Reaction of in situ generated copper(II)-monosubstituted Keggin polyoxometalates and copper(II)-bipyridine-oxalate complexes in the corresponding alkaline acetate buffer led to the formation of hybrid metal organic-inorganic compounds K(2)[{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(H(2)O)(2)(mu-ox)}(2)].14H(2)O (1), K(14)[{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(mu-ox)}](2)[SiW(11)O(39)Cu(H(2)O)].55H(2)O (2), (NH(4))(4)[{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(mu-ox)}].10H(2)O (3), and Rb(4)[{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(mu-ox)}].10H(2)O (4). Their structures have been established by single-crystal X-ray diffraction. The main structural feature of these compounds is the presence of copper(II)-monosubstituted alpha-Keggin polyoxoanions as inorganic building blocks, on which the mu-oxalatodicopper metalorganic blocks are supported. Compound 1contains the discrete hybrid polyanion [{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(H(2)O)(2)(mu-ox)}(2)](2)(-), whereas the polymeric hybrid polyanion [{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(mu-ox)}(2)](n)(4)(n)(-) gives a monodimensional character to compounds 2-4. Magnetic and EPR results are discussed with respect to the crystal structure of the compounds. DFT calculations on both the [Cu(2)(bpy)(2)(H(2)O)(4)(mu-ox)](2+) cationic complex and the metalorganic blocks have been performed in order to determine the optimized geometry and the magnetic coupling constants, respectively.

The first decavanadate-based microporous hybrid, namely, [Cu(cyclam)][{Cu(cyclam)}2(V10O28)]·10H2O(1, cyclam = 1,4,8,11-tetraazacyclotetradecane) has been prepared by reaction of (VO3) -anions and {Cu(cyclam)} 2+ complexes in NaCl (aq) at pH 4.6-4.7, and characterized by elemental analyses, thermogravimetry, and X-ray diffraction techniques (powder, single-crystal). Compound 1 exhibits a POMOF-like supramolecular open-framework built up of covalent decavanadate/metalorganic layers with square-like voids, the stacking of which is aided by interlamellar cementing complexes and generates water-filled channels with approximate cross-sections of. 10.4 × 8.8 Å 2 . The framework is robust enough to remain virtually unaltered upon thermal evacuation of all water molecules of hydration, as demonstrated through single-crystal X-ray diffraction studies on the anhydrous phase 1a. This permanent microporosity renders interesting functionality to 1, such as selective adsorption of CO2 over N2 and remarkable activity as heterogeneous catalyst toward the H2O2-based oxidation of the highly-stable, tricyclic alkane adamantane.Porous crystalline materials such as metal organic frameworks (MOFs) have attracted great attention due to their wide range of relevant applications. 1 These materials are constructed by coordination of metal ions or metalcontaining units (nodes) to organic bridging ligands (linkers) to form open crystalline frameworks with permanent porosity. This feature qualifies them as suitable candidates for gas storage and separation, ion exchange, host-guest chemistry, magnetism, biomedicine and catalysis. 2 However, the synthesis of MOFs usually requires harsh conditions (e.g. high temperature or pressure, prolonged reaction times, harmful solvents, etc.), and removal of guest molecules from their cavities often leads to the collapse of the porous structure when flexible linkers are used. In this context, the incorporation of rigid and voluminous species such as metal clusters could increase the overall robustness

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.

Zinc(II) salphen complexes equipped with additional alkoxy donor groups at the 3-position of the salicylideneimine groups have been prepared to bind metal acetates in a second coordination sphere close to the central Zn(II) ion. The isolated binuclear monosalphen complexes have been studied in detail using NMR and MS techniques. Further synthesis has revealed that the formation of binuclear species from the parent salphen ligands is dependent on the nature of the bridging group between the two salicylideneimine groups and is prevented by replacement of one of the alkoxy substituents for a bulky t-Bu group. One of the binuclear Zn2 complexes was crystallographically characterized and can be regarded as a structural model for the intermediate stage of the transmetalation of the central Zn(II) center within these dinuclear compounds by other metal acetate salts. Furthermore, the X-ray diffraction structure also relates well with some intermediate structural stages of the buildup of various polynuclear salen structures.