CdSO4 Topology Research Articles

Synthesis, structure and property investigation of a three-dimensional Zn(II) metal–organic frameworks

A new three-dimensional Zn(II) complex named [Zn(1,3-BMIB)(TBIP)⋅2H2O][Formula: see text] (1) (containning 1,3-BMIB = 1,3-bis(2-methyl-1H-imidazol-1-yl)benzene, H2TBIP=5-tert-butyl isophthalic acid) had been prepared by hydrothermal synthesis. Systematic structural characterization, especially the single crystal X-ray diffraction method, discreetly reveal the complex 1 exhibits three-dimensional (3D) framework with CdSO4 topology. The 3D crystrals 1 display solid-state fluorescence behavior at room temperature, indicating the potential of the candidate materials for absorbing and using visible light. The photocatalytic properties of compound 1 were estimated through the model photodecomposition dye pollutants using methylene blue (MB) and rhodamine B (RhB) under visible light irradiation.

Synthesis, structure and photocatalytic degradation of organic dyes of a copper(II) metal-organic framework (Cu-MOF) with a 4-coordinated three-dimensional CdSO4 topology.

Metal-organic frameworks (MOFs) have attracted much interest in the fields of gas separation and storage, catalysis synthesis, nonlinear optics, sensors, luminescence, magnetism, photocatalysis gradation and crystal engineering because of their diverse properties and intriguing topologies. A Cu-MOF, namely poly[[(μ2-succinato-κ2O:O'){μ2-tris[4-(1,2,4-triazol-1-yl)phenyl]amine-κ2N:N'}copper(II)] dihydrate], {[Cu(C4H4O4)(C24H18N10)]·2H2O}n or {[Cu(suc)(ttpa)]·2H2O}n, (I), was synthesized by the hydrothermal method using tris[4-(1,2,4-triazol-1-yl)phenyl]amine (ttpa) and succinate (suc2-), and characterized by IR, powder X-ray diffraction (PXRD), luminescence, optical band gap and valence band X-ray photoelectron spectroscopy (VB XPS). Cu-MOF (I) shows a twofold interpenetrating 4-coordinated three-dimensional CdSO4 topology with point symbol {65·8}. It presents good photocatalytic degradation of methylene blue (MB) and rhodamine B (RhB) under visible-light irradiation. A photocatalytic mechanism was proposed and confirmed.

Sonochemical synthesis of two nano-sized nickel(II) coordination polymers derived from flexible bis(benzimidazole) and isophthalic acid ligands

Two new Ni(II) coordination polymers (CPs), [Ni(L1)(IPA)]n (1) and [Ni(L2)(IPA)·H2O]n (2) (L1 = 1,6-bis(benzimidazol-1-yl)hexane, L2 = 1,6-bis(5,6-dimethylbenzimidazol-1-yl)hexane, H2IPA = isophthalic acid) were synthesized by hydrothermal and sonochemical process. X-ray crystal structure analysis revealed that 1 possesses a 4-connected 3D architecture with a 65.8 CdSO4 topology, while 2 exhibits a 2D layer, which can be classified as a honeycomb 63-hcb network. The results indicate that Ni(II) mixed CPs structurally modulated by the flexible bis(benzimidazole)-involved co-ligands. The role of ultrasound irradiation power, reaction time and reaction temperature on the size and morphology of the nano-sized 1 and 2 were investigated in detail. Further, fluorescence and photocatalytic activities of nano-sized CPs for degradation of methylene blue (MB) are presented.

Metal(II) Coordination Polymers Derived from Mixed 4-Imidazole Ligands and Carboxylates: Syntheses, Topological Structures, and Properties.

Four new metal–organic coordination polymers [Cu(L)(mpa)]·3H2O (1), [Co(L)(mpa)]·H2O (2), [Zn(L)(mpa)]·H2O (3), and [Cd(L)(mpa)(H2O)]·H2O (4) were synthesized by reactions of the corresponding metal(II) salts based on mixed ligands of 1,4-di(1H-imidazol-4-yl)benzene (L) and 4-methylphthalic acid (H2mpa), respectively. The structures of the complexes were characterized by elemental analysis, FT-IR spectroscopy, and single-crystal X-ray diffraction. Compound 1 exhibits a binodal 4-connected three dimensional (3D) architecture with (65·8)-CdSO4 topology, while complexes 2 and 3 are isostructural and have two-dimensional (2D) layer structure with (4, 4) sql topology based on the binuclear metal subunits. Complex 4 has the same 2D layer structure with (4, 4) sql topology as complexes 2 and 3, but the inclined interpenetration of parallel sets of layers result in the formation with 2D + 2D → 3D framework. The activated sample 1 shows selective CO2 uptake over N2. The photoluminiscent properties together with quantum yield (QY) and luminescence lifetime are also investigated for complexes 3 and 4 in the solid state at room temperature.

A new Zn(ii) metal–organic framework having 3D CdSO4 topology as luminescent sensor and photocatalyst for degradation of organic dyes

A new Zn(ii) metal–organic framework having 3D CdSO4 topology synthesized and deployed as a dual channel luminescent sensor for ferric ion and nitroaromatics, and a photocatalyst for the degradation of organic dyes.

Water-Resistant and Transparent Plastic Films from Functionalizable Organic Polymers: Coordination Polymers as Templates for Solid-State [2+2]-Photopolymerization.

An organic polymer containing cyclobutanes and amides as backbones and pyridyl groups as sidearms was synthesized by single-crystal-to-single-crystal (SCSC) [2+2]-photopolymerization in the coordination polymers (CPs) of diene. The diene molecule was photo-inactive in its crystals and formed a triply intertwined 1D-helical CP with Cd(NO3 )2 and Cu(NO3 )2 salts. The 1D-CP was transformed into a coordination polymer of organic polymers containing threefold interpenetrated 3D-networks of CdSO4 topology through a [2+2]-reaction in SCSC manner upon irradiation. The organic polymer was separated from its CPs and found to have an unusually high degree of polymerization for this type of reaction. Furthermore, the organic polymer was amenable for N-alkylation reactions such as methylation, propylation, and decylation. The formate salts of the organic polymer and the methylated polymer were shown to form plastic films with a combination of properties such as high transparency, tensile strengths, gas permeability, thermal stability, water-resistance, and resistance to other organic solvents. The methylated polymer was also able to capture chromate ions and anionic dyes from aqueous solutions.

Porous Coordination Polymers Containing Pyridine-3,5-Bis(5-azabenzimidazole): Exploration of Water Sorption, Selective Dye Adsorption, and Luminescent Properties

Six novel coordination polymers of Cd(II) and Zn(II) have been designed and synthesized using pyridine-3,5-bis(5-azabenzimidazole), L, and various angular dicarboxylates as linkers. The dicaboxylates used are 4,4′-oxobisbenzoate (OBA), isophthalate (IPA) and 1,4-phenylene diacetate (PDA). All the six complexes are found to exhibit general formula of {[M(L) (dicarboxylate)]·xDMF·yH2O}n. The four complexes containing OBA and IPA exhibited two-dimensional layered structures with grid like cavities of dimensionalities 18 × 15 and 17 × 10 A2, while those with PDA exhibited 3D-network consisting of CdSO4 topology. The coordination networks are propagated by M2(RCO2)2 SBUs and exhibit guest accessible volume of 23–33%. The XRPD and gas sorption studies confirm their stability and porous nature. Further, these materials exhibited a greater preference for the adsorption of water or alcohol vapors over nitrogen. The alcohol sorption found to depend on the size of the molecules that is they have shown greater abilit...

Syntheses, structures and magnetism of four Ni(II)/Co(II) interpenetrating coordination polymers based on 1,4-bis(4-(imidazole-1-yl)benzyl)piperazine

Four novel interpenetrating coordination polymers have been hydrothermally synthesized based on a long flexible N-donor ligand (bibp) and different polycarboxylates, namely [Ni(1,3-bdc)(bibp)(H2O)]·0.5H2O (1), [Ni(btec)0.5(bibp)1.5]·H2O (2), [Co(btec)0.5(bibp)1.5]·H2O (3) and [Co(oba)(bibp)]·2H2O (4) (bibp=1,4-bis(4-(imidazole-1-yl)benzyl)piperazine, 1,3-bdc=1,3-benzenedicarboxylate, btec=1,2,4,5-benzenetetracarboxylate, oba=4,4′-oxybisbenzoate). Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra and TG analyses. Compound 1 shows a 2-fold interpenetrating 3D framework with CdSO4 topology. Compounds 2 and 3 exhibit 2-fold interpenetrating pcu frameworks. Compound 4 is a 2D→3D interdigitated network formed from 2D→2D threefold interpenetrating motifs. In addition, the magnetic properties of compounds 1–4 have also been investigated in the temperature range 2–300K.

Two novel 3D self-threading coordination polymers with CdSO4 topology: Syntheses, structures and properties

Two new isostructural metal-organic frameworks, namely [Co(HL)(bpp)]·0.5H2O (1) and [Zn(HL)(bpp)]·3H2O (2) (H3L=5-(2′-carboxy-biphenyl-4-ylmethoxy)-isophthalic acid, bpp=1,3-bis(4-pyridyl)propane), have been hydrothermally synthesized and further characterized by single crystal X-ray diffraction, powder X-ray diffraction, elemental analyses, IR spectra and TG analyses. Compounds 1 and 2 exhibit interesting 3D frameworks of (65.8)-CdSO4 topology with dangling arm (i.e. the uncoordinated 2′-carboxy-biphenyl-4-ylmethoxy group of HL ligand). The remarkable feature of these two compounds is that each dangling arm threads into two 6-membered rings belonging to the 3D net itself, displaying the self-threading character. The magnetic properties of 1 and photoluminescence of 2 have also been investigated.

Synthesis, Structures, and Luminescent Properties of Two Four‐connected Polymers Based on 2, 2‐Dimethylsuccinic Acid

AbstractThe polymers [Cd(L)(H2O)] (1) and [Zn(L)(4, 4′‐bipy)(H2O)3] (2) (L = 2, 2‐dimethylsuccinated anion) were synthesized under hydrothermal conditions and characterized by IR spectrosopy, elemental analyses, and single‐crystal X‐ray diffraction analysis. The latter reveals that the polymer 1 exhibits a four‐connected dia‐topology net based on the novel tetranuclear CdII units, whereas polymer 2 displays a 4‐connnected CdSO4 topology net. Moreover, the photoluminescent properties of 1 and 2 were investigated.

Cd(II) and Cu(II) coordination polymers based on a multidentate N-donor ligand: syntheses, crystal structures, optical band gaps, and photoluminescence

Four Cd(II)- and Cu(II)-containing coordination polymers (CPs) based on a multidentate N-donor ligand and varied dicarboxylate anions, [Cd(3,3′-tmbpt)(p-bdc)]·2.5H2O (1), [Cd(3,3′-tmbpt)(m-bdc)]·2H2O (2), [Cu(3,3′-tmbpt)(m-bdc)]·H2O (3), and [Cu(3,3′-tmbpt)(p-bdc)]·2H2O (4), where 3,3′-tmbpt = 1 − ((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole, p-H2bdc = 1,4-benzenedicarboxylic acid, and m-H2bdc = 1,3-benzenedicarboxylic acid, have been prepared hydrothermally. The structures of the compounds were determined by single-crystal X-ray diffraction analyses and further characterized by infrared spectra and elemental analyses. Compound 1 exhibits a 3-D twofold interpenetrating framework with a 65·8 CdSO4 topology. Compound 2 is a 2-D layer containing meso-helical chains with a 44·62 sql topology. Compound 3 shows a 1-D → 3-D interdigitated architecture while 4 displays a 2-D → 3-D interdigitated architecture. The structural differences of the compounds indicate that the dicarboxylate anions and the central metal ions play important roles in the resulting structures of CPs. Optical band gaps and solid-state photoluminescent properties have also been studied.

Synthesis and Characterization of Polyhedral-Based Metal–Organic Frameworks Using a Flexible Bipyrazole Ligand: Topological Analysis and Sorption Property Studies

Six porous metal–organic frameworks (MOFs), {[Ni(BTC)0.66(BPz)2]·2MeOH·4H2O}n (1), {[Co(BTC)0.66(BPz)2]·2MeOH·4H2O}n (2), {[Mn(BTC)0.66(BPz)2]·2MeOH·4H2O}n (3), {[Cd(BDC)(BPz)(H2O)]·2MeOH·DMF}n (4), {[Cd2(NH2-BDC)2(BPz)(H2O)]·MeOH·H2O·DMF}n (5), and {[Co(BDC)(BPz)(H2O)]}n (6) (where H3BTC = 1,3,5-benzenetricarboxylic acid, H2BDC = 1,4-benzenedicarboxylic acid, NH2-H2BDC = 2-amino-1,4-benzenedicarboxylic acid, and BPz = 3,3′,5,5′-tetramethyl-4,4′-bipyrazole), were obtained through a solvent diffusion technique and characterized. The networks exhibit a variety of topologies: 1, 2, and 3 are isostructural and possess octahedral and cuboctahedra type cages and exhibit 3,6-c binodal net having loh1 topology, 4 is a two-dimensional MOF having one-dimensional open channels with a 4-c uninodal net having sql topology, 5 exhibits a three-dimensional (3D) porous MOF having a 3,3,4,8-c net with a new topology having the name, skr1, whereas 6 discloses a 3D nonporous network which exhibits a 4-c uninodal net having CdSO4 topology. Being isostructural, gas sorption studies of 1–3 show nearly the same CO2 sorption at 195 K of ∼90 mL g–1, whereas 4 and 5 show a maximum uptake of 42 and 37 mL g–1 at 195 K. Vapor sorption studies of 1–3 reveal stepwise uptake of water with a final amount reached to nearly 350 mL g–1, whereas 4 and 5 show maximum uptake of 110 and 90 mL g–1, respectively. Compared to the free ligand BPz, photoluminescence studies of 4 and 5 show red shifts and emit in the blue-green region with λmax at 430 and 472 nm for 4 and 5, respectively.

Two New 3D Zn(II)/Cu(II) Coordination Polymers Based on N,N′-Di(3-pyridyl)succinamide and Two Different Aromatic Dicarboxylates: Syntheses, Crystal Structures and Properties

Two new 3D transition metal coordination polymers [Zn(1,3-BDC)(L)0.5] (1) and [Cu(5-AIP)(L)0.5] (2) [L = N,N′-di(3-pyridyl)succinamide, 1,3-H2BDC = 1,3-benzenedicarboxylic acid, 5-H2AIP = 5-aminoisophthalic acid] have been hydrothermally synthesized and structurally characterized by elemental analyses, IR, TG and single crystal X-ray diffraction analysis. In complex 1, two carboxyl groups with monodentate modes from two 1,3-BDC ligands connect two Zn(II) ions to form a dinuclear {Zn2} SBUs, then the adjacent {Zn2} SBUs are connected by two pairs of 1,3-BDC ligands and two L ligands to construct a 3D coordination network with the large square-shape grids. Finally, the complex 1 exhibits a 4-connected CdSO4 topology with the threefold interpenetrating feature. Complex 2 is a 3D coordination framework constructed by the ligands L and 5-AIP anions, which represents a binodal (3,8)-connected {42·6}2{44·610·79·85} topology. The different coordination modes of metal ions and two dicarboxylates play important roles in the formation of coordination frameworks for title complexes. In addition, the thermal stabilities, the fluorescent properties of complexes 1–2 and the electrochemical behavior of complex 2 modified carbon paste electrode have also been investigated. Two new 3D coordination polymers, [Zn(1,3-BDC)(L)0.5] (1) and [Cu(5-AIP)(L)0.5] (2), have been hydrothermally synthesized. Complex 1 represents a threefold interpenetrating CdSO4 topology, complex 2 exhibits a binodal (3,8)-connected {42·6}2{44·610·79·85} topology. The different coordination modes of metal ions and dicarboxylates play important roles in the formation of final structures for title complexes.

Syntheses, crystal structures, and properties of four coordination polymers with a new bifunctional ligand

Four new coordination polymers, {[Cd2(L)2·H2O]·4DMF·14H2O}n (1), {[Cd (L)]·2DMF·6H2O}n (2), {[Zn2(L)2]·4DMF·5H2O}n (3) and {[Cu (L)]·2DMF}n (4) (H2L=2,5-bis((4H-1,2,4-triazol-4-yl)carbamoyl)terephthalic acid), have been synthesized under solvothermal conditions and structurally characterized by single-crystal X-ray diffraction. All of them exhibit three-dimensional structures possessing one-dimensional channels filled with solvent molecules. 1 is a 3D framework with large 1D channels (6.60×8.56Å2) filled with free DMF molecules and the 3D structure of 1 is a new (4, 8) network with Schläfli symbol {416.612}{44.62}2. 2 and 3 with different metal centers have similar structure except for the numbers of free water molecules. They both feature a (4, 4)-connected 3D network of {65.10} {65.8} topology with left- and right-handed helical chains along b-axis. While 4 is a 3D framework with typical CdSO4 topology. In addition, 1–3 show strong fluorescent emissions at room temperature, which can be assigned to the ligand-to-ligand charge transfer (LLCT) emissions.

Three-Fold Interpenetrated CdSO4 Topology in a Co(II) Coordination Polymer Constructed From Pamoic Acid and N-Containing Auxiliary Ligand

A new Co(II) compound, namely [Co(pam)(bpa)(H2O)2]n n(DMF) (1 H2pam = pamoic acid, bpa = 1,2-di(4-pyridyl)ethylene, DMF = N, N’-dimethylformamide), has been successfully synthesized and structurally characterized. Single-crystal X-ray analysis reveals that 1 is a 3-fold interpenetrated three-dimensional (3D) framework. Topological analysis shows that this compound can be simplified into a four-connected CdSO4 topological network. TG analysis reveals that compound 1 can be stable up to 316ºC.

Synthesis, structure and property of Ni(II) coordination polymers with mixed dicarboxylate and benzoimidazol-containing ligands

Four new Ni(II) complexes [Ni(L)(SO4)(H2O)2]·H2O (1), [Ni3(L)4(p-BDC)3(H2O)6]·6H2O (2), [Ni(L)(m-BDC)(H2O)2]·0.5H2O (3) and [Ni(L)(BPDC)(H2O)2] (4) have been prepared by reactions of 3,5-di(1H-benzimidazol-1-yl)pyridine (L) with nickel sulfate in the presence of auxiliary ligands of phthalic acid (o-H2BDC), terephthalic acid (p-H2BDC), isophthalic acid (m-H2BDC) and biphenyl-4,4′-dicarboxylic acid (H2BPDC), respectively. Interestingly, phthalate (o-BDC2−) did not take part in formation of 1, instead SO42- was found in 1. Complex 2 with p-BDC2− shows different two-dimensional (2D) network from 1 while 3 has one-dimensional (1D) chain structure. Complex 4 is a three-dimensional (3D) framework with CdSO4 topology. The thermal stability and adsorption property of the complexes were investigated. Furthermore, it was found that complexes 1–4 can catalyze acetalization reaction of aldehydes with methanol, and 1 gives the highest yield.

Two isostructural 3D metal–organic frameworks constructed from 1D [H2Mo4O14]n2n− chains and the flexible bis-pyridyl-bis-amide ligand

Abstract Two new isostructural metal–organic frameworks based on 1D [H2Mo4O14]n2n − chains and the flexible N,N′-bis(3-pyridinecarboxamide)-1,2-ethane (L), [M(L)(H2Mo4O14)(H2O)2] (M = CoII for 1, NiII for 2), have been hydrothermally synthesized and characterized by single crystal X-ray diffraction. In the title complexes, the unusual 1D [H2Mo4O14]n2n − chains are linked by the MII ions to form a 2D inorganic bimetallic layer. The adjacent 2D layers are further connected by the L ligands to construct a 3D framework with CdSO4 topology. The electrochemical behaviors and the photocatalytic activities of the title complexes have been investigated.

Syntheses, structures and magnetic properties of three Co(II) coordination architectures based on a flexible multidentate carboxylate ligand and different N-donor ligands

Three new cobalt complexes, {[Co5(tci)2(bimb)3(µ3-O)2(H2O)2]·3DMF·4H2O}n (1), {[Co3(tci)2(bib)]·2DMF·2H2O}n (2) and {[Co(Htci)(bpea)0.5]·H2O}n (3) (H3tci = tris(2-carboxyethyl)isocyanurate, bimb = 4,4′-bis(imidazol-1-yl)biphenyl, bib = 1,4-bis(imidazol-1-yl)benzene, bpea = 1,2-bis(4-pyridyl)ethane, DMF = N,N′-dimethylformamide), have been successfully synthesized through the assembly of Co(II) ions, H3tci and different N-donor ligands, respectively. All complexes were structurally characterized by single crystal X-ray diffraction, elemental analyses, IR spectra, thermogravimetric (TG) analyses and X-ray powder diffraction (XRPD). Complex 1 exhibits a 3D three-fold parallel interpenetrated 3D → 3D structure with (65·8) CdSO4 topology. Complex 2 is built from [Co3(µ2-Ocarboxyl)2(CO2)4] clusters and linear bib ligands, displaying a two-fold parallel interpenetrated (3,8)-connected (43)2(46·618·84) topology, while complex 3 is a 3D pillar-layered structure involving an infinite -Co-(µ2-Ocarboxyl)(CO2)-Co-chain. The diverse structures of the three complexes indicate that the skeletons of different N-donor ligands play an important role in the assembly of such different frameworks. In addition, magnetic investigation indicates that besides spin-orbit coupling of Co(II) ions, there exist antiferromagnetic exchange interactions in Co5 and Co3 clusters of 1 and 2, respectively.

A zinc-organic coordination polymer of glycine-functionalized naphthalenediimide ligand

Abstract The first metal–organic coordination polymer of amino-acid functionalized naphthalenediimide (NDI) ligand, [Zn(Gly-NDI)(DMF)2]n (1), has been synthesized and characterized. Single-crystal X-ray diffraction revealed that the Zn ions are linked by anti-conformational Gly-NDI ligands, and 1 displays a one-dimensional zigzag chain coordination polymer. These chains are cross-linked through strong π···π stacking interactions between NDI cores to give a three-dimensional supramolecular framework with square planar 4-connected CdSO4 (cds) topology. The thermal stability and fluorescence emissions of 1 were also investigated.

Muconate bridged coordination polymers of Cu(II): Effect of auxiliary ligand on their structural architectures

Two coordination polymers [Cu2(2,2′-bpy)2(muco)2(H2O)2](H2O)2, (1) and [Cu(4,4′-bpy)(muco)(H2O)2], (2) [H2muco=trans,trans-muconic acid or 1,3-butadiene-1,4-dicarboxylic acid, 2,2′-bpy=2,2′-bipyridyl and 4,4′-bpy=4,4′-bipyridyl] have been synthesized by the reaction of muconate dianion with Cu(NO3)2·3H2O in presence of auxiliary ligands 2,2′-bpy and 4,4′-bpy respectively. Single crystal X-ray crystallographic structure determination reveals that 1 has one-dimensional (1D) structural motif and an extensive H-bonding pattern gives rise to 3D supramolecular network in the crystal of 1. On the contrary, 2 exhibits threefold interpenetrating three-dimensional (3D) net-work with CdSO4 topology. In the formation of these complexes, the auxiliary ligand has a vital role in directing the solid-state structure with defined topological network.