Caridad Ruiz-Valero

Rare-earths as catalytic centres in organo-inorganic polymeric frameworksElectronic supplementary information (ESI) available: selected bond angles and hydrogen interactions in 1, 2, 3; coordination environment of the two scandium atoms in 1; coordination modes of the three crystallographically independent carboxylate groups for 2 and 3. See http://www.rsc.org/suppdata/jm/b3/b314220e/

New 3D polymeric succinates of rare-earths have been synthesised: [Sc2(C4H4O4)2.5(OH)], [Y2(C4H4O4)3(H2O)2]·H2O, [La2(C4H4O4)3(H2O)2]·H2O, and their structures solved by single crystal XRD. They were obtained as single phases, characterised and tested as heterogeneous catalysts as Lewis acids in the acetalization of aldehydes and as redox agents in the oxidation of sulfides showing them to be effective and selective catalysts, easy to recover and reusable. The scandium, yttrium and lanthanum oxides were also tested in the same catalytic reactions to prove the effect of the porous organo-inorganic framework.

One teflon®-like channelled nanoporous polymer with a chiral and new uninodal 4-connected net: sorption and catalytic properties

Zn(C17H8F6O4) is the first example of a fluoro-lined nanotube organo-inorganic 3D polymeric chiral structure, which possesses two different types of isolated channels, one of them being laid out with a double spiral of CF3-groups from the ligand molecule; the structure is a new uninodal 4-connected net that only exists when bent ligands connect the centres, and the compound exhibits selective sorption and catalytic chiral recognition properties.

(NH4)2Ge7O15: A Microporous Material Containing GeO4 and GeO6 Polyhedra in Nine‐Rings

GeO4tetrahedra and GeO6octahedra, which form nine-rings (see sketch on the right), feature in the unprecedented structure of the microporous solid, (NH4)2Ge7O15. This compound provides the first evidence that in the GeO2/NH4+ system the cubic (NH4)3HGe7O16⋅n H2O is not the only existing phase, but depending on the GeO6/GeO4 ratio, differently charged frameworks can be generated.

The first isolated antineoplastic Ru(IV) complex: Synthesis and structure of [Cl2(1,2-cyclohexanediaminotetraacetate)Ru]·2H2 O

Abstract Treatment of ruthenium(III) chloride with solid cyclohexanediaminetetraacetic acid (H4cdta) affords the water soluble complex [Ru(H2cdta)Cl2]·2H2O (1), the first isolated Ru4+ compound showing cytostatic activity. Complex 1 has been characterized by X-ray diffraction, electronic spectroscopy and magnetic studies. The molecular structure indicates that the chelating ligand acts a tetradentate, showing two free carboxylic groups. The octahedral coordination around the metal ion is completed by two chlorine atoms.

A Germanium Zeotype Containing Intratunnel Transition Metal Complexes

A new zeolite-type structure is adopted by (NH(4))(+)[M(NH(3))(2)](+)(Ge(9)O(19))(2-) (M=Cu, Ag; shown in the picture). These compounds are the first microporous germanates containing a transition metal complex inside their tunnels. The large separation between the metal centers and the unhindered access of reactants to these active sites through uniformly sized channels make these materials a good point of departure for designing new catalysts.

Bridged 3,5-disubstituted pyrazolate ligands as support of metallomesogens containing [Pd(η3-C3H5)]+ fragments: X-ray crystal structure of [Pd(η3-C3H5)(μ-pzR2)]2·CH2Cl2 (R=C6H4OC12H25). Part III

Abstract The mesomorphic properties of two new long-chain 3,5-(4-n-alkoxyphenyl)pyrazoles HpzR2 (R=C6H4OCnH2n+1, n=16, 18) have been studied and compared with those of related compounds containing shorter chains (n=4, 6, 8, 10, 12, 14). For liquid crystal purposes, the derivative with 14 carbon atoms in the chain behaves as the best compound on the basis of the lowest melting point and the widest stability range of the mesophases. New Pd(II) complexes of formula [Pd(η3-C3H5)(μ-pzR2)]2 (R=C6H4OCnH2n+1, n=8, 10, 12, 14, 16, 18) (1–6) containing the mesomorphic ligands as pyrazolate-bridging groups have been prepared and characterised. In solution, three conformational isomers (two symmetric and one asymmetric corresponding to different orientations of the allyl groups) have been found. In the solid state, the X-ray crystal structure of 3 (n=12) evidenced the asymmetric isomer. The structure shows a bowlic core drawn on the basis of the boat-like conformation of the six-membered ring Pd(NN)2Pd. However, a rod-like shape could also be considered by taking the molecular dimensionality into account (47.80 A in length×4.75 A in wide). The Pd-complexes 2–6 were found to have liquid crystal properties exhibiting enantiotropic smectic phases consistent with the molecular characteristics. Moreover, the molecular packing of 3 is described as the layer-like type in which the molecules are parallel to the c-axis but tilted off the layer, this fact appearing similar to the molecular ordering in the smectic fluid phases.

Sr9Ni6.64O21: A New Member (n= 2) of the Perovskite-RelatedA3n+3An′B3+nO9+6nFamily

Crystals of a new phase Sr{sub 9}Ni{sub 6.64}O{sub 21} were grown. This compound in the n = 2 member of the A{sub 3n+3}A{sub n}{prime}B{sub n+3}O{sub 6n+9} series. The composition and the crystal structure have been established form X-ray single crystal diffraction data. The structure contains face-shared chains of NiO{sub 6} polyhedra parallel to the c axis and is related with hexagonal 2H polytype perovskite. Sr{sub 9}Ni{sub 6.64}O{sub 21} crystallizes in the space group R3c (No. 167) with a = 9.467(2) {angstrom}, c = 35.87(5) {angstrom}, V = 2784.(4) {angstrom}{sup 3}, and Z = 6. A comparison is made between the structure of the title compound and the other members of the series.

New catalytically active neodymium sulfate

Two novel isotopic rare earth sulfates, R(SO4)2·NH4 (R = Nd, Eu), have been synthesized hydrothermally at 170 °C for 5 days. The crystal structures of these compounds have been established by single crystal X-ray diffraction to be the monoclinic space group P21/c, with a = 8.867(1), b = 7.187(1), c = 10.804(2) A, β = 91.653(3)° and Z = 4 for Nd(SO4)2·NH4. The structure can be conceived as being formed of parallel layers [R(SO4)2]−, in which a honeycomb (6, 3) layer of sharing edge RO9 polyhedra is bonded to different isolated SO4 tetrahedra. Inside the inter-block space a row of NH4+ ions are hosted, which connect the layers through hydrogen bonds. The magnetic measurements, and catalytic studies of the Nd(SO4)2·NH4 in alkene hydrogenation, and selective oxidation of organic sulfides are reported. This material shows good activity and selectivity, and can be reused for at least four cycles without significant loss in catalytic activity.

From rational octahedron design to reticulation serendipity. A thermally stable rare earth polymeric disulfonate family with CdI2-like structure, bifunctional catalysis and optical properties

A new family of lanthanide disulfonates Ln(OH)(NDS)(H2O), (Ln = La, Pr and Nd; NDS=1,5-naphthalenedisulfonate) was designed and hydrothermally synthesized; this is the first example of a disulfonate ligand coordinated to six different Ln atoms; these materials, with high thermal stability, act as active and selective bifunctional catalysts in oxidation and epoxide ring opening; strong luminescence from the optically active Nd center was observed.

Synthesis and crystal structure of the layer compound Sb3TeO6Cl

The mixed oxohalide Sb3TeO6Cl has been obtained and characterized for the first time. The structure has been determined by single-crystal X-ray techniques, using diffractometer data. The compound crystallizes in the orthorhombic space group Immm, with a= 4.1283(8), b= 9.390(3), c= 12.968(8)A, and Z= 2. Refinement led to a final R value of 0.037 using 278 observed reflections. The co-ordination of the heavy atom can be considered as a distorted trigonal bipyramid with the lone pair directed towards one of the equatorial positions. The crystal consists of parallel layers of (Sb3TeO6)n+ perpendicular to the c axis, the isolated Cl– anions being situated between these layers. Thus, Sb3TeO6Cl is an example of a positively- charged network structure.