Hybrid Inorganic−Metalorganic Compounds Containing Copper(II)-Monosubstituted Keggin Polyanions and Polymeric Copper(I) Complexes.

Abstract

Four hybrid inorganic-metalorganic compounds containing copper(II)-monosubstituted Keggin polyoxotungstates, K3[Cu(I)(4,4'-bpy)]3[SiW11Cu(II)O39].11H2O (1), (paraquat)3[SiW11Cu(II)O39].6H2O (2; paraquat = N,N'-dimethyl-4,4'-bipyridinium), K3[Cu(I)(4,4'-bpy)]3[GeW11Cu(II)O39].11H2O (3), and Na2[Cu(I)(4,4'-bpy)]3[PW11Cu(II)O39(H2O)].4H2O (4), have been synthesized under autogenous pressure hydrothermal conditions and characterized by elemental analysis and infrared spectroscopy (FT-IR). The crystal structures of 1, 2, and 4 have been established by single-crystal X-ray diffraction. The crystal packings are characterized by the presence of monodimensional extended entities: either the polymeric polyanion [SiW11CuO39]n(6n-) (2), the cationic [Cu(4,4'-bpy)]n(n+) chain (4), or both simultaneously as in compound 1, where the inorganic and metalorganic sublattices are mutually perpendicular. To asses the influence of packing in the copper(I) complex structural diversity found in compounds 1 and 4, a search in the CSD database has been performed and the resulting geometrical features have been analyzed and compared with experimental crystallographic data and DFT calculations.

Direct Hydroxylation of Benzene to Phenol with Molecular Oxygen over Pyridine-modified Vanadium-substituted Heteropoly Acids

“…Keggin-type heteropoly acids have many advantages which make themselves economically and environmentally attractive in both academic and industrial significance. They are a kind of the acidic and redox catalysts for various reactions since their strong acidity and redox property can be controlled by replacing the protons with metal cations and/or by changing the heteroatom or the framework transition-metal atoms [7][8][9]. On the other hand, organic/ inorganic hybrid materials are extremely interesting as catalytic materials [10][11][12].…”

Keggin POMs Modified by Bonding to Multitrack Cu(bipy) Chains through Linearly Arrayed Terminal and Bridging Oxygen Atoms of the M3O13 Triad

“…Especially, Cu-bipy complex units have been widely used in magnetic and catalytic materials, [14] and some POM-based Cu-bipy polymers with interesting structures have been reported quite recently. [15] Hydrothermal synthesis represents a fast and excellent method to afford new POM structures. Although the hydrothermal synthesis employing the usual mixture of polyoxometalate, transition-metal salt, and nitrogencontaining ligand has been intensively extended, there is still abundant scope for the construction of intricate structures for new materials.…”

New Synthetic Routes to Polyoxometalate Containing Ionic Liquids

“…[62] assignment TPA THexA THA TOA SiW 11 Cu SiW 11 and at around 1380 cm -1 for the symmetric deformation of the CH 3 group. [63] The CH 2 rocking vibration at around 720 cm -1 is relatively weak and may in some cases be overlaid by the combined as(W-O a -W) + as(C u -O) b valence vibration of the cluster with its centre at around 750 cm -1 .…”