Pts Topology Research Articles

Metal–organic frameworks based on naphthalene-1,5-diyldioxy-di-acetate: structures, topologies, photoluminescence and photocatalytic properties

Using a novel hemi-rigid ditopic ligand, naphthalene-1,5-diyldioxy-di-acetic acid (H2L), five metal(II)-complexes formulated as Mn(L)(DMF) (1), Cd(L)(H2O)2 (2), Pb(L)(DMF) (3), Cd(L)(phen) (phen = phenanthroline) (4) and Cd5(L)5(2,2′-bpy)2 (2,2′-bpy = 2,2′-bipyridine) (5) have been hydro(solvo)thermally synthesized and structurally characterized by single-crystal X-ray diffraction. Complex 1 features a 4-nodal (4,6)-connected three-dimensional (3D) network with an unusual (42.63.8)(45.6)(48.66.8)2 topology, complex 2 exhibits a uninodal 3-connected two-dimensional (2D) framework with a (82.10) topology, complex 3 shows a 2-nodal (3,4)-connected 3D fsh-3,4-P21/c net with a (83)2(85.10) topology, complex 4 presents a 2-nodal 3D architecture with (42.84)-ptS topology, and complex 5 shows a novel 6-nodal (3,4,5,6)-connected 3D framework with an unusual (42.6)2(42.83.10)(43.62.85)2(43.62.8)2 (45.6.84)2(46.87.102) topology. H2L displays different coordination modes in the five complexes. Complexes 1–3 are hybrid metal oxides based on extended inorganic metal–oxygen–metal chains. The H2L ligand has the preference for the formation of M–O–M linkage in the absence of a N-donor. Complex 1 exhibits antiferromagnetic property and complexes 2–5 show different photoluminescence and photocatalytic properties.

Effect of metal ions on the structures of metal–organic frameworks based on mixed ligands

Abstract Two metal–organic frameworks, namely, [Zn(L)(phen)(H 2 O)] n ( 1 ) and [Cd(L)(phen)] n ( 2 ), where H 2 L = 2,2′-(naphthalene-1,5-diylbis(oxy))diacetic acid and phen = 1,10-phenanthroline, have been synthesized under hydrothermal conditions and characterized by single crystal X-ray diffraction analyses, powder X-ray diffraction and thermogravimetric analysis. Compound 1 can be described as a 3D supramolecular architecture formed via the strong π–π interactions. While, compound 2 , obtained by changing the metal ions, exhibits a 3D metal–organic frameworks of PtS topology with the square window (the dimensions is 11.454 × 25.847 A). The different structures between 1 and 2 indicate that metal ions have significant effects on the final complexes. Moreover, compounds 1 and 2 show good luminescent properties in the solid state at room temperature.

Selective Incorporation of Auxiliary Organic Ligands in Metal–Organic Frameworks Based on Twisted Π-Shaped Building Blocks

Hydrothermal reactions of Cu(II) salts and 2,2′,4,4′-biphenyltetracarboxylic acid (2,2′,4,4′-H4bptc) in the presence of pyridyl ligands yielded three isomorphous 3D metal–organic coordination polymers formulated as [Cu2(2,2′,4,4′-bptc)(L)x]·H2O [x = 2 for L = pyridine; x = 1 for L = bis(4-pyridyl)ethene and bis(4-pyridyl)ethane]. In the structure, the distorted paddlewheel [Cu2(COO)4] motif and the twisted Π-shaped 2,2′,4,4′-bptc serve as dissimilar 4-connected SBUs to generate a 3D [Cu2(2,2′,4,4′-bptc)] mother framework with the PtS topology, which selectively accommodates pyridine or bis(pyridyl) ligands of appropriate size.

Three interpenetrated copper(II) coordination polymers based on a V-shaped ligand: Synthesis, structures, sorption and magnetic properties

Three new CuII coordination polymers, [Cu2(oba)2(H2O)(DMF)]·3H2O (1), [Cu4(oba)4(DMF)4]·4H2O·DMF (2) and [Cu2(oba)(hmp)2] (3) (H2oba = 4,4′-oxybis(benzoic acid), Hhmp = 2-pyridine methanol, DMF = N,N′-dimethylformamide) were synthesized by solvothermal reactions and characterized by single-crystal X-ray diffraction. Both complexes 1 and 2 take three-dimensional (3D) three-fold interpenetrating PtS topology with 1D channels. In complex 3, Cu4 clusters were formed by the chelating hmp ligands, and then the clusters were further linked by oba ligands to form a 3D three-fold interpenetrating dia topology network. For 2, N2 sorption shows type I isotherm with BET surface areas of 562 m2 g−1 and Langmuir surface area of 747 m2 g−1, respectively. At 77 and 87 K, the hydrogen uptakes of complex 2 are 0.89 wt% and 0.57 wt%, respectively. Magnetic investigation showed the ferromagnetic coupling between CuII ions and very weak antiferromagnetic interaction between Cu4 clusters in complex 3.

Synthesis and characterization of a three dimensional zinc(II) metal-organic framework constructed from flexible 1,2,3,4-tetra-(4-pyridyl)-butane ligand

Employing the flexible tetrapodal ligand 1,2,3,4-tetra-(4-pyridyl)-butane (TPB) along with fumaric acid (H 2FMA) as the bridges, a metal-organic framework of [Zn(TPB)(FMA)·(2H 2O)] ( 1) was obtained and characterized by elemental analysis, spectral method (IR), single crystal X-ray diffraction, thermal gravimetric analysis (TGA) and fluorescent property. This polymer exhibits a three dimensional (3D) dense network with an interesting (4,4)-connected PtS topology. It also displays good thermal stability and strong photoluminescence in the blue region band. Thus it may serve as a candidate of thermally stable blue-light-emitting photoluminescent material.

Temperature-controlled synthesis of two novel coordination polymers modeled by semi-rigid tetrapyridines

Solvothermal reactions of tetrakis(4-pyridyloxymethylene)methane (TPOM) with deprotonated benzoate (L1) in the presence of acetate (L2) of copper in H2O/CH3OH with reactant ratio 1 : 2 : 2 under different synthesis temperatures produced two new complexes, namely, {[Cu2(TPOM)2(L1)2(L2)2]·Guest}n (1), and {[Cu4(TPOM)(L1)2(L2)4(OH)2]·6H2O}n (2). These complexes were characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. Complex 1 reveals a 3D crystal structure with a novel 2,3,4-connected 3-nodal topology constructed from the connection of Cu centers and TPOM ligands, which neutralized the mono-dentate carboxylates from different ligands coordinated to Cu ions. Complex 2 exhibits a distinct 3D framework with 2-nodal PtS topology, constructed from the connection of neutral Cu4 SBUs and TPOM ligands. The increasing reaction temperature must be responsible for the versatile coordination modes of carboxylates in 2 compared to the ones in 1, resulting in the formation of the distinct crystal structure. In addition, magnetic investigations on complex 2 revealed antiferromagnetic intra-tetramer interactions through the mixed hydroxo and carboxylato bridges.

Porous Coordination Polymers of Transition Metal Sulfides with PtS Topology Built on a Semirigid Tetrahedral Linker

Four novel porous metal sulfide coordination polymers, [M(tpom)S(x)(SH)(y)] x z(H(2)O) (metal-sulfide frameworks, denoted MSF-n, n = 1, Cd; 2, Mn; 3, Fe; 4, Co; x = 0, y = 2 for 1, 2, and 4 and x = 0.54, y = 1.46 for 3), were solvothermally prepared by using a quadridentate linker, tetrakis(4-pyridyloxymethylene)methane (tpom), in the presence of organic sulfur compound under an acidic conditions. MSF-n (n = 1-4) is isostructural and built upon the tetrahedral tpom linker and square planar MS(x)(SH)(y) unit, which form a binodal 4,4-connected porous framework with a 2-fold interpenetrated 4(2)8(4)-pts net. With rectangular pore channels of about 5 x 6 A(2) (interatomic distances between the nearest protruding H atoms across) running along both the crystallographic a and b directions, MSF-n possesses permanent porosity with a BET surface area of 575, 622, 617, and 767 m(2)/g for MSF-1, -2, -3, and -4, respectively, as estimated from N(2) adsorption measurements. MSF-n (n = 1-4) has hydrogen storage capacities of 1.03, 1.37, 1.29, and 1.58 wt % at 77 K and 1 atm, respectively, each corresponding to 2.0 H(2) molecules per unit cell. In addition, MSF-n (n = 1-4) can adsorb 24.1, 25.0, 21.6, and 24.1 wt % of carbon dioxide and 6.0, 6.1, 5.6, and 6.4 wt % of methane, respectively, at room temperature and 20 atm.

Generation of 2D and 3D (PtS, Adamantanoid) Nets with a Flexible Tetrahedral Building Block

The self-assembly of the flexible tetrahedral linker tetrakis[4-(carboxyphenyl)oxamethyl]methane acid with various transition metals (Cu, Co, and Mg) results in a 2D layered structure and 3D frameworks with PtS and adamantanoid topology. The PtS net exhibits permanent porosity, as confirmed by BET and gas adsorption experiments.

Metal-dependent dimensionality in coordination polymers of a semi-rigid dicarboxylate ligand with additional amide groups: Syntheses, structures and luminescent properties

Three new coordination polymers, [CdL(H 2O) 3·H 2O] n ( 1), [MnL(H 2O) 2] n ( 2) and [ZnL] n ( 3) (L = 2,2′-[1,4-bis(-benzamido)]diacetate) have been hydrothermally synthesized. Complex 1 and complex 2 are 1-D infinite zigzag chain and 2-D rectangular grid networks, respectively, in which are further stabilized by hydrogen bonds, thus affording two 3-D supramolecular frameworks. Complex 3 exhibits a (4, 4)-connected PtS topology. Moreover, an unusual phenomenon has been observed that the dimension of these coordination polymers gradually increases with the decrease of coordination numbers of metal ions. In addition, complex 1 exhibits a strong blue luminescence in the solid state at room temperature and may be potential candidate for luminescent materials.

Rational synthesis of a microporous metal–organic framework with PtS topology using a semi-rigid tetrahedral linker

The assembly of a semi-rigid tetrahedral linker tetrakis[4-(carboxyphenyl)oxamethyl]methane acid (H4X) with CuII yields a binodal 4,4-connected coordination framework of distorted PtS topology, which exhibits permanent porosity confirmed by gas adsorption experiments of N2, H2, CO2, and CH4.

Three-Dimensional Metal-Organic Frameworks Based on Functionalized Tetracarboxylate Linkers: Synthesis, Strucures, and Gas Sorption Studies

New tetracarboxylate ligands with dihydroxy (L(1)) and crown ether functionalities (L(2)) have been synthesized and treated with Cu(II) and Zn(II) ions to generate three-dimensional (3D) metal-organic frameworks (MOFs) with the compositions of [Cu(2)(L(1))(H(2)O)(2)].14DMF.10H(2)O, 5, [Cu(2)(L(2))(H(2)O)(2)].12DMF, 6, [Zn(6)(mu(4)-O)(L(1))(2)(L(1)-H(2))].35DMF.27H(2)O, 7, and [Zn(3)Na(2)(L(2))(2)(DMF)(2)].7DMF.14H(2)O, 8. The four compounds show different framework structures with different connectivities. Compound 5 exhibits the PtS topology whereas compound 6 has a [6(4).8(2)](3)[6(6)] topology. Compound 7 adopts a new [4.6(5)][4(2).6(8)][4(4).6(2)][4(5).6][4(8).6(10).8(3)] topology while compound 8 exhibits the Flu topology. The porosity and H(2) uptake were studied by gas sorption experiments and grand canonical Monte Carlo (GCMC) simulations. Compound 5 shows a high H(2) uptake of up to 1.11 wt % at 77 K.

Bis{μ-(E)-2-[(2-pyridylamino)(2-pyridylimino)methyl]benzato}bis[acetatozinc(II)] tetrahydrate

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.