Inorganic Organic Chains Research Articles

One pot-synthesis of the fourth category of dinuclear molybdenum(VI) oxalate series: Structure and study of thermal and redox properties

Three new dinuclear molybdenum(VI) oxalate (Pr2NH2)4·[Mo2O6(C2O4)2] (1), (iPr2NH2)4·[Mo2O6(C2O4)2] (2) and (HDabco)4[Mo2O6(C2O4)2]·2H2O (3) compounds, have been prepared by one pot-synthesis at room temperature and characterized by single crystal X-ray diffraction and vibrational spectroscopies. Each compound contains the binuclear [Mo2O6(C2O4)2]4− anion where each molybdenum is in an octahedral MoO6 environment. In compound (3), the interconnection between [Mo2O6(C2O4)2]4− anions, [HDabco]+ cations and water molecules (H2O) leads to an infinite inorganic-organic chain structure. Similarly, in compounds (1) and (2) the interactions between [Mo2O6(C2O4)2]4− anions and respectively [Pr2NH2]+ and [iPr2NH2]+ cations leads to an infinite inorganic-organic chain structure. A remarkable difference between the compounds is that in compounds (1) and (2) interactions between the chains involve only Van der Waals forces giving rise to layer-like structures, which also interact between them only by Van der Waals forces, whereas in compound (3) the chains interact also through hydrogen bonds giving a 3D supramolecular structure. The thermal properties of the compounds were investigated through thermogravimetric and differential thermal analyzes. The differences in the thermal decomposition of the compounds in the solid state are discussed in relation with their crystal structure. Cyclic voltammetry shows that the [Mo2O6(C2O4)2]4− anion can be reduced in both aprotic solvent and water.

Structural characterization, photoluminescence and sensing properties of two copper(I)-iodide compounds

Two copper(I) iodide compounds with formula of {[Cu2I2(2-mna)]·DMA} (1) and {[CuI(6-mna)]·DMSO} (2) (2-mna = 2‑mercaptonanicotinic acid; 6-mna = 6‑mercaptonanicotinic acid; DMA = dimethylacetamide; DMSO = dimethyl sulfoxide) have been prepared by reaction and evaporation between CuI and 2-mna/6-mna at room temperature. Four Cu atoms in 1 are linked by I− ions and 2-mna ligands into [Cu4I4(2-mna)2] units which are further linked into a 1D inorganic-organic chain by sharing CuI bonds. In 2, thiolate sulfur of 6-mna adopts μ2-coordination modes to bridge two Cu atoms, forming [Cu2(6-mna)2] building units, which are further connected by I− ions into 1D chain structure. It is worth mentioning that the Cu⋯Cu distances in 1 and 2 are shorter than the sum of the van der Waals radii of copper(I) (2.80 Å), implying the metal-metal bonding interactions. Interestingly, compounds 1 and 2 display blue and red fluorescence emission bands in the solid state, respectively. In particular, compound 2 exhibits the capability to selectively detect Fe3+ ion as a fluorescence “turn-off” sensor.

A coordination polymer based on dinuclear (pyrazinyl tetrazolate) copper(ii) cations and Wells-Dawson anions for high-performance supercapacitor electrodes.

A new coordination polymer, (H2bpe)(Hbpe)2{[Cu(pzta)(H2O)][P2W18O62]}·5H2O (1) (pztaH = 5-(2-pyrazinyl) tetrazolate, bpe = bis(4-pyridyl)ethylene), was synthesized by the hydrothermal method. The structure was determined by single crystal X-ray diffraction analyses and further characterized by the SEM, EDS, BVS, FTIR, and PXRD techniques. In 1, the [P2W18O62]6- (P2W18) clusters as bidentate connectors link [Cu(pzta)(H2O)]24+ dinuclear copper(ii) complexes to form inorganic-organic chains. These chains and the [H2bpe]2+ counter-cations are fused together via hydrogen bonding to form a 3D supramolecular architecture. While 1 was employed as the electrode in a supercapacitor, the cycling stability (90.7% capacitance retention after 1000 circles) and specific capacitance (168 F g-1 at a current density of 5 A g-1) of the 1-based electrode are better than those of the parent α-K6P2W18O62-based electrode, demonstrating more outstanding electrochemical performances of 1. Besides, the 1-based electrode showed excellent electrocatalytic activities towards the reduction of H2O2 and KIO3.

Introduction of secondary pyridyl-1H-tetrazole derivatives into Keggin–Ag–(1,10-phenanthroline) system for tuning dimensionalities and architectures: assembly and properties

By introducing three pyridyl-1H-tetrazole derivatives to Keggin–Ag-(1,10-phenanthroline) system, five new polyoxometalate-based inorganic–organic hybrid compounds with different dimensionalities and structures, [Ag3(4-ptz)2Na(phen)(HPMo12O40)]·2H2O (1), [Ag4(3-ptz)2(phen)2(HPMo12O40)] (2), [Ag4(3-ptz)2(phen)2(HVW12O40)] (3), [Ag3(3-bptzb)(phen)2(PMo12O40)] (4) and [Ag3(3-bptzb)(phen)2(VW12O40)] (5) (phen = 1,10-phenanthroline, x-ptzH = 5-(x-pyridyl)-1H-tetrazole (x = 3, 4), 3-bptzb = 1,4-bis(5-(3-pyridyl)-tetrazolyl)butane), have been synthesized under hydrothermal conditions. Compound 1 is a 1-D belt architecture constructed from an Ag-4-ptz metal–organic chain and two Ag–PMo12O40–Na–phen inorganic–organic chains. When 3-ptzH was introduced as secondary ligand in 2 and 3 instead of 4-ptzH, two isostructural architectures were obtained, which contain a 1-D zigzag Ag-3-ptz chain with phen ligands hanging on both sides of the chain. The Keggin anions connect adjacent Ag-3-ptz chains to construct 2-D networks. When the flexible 3-bptzb was selected, isostructural 4 and 5 with 2-D networks were obtained, which were constructed from binuclear subunits and Keggin–Ag inorganic chains. The influence of three pyridyl-1H-tetrazole derivatives as secondary ligands on the dimensionalities and architectures of 1–5 was discussed. The electrochemical and photocatalytic properties of the compounds were investigated.

Hydrothermal synthesis and electrochemical properties of a coordination polymer based on dinuclear (Pyrazinyl tetrazolate) Copper(II) cations and β-Octamolybdate Anions

A hybrid compound (H2bbi)[Cu2(pzta)2(H2O)2][ β-Mo8O26] (1) (pztaH = 5-(2-pyrazinyl) tetrazolate, bbi = 1,1’-(1,4-butanediyl)bis(imidazole), has been hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. In 1, the β-Mo8 clusters link dinuclear copper (II) complexes as bidentate connectors to form inorganic-organic chains. These chains and the [H2bbi]2+ counter-cations are fused together forming layers via hydrogen bonding interactions. The electrochemical properties of 1 were studied. The results indicate that 1 has an electrocatalytic activity towards the reduction of iodate ascribed to the Mo-centers.

Hydrothermal synthesis, crystal structure and heterogeneous catalytic activity of a novel inorganic–organic hybrid complex, possessing infinite La–O–La linkages

In this paper, a novel lanthanum coordination polymer formulated as {[La2(Hpdc)3(H2O)4]·2H2O}n (1, H3pdc=3,5-pyrazoledicarboxylic acid) has been synthesized by the reaction of H3pdc with chloride salt of La(III) under hydrothermal conditions and characterized by elemental analysis, FT-IR, TGA and single-crystal X-ray diffraction. The complex crystallized in the monoclinic system Cc space group. The single-crystal X-ray structural analysis revealed that central metal La atoms are nine-coordinate and linked by bridging μ2-OCOO- groups to form [La(1)-(μ2-OCOO−)2-La(2)]n inorganic–organic chains that produce a supramolecular polymeric framework structure. The three-dimensional structure of 1 is accompanied by non-coordinating water molecules. Thermal behavior and catalytic performance of 1 have also been studied. The complex 1 showed 100% selectivity and a conversion rate of 24% on the oxidation of thymol (T) to thymoquinone (TQ).

Inorganic–organic chain assemblies as lamellar nanoreactors for growing one-dimensional Cu(OH)2 and CuO nanostructures

One-dimensional Cu(OH)(2) or CuO nanostructures were fabricated using inorganic-organic chain assemblies, Cu(C(n)H(2n+1)X)(2)·nH(2)O (X = CO(2), SO(4)) as a lamellar nanoreactor, along with NaOH treatment. The shapes and aspect ratios of the Cu(OH)(2) or CuO nanostructures could be varied by adjusting the hydrophobicity of the lamellar nanoreactors.

Hydrothermal synthesis, structure and properties of two lanthanide benzenedicarboxylates, [La 2(isophth) 2(Hisophth) 2(H 2O) · H 2O] n and [Dy 4(isophth) 4(Ac) 4(H 2O) 8 · 2H 2O] n, possessing infinite Ln–O–Ln linkages

Two lanthanide benzenedicarboxylates, [La 2(isophth) 2(Hisophth) 2(H 2O) · H 2O] n 1 and [Dy 4(isophth) 4(Ac) 4(H 2O) 8 · 2H 2O] n 2 (H 2isophth = isophthalic acid, Ac = acetate) have been obtained by hydrothermal synthetic method and characterized by elementary analysis, IR, TG, and especially the X-rays single-crystal diffraction. The complexes 1 and 2 crystallize in the monoclinic system with P2 1/ c space group. The X-ray single-crystal structure analysis reveals that center metal ions Ln(III) are nine-coordinated and linked by μ 2-Ocoo − groups to form the [Ln2-(μ 2-Ocoo −) 2-Ln1] n inorganic–organic chains and finally to furnish the supramolecular framework structures. The thermogravimetric analyses were carried out to examine the thermal stability of these two complexes. Magnetic studies on the polycrystalline sample shows the existence of strong antiferromagnetic couplings between the adjacent Dy 3+ ions in compound 2.

Formation and Nonlinear Optical Properties of a Novel Polymeric Cadmium(II) Complex Bridged by Sulfur Ions

Abstract The title coordination polymer, [Cd(NH2NHCSNH2)(HS)2]n·nH2O, has been obtained by self-assembling from the reaction of a methanol/water (volume ratio, 1/1) solution containing cadmium chloride with equivalent amount of succinic acid and thiosemicarbazide. The X-ray crystal analysis reveals that the cadmium atoms are bridged by HS− ligands and mutual sulfur atoms which contribute to formation of the infinite one-dimensional (1D) inorganic–organic chain in a zig-zag way. The second harmonic generation (SHG) response of the complex is much stronger than that of urea.