dicarboxylato] 0.35-hydrate], {[Cd(C(16)H(8)O(8))(C(10)H(8)N(2))(2)].0.35H(2)O}(n), was obtained by reaction of Cd(CH(3)COO)(2).3H(2)O, 4,4'-bipyridine (4,4'-bpy) and biphenyl-3,3',4,4'-tetracarboxylic acid (H(4)L) under hydrothermal conditions. Each Cd(II) atom lies at the centre of a distorted octahedron, coordinated by four O atoms from three H(2)L(2-) ligands and N atoms from two monodentate 4,4'-bpy ligands. Each H(2)L(2-) ligand coordinates to three Cd(II) atoms through two carboxylate groups, one acting as a bridging bidentate ligand and the other in a chelating bidentate fashion. Two Cd atoms, two H(2)L(2-) anions and four 4,4'-bpy ligands form a ring dimer node, which links into an extended broad zonal one-dimensional chain along the c axis.
RESUMEN
A novel copper(II) coordination polymer, poly[[[aquacopper(II)]-mu3-2,2'-bipyridyl-3,3'-dicarboxylato-kappa4N,N':O:O'] dihydrate], {[Cu(C12H6N2O4)(H2O)].2H2O}n, was obtained by the reaction of CuCl2.2H2O and 2,2'-bipyridyl-3,3'-dicarboxylic acid (H2L) in water. In the molecule, each Cu(II) atom is five-coordinated and lies at the centre of a square-pyramidal basal plane, bridged by three L ligands to form a two-dimensional (4,4)-network. Each L moiety acts as a bridging tetradentate ligand, coordinating to three Cu(II) atoms through its two aromatic N atoms and two O atoms of the two carboxyl groups. The two-dimensional square-grid sheets superimpose in an off-set fashion through the inorganic water layer.
RESUMEN
Hydrolysis of dibenzyltin dichloride in ethanol has been found to give an unprecedented carbonate anion (CO(3) (2-))-bridged double-ladder organooxotin cluster, [(R(2)SnO)(3)(R(2)SnOH)(2)(CO(3))](2) (1, R = C(6)H(5)CH(2)), with five tin atoms in each ladder. With the aim of obtaining organooxotin clusters with large cavities suitable for host-guest chemistry, we used 1,1'-ferrocenedicarboxylic acid (H(2)L(a)) and hexanedioic acid (H(2)L(b)) to replace the carbonate anions (CO(3) (2-)), and thereby clusters [(R(2)SnO)(3)(R(2)SnOH)(2)L(a)](2) (2) and [(R(2)SnO)(3)(R(2)SnOH)(2)L(b)](2) (3) were obtained. When 1 was treated with benzoic acid (HL(c)) in different stoichiometric ratios (1:4, 1:10), ladder cluster (R(2)SnO)(3)(R(2)SnOH)(2)(L(c))(2) (4) and drum cluster [RSn(O)L(c)](6) (5) were obtained. Through the hydrolysis of Cy(2)SnCl(2) (Cy = C(6)H(11)) and (C(6)H(5)CH(2))(2)SnCl(2), two interesting ethanolate-modified clusters [Cy(2)(C(2)H(5)O)SnOSn(C(2)H(5)O)Cy(2)](2) (6) and [(R(2)SnO)(3)(R(2)SnOH)(R(2)SnOC(2)H(5))(CO(3))](2) (7) were obtained. All the tin atoms in these ladder clusters are five-coordinate surrounded by two alkyl groups and three O atoms, and have distorted trigonal-bipyramidal coordination environments with two carbon atoms and one O atom in the equatorial positions and two O atoms in the axial positions. The structures of all these compounds have been established by single-crystal X-ray diffraction analyses.