Pts Topology Research Articles

Anionic Porous Zn-Metalated Porphyrin Metal-Organic Framework with PtS Topology for Gas-Phase Photocatalytic CO2 Reduction.

Presented here are the synthesis and gas-phase photocatalytic CO2 reduction of an anionic porous Zn-metalated porphyrin metal-organic framework (MOF) induced by an ionic liquid. The desired CO2 affinity and deep conduction band position of the MOF catalyst provide strong kinetic and thermodynamic advantages for photocatalytic CO2 to CH4 conversion with high selectivity (∼70%) in H2O vapor.

Responsive Four-Coordinate Iron(II) Nodes in FePd(CN)4.

Metal node design is crucial for obtaining structurally diverse coordination polymers (CPs) and metal-organic frameworks with desirable properties; however, FeII ions are exclusively six-coordinated. Herein, we present a cyanide-bridged three-dimensional (3D) CP, FePd(CN)4 , bearing four-coordinate FeII ions, which is synthesized by thermal treatment of a two-dimensional (2D) six-coordinate FeII CP, Fe(H2 O)2 Pd(CN)4 ⋅4 H2 O, to remove water molecules. Atomic-resolution transmission electron microscopy and powder X-ray and neutron diffraction measurements revealed that the FePd(CN)4 structure is composed of a two-fold interpenetrated PtS topology network, where the FeII center demonstrates an intermediate geometry between tetrahedral and square-planar coordination. This four-coordinate FeII center with the distorted geometry can act as a thermo-responsive flexible node in the PtS network.

Highly Sensitive and Selective Luminescence Sensor Based on Two-Fold Interpenetrated MOFs for Detecting Glutamate in Serum.

Glutamate is a biomarker for many nervous system diseases, and sensitively detecting glutamate is meaningful in the clinic. Therefore, a unique 3D framework of Cd-MOF (1) is synthesized and characterized. A single-crystal X-ray study reveals that it is a two-fold interpenetration (4,4)-connected framework with a PtS topology, where a large 1D rhombic channel with a size of 8 × 14 Å exists and the total potential void volume can reach 62%. Luminescence results demonstrate that 1 has good luminescence stability and can sensitively detect glutamate in water with a detection limit of 1.15 × 10-7 mol/L, which makes it the most sensitive MOF-based luminescence sensor of glutamate to date. More importantly, it also can serve as a luminescence sensor to detect glutamate in serum, and the quenching concentration needs to be only 43.1 μmol/L, which is much lower than the harmful level of glutamate (400 μmol/L) in glioma patients' blood. Compound 1 can be used at least five cycles. These results show that 1 has a potential application in monitoring glutamate in clinical scenarios.

Temperature effect on the synthesis of two Ni-MOFs with distinct performance in supercapacitor

Two new metal-organic frameworks {[Ni0.5(DTA)0.5(H2O)]‧H2O}n (1) and [Ni(DTA)]n (2), where H2DTA = 2,5-di(1H-imidazol-1-yl)terephthalic acid, were constructed from the same reaction system at 120 °C and 180 °C, respectively. Different reaction temperatures were found to trigger different assembly processes and final structures. Single-crystal X-ray analyses show that compound 1 exhibits a 2D layered structure, further forming a 3D supramolecular by hydrogen bonding, while compound 2 shows 2-fold interpenetrating 3D framework with PtS topology. Compounds 1–2 have been evaluated as electrode materials for supercapacitors. The results show that compound 1 exhibits better electrochemical performance than 2. It may be ascribed to 2D layered structures facilitating electron transport and sufficient interlayer spaces available for the storage.

Heterometallic In(III)-Pd(II) Porous Metal-Organic Framework with Square-Octahedron Topology Displaying High CO2 Uptake and Selectivity toward CH4 and N2.

The targeted synthesis of metal-organic frameworks (MOFs) with open metal sites, following reticular chemistry rules, provides a straightforward methodology toward the development of advanced porous materials especially for gas storage/separation applications. Using a palladated tetracarboxylate metalloligand as a 4-connected node, we succeeded in synthesizing the first heterobimetallic In(III)/Pd(II)-based MOF with square-octahedron (soc) topology. The new MOF, formulated as [In3O(L)1.5(H2O)2Cl]·n(solv) (1), features the oxo-centered trinuclear clusters, [In3(μ3-O)(-COO)6], acting as trigonal-prismatic 6-connected nodes that linked together with the metalloligand trans-[PdCl2(PDC)2] (L4-) (PDC: pyridine-3,5-dicarboxylate) to form a 3D network. After successful activation of 1 using supercritical CO2, high-resolution microporous analysis revealed the presence of small micropores (5.8 Å) with BET area of 795 m2 g-1 and total pore volume of 0.35 cm3 g-1. The activated solid shows high gravimetric (92.3 cm3 g-1) and volumetric (120.9 cm3 cm-3) CO2 uptake at 273 K and 1 bar as well as high CO2/CH4 (15.4 for a 50:50 molar mixture) and CO2/N2 (131.7 for a 10:90 molar mixture) selectivity, with moderate Qst0 for CO2 (29.8 kJ mol-1). Slight modifications of the synthesis conditions led to the formation of a different MOF with an anionic framework, having a chemical formula [Me2NH2][In(L)]· n(solv) (2). This MOF is constructed from pseudotetrahedral, mononuclear [In(-COO)4] nodes bridged by four L4- linkers, resulting in a 3D network with PtS topology.

Coordination polymers constructed from tetrahedral-shaped adamantane tectons

Two rigid tetrahedral organic linkers derived from adamantane have been employed in constructing a 3-D, 4-fold interpenetrated framework featuring a PtS topology, [CuL1(H2O)2](BF4)2·8H2O (1) (L1 = 1,3,5,7-tetrakis{4-(4-pyridyl)phenyl}adamantane), and a 2-fold interpenetrated grid-like coordination polymer, [Mn(hfac)2(L2)0.5] (2) (L2 = 1,3,5,7-tetrakis(4-cyanophenyl)adamantane).

ChemInform Abstract: A New Member of Ferrous Sulfates, FeSO4·2H2O with PtS Topology Showing Spin‐Canted Long‐Range Antiferromagnetic Ordering.

AbstractThe title compound is solvothermally synthesized from a mixture of iron(III) citrate, 1,6‐hexamethylenediamine, HF, H2SO4, BuOH, and H2O (autoclave, 423 K, 2 d), followed by addition of N2H4 and HF to the reaction mixture (autoclave, 423 K, 5 d).

A New Structural Family of Gas-Sorbing Coordination Polymers Derived from Phenolic Carboxylic Acids.

The structure of Li(inox)⋅2/3 DMF (inox(-) =the N-oxide of the isonicotinate anion) consists of a 3D framework with solvent-filled, square cross-section channels of approximate dimensions 5.5×5.5 Å. Unfortunately, the Li(inox) framework is unstable upon removal of DMF from the channels. When the structurally related 4-hydroxybenzoic acid (H2 hba) was used in place of Hinox, and Zn(2+) in place of the Li(+) , a structurally similar but more robust network, Zn(hba), was obtained; the isostructural compound, Co(hba), may also be prepared. Longer ligands with phenolate and carboxylate functional groups at opposite ends, such as the dianions of 4-coumaric acid (H2 cma) and 4'-hydroxy-4-biphenylcarboxylic acid (H2 hbpc), in combination with Zn(2+) yield Zn(cma) and Zn(hbpc) frameworks, respectively, with the same PtS topology but with larger channels. The coordination polymers remain intact after desolvation and exhibit microporosity, showing the ability to sorb significant quantities of CO2 , CH4 , and H2 .

A new member of ferrous sulfates, FeSO4·2H2O with PtS topology showing spin-canted long-range antiferromagnetic ordering

A sanderite ferrous sulfate FeSO4·2H2O has been synthesized by the hydro/solvothermal method. Its crystal structure (Pccn, a=6.3160Å, b=7.7550Å, c=8.9880Å, V=440.2Å3, Z=4) can be regarded as the condensation of alternately corner-shared FeO4(H2O)2 octahedra and SO4 tetrahedra with a similar topology of PtS. By structural comparison with the known hydrated ferrous sulfates, the structural relation among them has been noted and discussed in detail. A variable temperature magnetic study shows a spin-canted long-range antiferromagnetic ordering in the low temperature regime, which might result from a possible phase transition during the cooling from the high temperature.

A PtS-like 3D Framework Constructed from 1,4-Phenylenediacetic Acid: Synthesis, Structure and Physical Properties

A novel coordination polymer [Pb(1,4-phda)]n (1) has been hydrothermally synthesized through the reaction of 1,4-phenylenediacetic acid (1,4-H2phda) with divalent lead salt and characterized by IR spectra, elemental analysis and single crystal X-ray diffraction. The crystal structure of complex (1) shows a novel three-dimensional framework with 4, 4-connected 3D PtS topology. Moreover, this framework is reinforced by C–H···O hydrogen bonds and Pb2+···π interaction. The thermal stability of the complex 1 was studied by thermal gravimetric analyses, and the photoluminescent property of complex 1 was also investigated.

Controllable assembly of three copper(II/I) metal–organic frameworks based on N,N′-bis(4-pyridinecarboxamide)-1,2-cyclohexane and 4,4′-oxydibenzoic acid: From three-dimensional interpenetrating framework to one-dimensional infinite chain

By adjusting molar ratio of the reactants (metal salt and two types of ligands), three new CuII/I metal–organic frameworks, [CuII2(4,4′-oba)2(H2O)2]·H2O (1) and [CuI2(4-bpah)2(μ2-OH)(μ3-Cl)]·∼H2O (2) and [CuII(4-bpah)2(4,4′-oba)(H2O)] (3) (4,4′-H2oba=4,4′-oxydibenzoic acid and 4-bpah=N,N′-bis(4-pyridinecarboxamide)-1,2-cyclohexane), have been prepared and structurally characterized by single-crystal X-ray diffraction analyses. When Cu:4-bpah:4,4′-H2oba ratio is 4:1:2, complex 1 is a 5-fold interpenetrated three-dimensional (3D) framework with 4-connected PtS topology, which contains 4,4′-oba ligand. Complex 2 exhibits a 2D network with Cu:4-bpah:4,4′-H2oba ratio of 4:2:1, which contains 1D [CuI2(μ2-OH)(μ3-Cl)]n chains and 4-bpah ligand. Complex 3 is a 1D infinite chain based on 4-bpah and 4,4′-oba mixed ligands with Cu:4-bpah:4,4′-H2oba ratio of 4:2:3. The results reveal that 1–3 are particularly sensitive to the molar ratio of the reactant metal salts and organic ligands in this system. The fluorescent, electrochemical, and photocatalytic properties of 3 were investigated.

Synthesis, structure, and magnetism of three manganese-organic framework with PtS topology

Three 3D manganese-organic frameworks, Mn2(BPTC)(DMF)2(H2O)·DMF·3H2O (1), Mn2(BPTC)(bipy)(DMF)·DMF·H2O (2), and Mn2(BPTC)(phen)(DMF)·EtOH (3), have been solvothermally synthesized using 3,3′,5,5′-biphenyltetracarboxylic acid (H4BPTC). All complexes are characterized by PXRD, EA, IR and TG. The results show that they all bear the PtS topology with (42.84) (42.84) for the vertex symbols of the planar and tetrahedral nodes, in which the BPTC ligand is considered as a square-planar 4-connected linker, and every binuclear SBU connected to the four BPTC ligands is simplified into tetrahedral 4-connected nodes. Because the three coordination sites of one metal center of SBU are occupied by the coordinated solvent molecules, complex 1 exhibits low stability. After substituting 2,2′-bipy or 1,10-phen for two coordinated solvent molecules, complexes 2 and 3 display evidently higher structure stability. The magnetism property of complex 2 is also discussed in detail.

Topological Diversities and Luminescent Properties of Lanthanide Metal–Organic Frameworks Based on a Tetracarboxylate Ligand

The reaction of 5,5′-(1,2-ethynediyl)bis(1,3-benzenedicarboxylic acid) (H4EBDC) and dinuclear lanthanide building blocks generates five new three-dimensional lanthanide metal–organic frameworks (Ln-MOFs) with different topologies under mild conditions. Isomorphic compounds |C2H7N|[Ln2(EBDC)(NO3)2(C3H7NO)4] [Ln = Eu (1), Tb (2), or Er (3)] crystallize in monoclinic symmetry space group C2/c and adopt PtS topology. Under modified conditions, new phases |(NO3)0.5(H3O)0.5|[Yb2(EBDC)(NO3)2(C3H7NO)4] (space group C2/c, compound 4) and |(H3O)2(C3H7NO)2.5|[Eu2(EBDC)2(C3H7NO)(H2O)] (space group P21/c, compound 5) are obtained. In 4, both of the inorganic and organic building blocks can be simplified into a four-coordinate node, forming an Lvt topological network. For compound 5, the dinuclear Ln unit works as an 8-connected node and the organic ligand serves as a 4-connected node; these two kinds of nodes connect and then present an unprecedented (4,8)-connected topology. The aforementioned Ln-MOFs are all characterized by elemental analysis, infrared spectroscopy, and thermogravimetric analysis, and their luminescent properties have been studied, showing emission characteristic of inorganic species at room temperature.

Hydrothermal Syntheses and Crystal Structures of Two New Nickel(II) Coordination Polymers Based on the Semrigid Carboxylate and Imidazole-Containing Ligands

Two new metal coordination polymers, {[Ni(bda)(L1)(H2O)2] ·2H2O}n (1) and {[Ni2(bda)2(bib)2]·H2O}n (2) [H2bda = benzophenone -2,4 -dicarboxylic acid, L1 = 1,4-bis (imidazol-1-yl)benzene and L2 = 1,4-bis(1-imidazol-yl)-2,5-dimethyl benzene] have been successfully synthesized and structure characterized by IR, elemental analysis and X-ray diffraction. Complex 1 shows a two-dimensional layer structure with an hcb topological net and complex 2 exhibits a three-dimensional structure with a PtS topological net. The results indicate that when the N-donor ligands are changed, the topological nets of 1 and 2 are different from to an hcb topology to a PtS topology.

Simultaneous Growing of Two New Cd(II) Metal–Organic Frameworks with 2,6-Naphthalendicarboxylic Acid as New Precursors for Cadmium(II) Oxide Nanoparticles: Thermal, Topology and Structural Studies

Crystal structure and thermal stability of two new 3D Cd(II) metal–organic frameworks (MOF) containing 2,6-naphthalenedicarboxylate, [Cd(NDC)(DMF)], 1, and [Cd3(NDC)4], 2 (H2NDC = 2,6-naphthalenedicarboxylic acid; DMF = N,N-dimethylformamide) have been studied. These two MOFs grow simultaneously within the same solution to give multiple crystals that are due to the general lability of Cd(II) complexes. Structure 1 shows a 3D neutral metal–organic framework with PtS topology and crystallizes in the triclinic system, space group P-1 (No. 2), whilst 2 crystallizes in the orthorhombic system, space group Fdd2 (No. 43) with body-centered cubic bcu-(424.64) topology. The elongated nature of NDC results in large cavities in both compounds; however, the pores are filled by coordinated DMF molecules in 1. The thermal stability of 1 and 2 were studied by thermogravimetry and show stability to 400 °C for 1 and continuous weight loss for 2. CdO nanoparticles were prepared by direct calcination of 1 and 2 at 600 °C. The CdO nanoparticles were characterized by X-ray powder diffraction and its morphology were studied by scanning electron microscopy. The results show that the CdO is pure and has a uniform morphology.

PtS-Related {[CuI(F4TCNQII–)]−}∞ Networks

A series of compounds of composition A[CuI(F4TCNQII–)] (A = a quaternary ammonium or phosphonium cation, F4TCNQII– = the dianionic form of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane) have been synthesized and structurally characterized. In each structure, an anionic [CuI(F4TCNQII–)]− framework possessing the topology of PtS is formed with the Cu(I) center serving as a tetrahedral 4-connecting center and the F4TCNQ2– anion acting as a planar 4-connecting unit. Although a PtS topology is observed for six different compounds, the anionic framework shows significant geometric variation depending upon the identity of the cation. Very similar structures are obtained when the organic cation is NMe4+, NMe2Pr2+, or NMe2Bu2+. A distorted anionic structure possessing the same connectivity is generated when the cation is NEt4+, and anionic frameworks with a different connectivity, but still related to PtS, are obtained when the much larger quaternary phosphonium cations are employed. Of interest in the stru...

Synthesis, Structure, and Characterization of a Microporous Metal‐Organic Framework with PtS Topology

AbstractThe microporous metal‐organic framework Cd2(ABTC)(H2O)(DMA)2·H2O·3DMA (1) (H4ABTC = 3, 3′,5, 5′‐azobenzenetetracarboxylic acid; DMA = N,N′‐dimethylacetamide) was prepared by solvothermal reaction and characterized. X‐ray structure analysis revealed that compound 1 is a three‐dimensional (3D) open framework with 2D channels. The topology is based on a PtS net, constructed of 4‐connected rectangular ABTC4– units with 4‐connected tetrahedral dinuclear Cd2(CO2)4(H2O)(DMA)2 secondary building units (SBUs). The solid‐state excitation‐emission spectra showed that the strongest emission peak is at 403 nm upon excitation at λ = 287 nm.

A porous Mn(v) coordination framework with PtS topology: assessment of the influence of a terminal nitride on CO2 sorption

A new coordination framework material, [Zn{MnN(CN)4(H2O)}]·2H2O·MeOH, has been characterised crystallographically and the effect of a terminal nitride on the N2, H2 and CO2 sorption capacities of the material assessed through porosimetery measurements and DRIFTS.

Three 3d–4f heterometallic coordination polymers based on polydentate ligand and sulfate: Synthesis, crystal structure and photoluminescent properties

Abstract Three heterometallic coordination polymers [Gd 2 Cu(Hbidc) 2 (SO 4 ) 2 (H 2 O) 7 ] n ( 1 ), [Eu 2 Cu(Hbidc) 2 (SO 4 ) 2 (H 2 O) 7 ] n ( 2 ), and [Dy 2 Cu(Hbidc) 2 (SO 4 ) 2 (H 2 O) 7 ] n ( 3 ) (H 3 bidc = 1 H -benzimidazole-5,6-dicarboxylic acid) have been synthesized under hydrothermal conditions. They are characterized by elemental analysis (EA), infrared (IR) spectroscopy, thermogravimetric analysis (TGA), single crystal X-ray diffraction, and power X-ray diffraction (XRD). The results reveal that all complexes present almost identical three-dimensional (3D) PtS topology framework structures. The photoluminescent properties of 2 and 3 are investigated.

The synthesis, structure, and magnetic studies of one supramolecular PtS net

A new 2-D coordination polymer, Co(H2O)2(Hoba)2 (1) [H2oba = 4,4′-oxybis(benzoic acid)], was synthesized under hydrothermal conditions. Polymer 1 has been characterized by single-crystal X-ray diffraction and TG analysis. Through hydrogen bonds 1 shows a supramolecular four-connecting 3-D matrix with 4284 PtS topology. Magnetic studies reveal antiferromagnetic interactions.