Assembly of the highest connectivity Wells-Dawson polyoxometalate coordination polymer: the use of organic ligand flexibility

Through tuning the length of flexible bis(triazole) ligands and different metal ion coordination geometries, four Wells-Dawson polyoxoanion-based hybrid compounds, [Cu-6(btp)(3)(P2W18O62)] center dot 3H(2)O (1) (btp = 1,3-bis(1,2,4-triazol-1-yl)propane), [Cu-6(btb)(3)((P2W18O62) center dot 2H(2)O (2), [Cu-3(btb)(6)(P2W18O62)] center dot 6H(2)O (btb = 1,4-bis(1,2,4-triazol-1-yl)butane) (3), and [Cu-3(btx)(5.5)((P2W18O62) center dot 4H(2)O (btx = 1,6-bis(1,2,4-triazol-1-yl)hexane) (4), were synthesized and structurally characterized. in compound 1, the metal-organic motif exhibits a ladder-like chain, which is further fused by the ennead-dentate [P2W18O62](6-) anions to construct a 3D structure. In compound 2, the metal-organic motif exhibits an interesting Cu-btb grid layer, and the ennead-dentate polyoxoanions are sandwiched by two Cu-btb layers to construct a 3D structure

Topological Diversity of Coordination Polymers Containing the Rigid Terephthalate and a Flexible N,N'-Type Ligand: Interpenetration, Polyrotaxane, and Polythreading

Reactions of zinc(II) or cadmium(II) salts with terephthalic acid (H(2)tp) and 1,3-bis(4-pyridyl) propane (bpp) have afforded four coordination polymers at room temperature, [Zn(mu-tp)(mu-bpp)](n)center dot 2nH(2)O (1), [Cd-2(mu-tp)(2)(mu-bpp)(3)](n)center dot 2nH(2)O (2), [Cd(mu-tp)(mu-bpp)(H2O)](n)center dot nH(2)O (3), and [Cd-2(mu-tp)(mu-bpp)(2)(bpp)(2)Br-2](n) (4). Single-crystal X-ray diffraction has revealed interesting topological features for these compounds.

Self-assembly of p-sulfonatocalix[4]arene and a Ag-hmt coordination polymer into a porous structure

A novel porous material constructed from p-sulfonatocalix[4]arene molecules and a Ag-I coordination polymer has been structurally characterized. The porous supramolecular complex features a bilayer arrangement of p-sulfonatocalix[4]arene molecules linked by a Ag-I-hmt (hmt: hexamethylene- tetramine) coordination polymer through metal-ligand bonding, hydrogen bonding and host-guest interactions.

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.

Construction of coordination networks with high connectivity: a new 8-connected self-penetrating network based on tetranuclear metal clusters

Two highly connected cobalt(II) and zinc(II) coordination polymers with tetranuclear metal clusters as the nodes of network have been prepared, being the first example of an 8-connected self-penetrating net based on a cross-linked alpha-Po subnet.

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 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.

Poly[[diaqua-mu-4,4 '-bipyridine-dinitratodi-mu-L-tyrosinato-dicopper(II)]: a chiral two-dimensional coordination polymer

The title compound, [Cu-2(C9H10NO3)(2)(NO3)(2)(C10H8N2)-(H2O)(2)](n), contains Cu-II atoms and L-tyrosinate (L-tyr) and 4,4'-bipyridine (4,4'-bipy) ligands in a 2:2:1 ratio. Each Cu atom is coordinated by one amino N atom and two carboxylate O atoms from two L-tyr ligands, one N atom from a 4,4'-bipy ligand, a monodentate nitrate ion and a water molecule in an elongated octahedral geometry. Adjacent Cu atoms are bridged by the bidentate carboxylate groups into a chain. These chains are further linked by the bridging 4,4'-bipy ligands, forming an undulated chiral two-dimensional sheet. O-H center dot center dot center dot O and N-H center dot center dot center dot O hydrogen bonds connect the sheets in the [100] direction. This study offers useful information for the engineering of chiral coordination polymers with amino acids and 4,4'-bipy ligands by considering the ratios of the metal ion and organic components.

Constructing mixed-metal coordination polymers from copper(II)-pyridinedicarboxylate metalloligands

In the mixed-metal complex catena-poly[bis[diaquasilver(I)] [bis[aquacopper(II)]-mu(3)-pyridine-2,5-dicarboxylato-2': 1: 1'kappa N-5,O-2: O-5: O-5, O-5'-mu-pyridine-2,5-dicarboxylato-2: 1 kappa(4) N, O-2: O-5, O-5'-disilver(I)-mu(3)-pyridine-2,5-dicarboxylato-1: 1': 2 '' kappa(5) O-5, O-5': O-5: N, O-2-mu pyridine-2,5-dicarboxylato-1': 20 ''kappa(4) O-5, O-5': N, O-2] hexahydrate], {[Ag(H2O)(2)][AgCu(C7H3NO4)(2)(H2O)] center dot 3H(2)O}(n), a square-pyramidal Cu-II center is coordinated by two N atoms and two O atoms from two pyridine-2,5-dicarboxylate (2,5-pydc) ligands and a water molecule, forming a [Cu(2,5-pydc)(2)-( H2O)](2-) metalloligand. One Ag I center is coordinated by five O atoms from three 2,5-pydc ligands and, as a result, the [Cu(2,5-pydc)(2)(H2O)](2-) metalloligands act as linkers in a unique mu(3)-mode connecting Ag-I centers into a one-dimensional anionic double chain along the [101] direction.

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.

Supramolecular isomerism in zinc hydroxide coordination polymers with pyridine-2,4-dicarboxylic acid: Two polymorphs with centrosymmetric two-dimensional and acentric three-dimensional coordination networks

Reactions of Zn(BF4)(2) and pyridine-2,4-dicarboxylic acid (2,4-pydcH(2)) in the presence of 1,2-bis( 4-pyridyl) ethylene or 1,3-bis(4-pyridyl) propane under hydro(solvo) thermal conditions yielded two polymorphic metal-organic coordination polymers formulated as Zn-2(OH)(2)(2,4-pydc) (1 and 2). Polymorph 1 features a two-dimensional (2-D) layer-like structure that is constructed by 2,4-pydc ligands bridging between the Zn-OH-Zn double-chain units. Each single Zn-OH-Zn chain is composed of mu(2)-OH groups connecting trigonal bipyramidal and tetrahedral Zn centers. Polymorph 2 is a 3-D coordination polymer containing 2-D Zn-OH-Zn sheets that consist of mu(2)- and mu(3)-OH groups and trigonal bipyramidal Zn centers. The sheets are pillared by 2,4-pydc ligands to form an acentric structural architecture. 1 and 2 are rare examples that the two polymorphs exhibit a centrosymmetric 2-D coordination network and an acentric 3-D coordination network, respectively. The different structures lead to differences in photoluminescent properties and thermal stabilities for 1 and 2.

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.

The first polyoxometalate polymer constructed by assembly of the heptamolybdic anion and copper coordination groups

The first example of one-dimensional organic-inorganic polymetallic coordination polymer based on heptamolybdate anions, formulated (NH4)[Cu(en)(2)][Na(en)Cu(en)(2)(H2O)(Mo7O24)].4H(2)O (en = ethylenediamine) (1) has been hydrothermally synthesized and characterized by element analysis, IR, EPR, CV and single crystal X-ray diffraction. The structure of 1 is fabricated by self-assembly of integrated heptamolybdic anions without collapse of primary structure and copper-ethylenediamine(en) coordination groups into one-dimensional zigzag-shaped chains.