New copper(I) cyanide networks: interpenetration, self-penetration and polymorphism

The structures Of four alkali-metal copper (I) cyanides, KCu2(CN)(3)(H2O)-H-.-II (I), K2Cu3(CN)(5) (II), CsCu3(CN)(4) (III) and KCu3(CN)(4) (IV) are described. Three of these, ((II)-(IV)), with previously unknown ACN:CuCN ratios have new copper-cyanide frameworks, whilst (1) is a new polymorph of KCu2(CN)(3)(H2O)-H-.. These structures are discussed in terms of assembly from the simple building units Cu(CN)(2/2), Cu(CN)(3/2), Cu(CN)(2/2)(CN)(1/1) and Cu(CN)(4/2). Compounds (I), (II) and (III) are layered materials based on (6,3) nets containing (CuCN)(6) rings (I) and (CuCN)(8) rings (II) and (III). In compound (IV), (4,4) nets containing (CuCN)(12) rings link to generate a three-dimensional network. Both (III) and (IV) are examples of interpenetrating solids in which two and four identical networks interweave, respectively. These materials illustrate the structural versatility of copper (I) in cyanide frameworks. (c) 2006 Elsevier SAS. All rights reserved.

Trinuclear cu(ll) complexes containing peripheral ketonic oxygen bridges and a mu(3)-OH core: Syntheses, crystal structures, spectroscopic and magnetic properties

Four new trinuclear copper(II) complexes, [(CuL1)(3)(mu(3)-OH)](ClO4)(2)center dot H2O (1), [(CuL2)(3)(mu(3)-OH)](CIO4)(2) (2), [(CuL3)(3)-(mu(3)-OH)](ClO4)(4)center dot H2O (3), and [(CuL4)(3)(mu(3)-OH)](ClO4)(2)center dot H2O (4), where HL1 = 8-amino-4,7,7-trimethyl-5-azaoct-3-en-2-one, HL2 = 7-amino-4-methyl-5-azaoct-3-en-2-one, HL3 = 7(ethylamino)-4-methyl-5-azahept-3-en-2-one, and HL4 = 4-methyl-7-(methylamino)-5-azahept-3-en-2-one, have been derived from the four tridentate Schiff bases (HL1, HL2, HL3, and HL4) and structurally characterized by X-ray crystallography. For all compounds, the cationic part is trinuclear with a CU3OH core held by three carbonyl oxygen bridges between each pair of copper(II) atoms. The copper atoms are five-coordinate with a distorted square-pyramidal geometry; the equatorial plane consists of the bridging oxygen atom of the central OH group together with three atoms (N, N, O) from one ligand whereas an oxygen atom of a second ligand occupies the axial position. Magnetic measurements have been performed in the 2-300 K temperature range. The experimental data could be satisfactorily reproduced by using an isotropic exchange model, H = -J(S1S2+S2S3+S1S3) yielding as best-fit parameters: J = -66.7 and g = 2.19 for 1, J = -36.6 and g = 2.20 for 2, J = -24.5 and g = 2.20 for 3, and J = -14.9 and g = 2.05 for 4. EPR spectra at low temperature show the existence of spin frustration in complexes 3 and 4, but it has not been possible to carry out calculations of the antisymmetric exchange parameter, G, from magnetic data. In frozen methanolic solution, at 4 K, hyperfine splitting in all complexes and spin frustration in complex 4 seem to be confirmed. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

A new tetrameric Cu-II cluster with square topology exhibiting ferro- and antiferromagnetic magnetic pathways: which is which?

[Cu4L2(bpy)(4)(H2O)(3)](ClO4)(4).2.5H(2)O, 1, a new tetranuclear Cu-II cluster showing square planar geometry, formed with aspartate bridging ligand (L) has been synthesized. The global magnetic coupling is ferromagnetic but theoretical DFT/B3LYP calculations are necessary to assign which Cu-L-Cu side is ferro or antiferromagnetically coupled.

Synthesis, structure and properties of a mononuclear and an end-on double azido-bridged copper(II) complex incorporating an N,N,N,O-coordinating tripodal ligand

The blue coloured complex [Cu(HL)(H2O)(ClO4)]ClO.H2O.MeOH (1.H2O.MeOH) has been synthesised in excellent yields by reacting Cu(ClO4)(2).6H(2)O with N,N-bis(2-methylpyridyl)(3,5-dimethyl-2-hydroxybenzyl)amine (HL) in methanol. The same reaction, when carried out in the presence of sodium azide, afforded a dark-blue complex of formula [Cu-2(HL)(2)(mu-1,1-N-3)(2)](ClO4)(2) (2). The crystal and molecular structures of the complexes have been solved. Variable-temperature magnetic susceptibility data in the range of 2-300 K for 2 reveal the existence of an antiferromagnetic interaction through an end-on azido linker. Temperature-dependent susceptibility studies for 2 were fitted using the Bleaney-Bowers expression, which led to the parameters J = -3.2 cm(-1), g = 2.12 and R = 2.14 x 10(-4). (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Synthesis, crystal structure and reactivity of copper(II) complexes of tetradentate N2S2 donor ligands

Two new hexa-coordinated mononuclear copper(II) complexes of two ligands L-1 and L-2 containing NSSN donor sets formulated as [Cu(L)(H2O)(2)](NO3)(2) [1a, L = 1,2-bis(2-pyridylmethylthio)ethane (L-1), 1b L = 1,3-bis(2-pyridyl-methylthio)propane (L-2)] were synthesized and characterized by physico-chemical and spectroscopic methods. In 1a the single crystal X-ray crystallography analysis showed a distorted octahedral geometry about copper(II) ion. The crystal packing evidences pairs of complexes arranged about a center of symmetry and connected through a H-bond occurring between aquo ligands and nitrate anions. On reaction with chloride and pseudohalides (N-3(-) and SCN-), in acetonitrile at ambient temperature. complexes 1 changed to monocationic penta-coordinated mononuclear copper(H) species formulated as [Cu(L)(Cl)]NO3 (2), [Cu(L)(N-3)]NO3 (3). and [Cu(L)(SCN)]NO3 (4). These copper(II) complexes have been isolated in pure form from the reaction mixtures and characterized by physico-chemical and spectroscopic tools. The solid-state structure of 2a, established by X-ray crystallography, shows a trigonal bipyramidal geometry about the metal ion with a trigonality index (tau) of 0.561. (C) 2009 Elsevier B.V. All rights reserved.

Novel supramolecular network in tri- and mono-nuclear oxovanadium(V)-salicyl-hydroximate: Synthesis, structure and catalytic oxidation of hydrocarbons using H2O2 as terminal oxidant

oxovanadium(V) salicylhydroximate complexes, [VO(SHA)(H2O)]center dot 1.58H(2)O (1) and [V3O3(CSHA)(3) (H2O)(3)]center dot 3CH(3)COCH(3) (2) have been synthesized by reaction of VO43- with N-salicyl hydroxamic acid (SHAHS) and N-(5-chlorosalicyl) hydroxamic acid (CSHAH(3)), respectively, in methanol medium. Compound 1 on reaction with pyridine 2,6-dicarboxylic acid (PyDCH2) yields mononuclear complex [VO(SHAH(2))(PyDC)] (3). Treatment of compound 3 with hydrogen peroxide at low pH (2-3) and low temperature (0-5 degrees C) yields a stable oxoperoxovanadium(V) complex H[VO(O-2)(PyDC)(H2O)]center dot 2.5H(2)O (4). All four complexes (1-4) have been characterized by spectroscopic (IR, UV-Vis, V-51 NMR) and single crystal X-ray analyses. Intermolecular hydrogen bonds link complex 1 into hexanuclear clusters consisting of six {VNO5} octahedra surrounded by twelve {VNO5} octahedra to form an annular ring. While the molecular packing in 2 generates a two-dimensional framework hydrogen bonds involving the solvent acetone molecules, the mononuclear complexes 3 and 4 exhibit three-dimensional supramolecular architecture. The compounds 1 and 2 behave as good catalysts for oxygenation of benzylic, aromatic, carbocyclic and aliphatic hydrocarbons to their corresponding hydroxylated and oxygenated products using H2O2 as terminal oxidant; the process affords very good yield and turnover number. The catalysis work shows that cyclohexane is a very easily oxidizable substrate giving the highest turnover number (TON) while n-hexane and n-heptane show limited yield, longer time involvement and lesser TON than other hydrocarbons. (C) 2008 Elsevier Ltd. All rights reserved.

Novel lanthanide luminescent materials based on complexes of 3-hydroxypicolinic acid and silica nanoparticles

New lanthanide complexes of 3-hydroxypicolinic acid (HpicOH) were prepared: [Ln(H2O)(picOH)(2)(mu-HpicO)].3H(2)O (Ln = Eu, Tb, Er). The complexes were characterized using photoluminescence, infrared, Raman, and H-1 NMR spectroscopy, and elemental analysis. The crystal structure of [Eu(H2O)(picOH)(2)(mu-HpicO)] . 3H(2)O 1 was determined by X-ray diffraction. Compound 1 crystallizes in a monoclinic system with space group P2(1)/c and cell parameters a = 9.105(13) Angstrom, b = 18.796(25) Angstrom, and c = 13.531(17) Angstrom, and beta = 104.86(1) deg. The 3-hydroxypicolinate ligands coordinate through both N,O- or O,O- chelation to the lanthanide ions, as shown by X-ray and spectroscopic results. Photoluminescence measurements were performed for the Eu(III) and Tb(III) complexes; the Eu(III) complex was investigated in more detail. The Eu(III) compound is highly luminescent and acts as a photoactive center in nanocomposite materials whose host matrixes are silica nanoparticles.

MULTIMODE quantum calculations of intramolecular vibrational energies of the water dimer and trimer using ab initio-based potential energy surfaces

We report vibrational configuration interaction calculations of the monomer fundamentals of (H2O)(2), (D2O)(2), (H2O)(3), and (D2O)(3) using the code MULTIMODE and full dimensional ab initio-based global potential energies surfaces (PESs). For the dimer the HBB PES [Huang , J. Chem. Phys 128, 034312 (2008)] is used and for the trimer a new PES, reported here, is used. The salient properties of the new trimer PES are presented and compared to previous single-point calculations and the vibrational energies are compared with experiments. (C) 2008 American Institute of Physics.

Engineering Pt in ceria for a maximum metal-support interaction in catalysis

Conventional supported metal catalysts are metal nanoparticles deposited on high surface area oxide supports with a poorly defined metal−support interface. Typically, the traditionally prepared Pt/ceria catalyzes both methanation (H2/CO to CH4) and water−gas shift (CO/H2O to CO2/H2) reactions. By using simple nanochemistry techniques, we show for the first time that Pt or PtAu metal can be created inside each CeO2 particle with tailored dimensions. The encapsulated metal is shown to interact with the thin CeO2 overlayer in each single particle in an optimum geometry to create a unique interface, giving high activity and excellent selectivity for the water−gas shift reaction, but is totally inert for methanation. Thus, this work clearly demonstrates the significance of nanoengineering of a single catalyst particle by a bottom-up construction approach in modern catalyst design which could enable exploitation of catalyst site differentiation, leading to new catalytic properties.

Cyclam derivatives containing three acetate pendant arms: synthesis, acid-base, metal complexation and structural studies

The ligands 1,4,8,11-tetraazacyclotetradecane-1,4,8-triacetic-11-methylphosphonic acid (H(5)te3a1p) and 1,4,8,11-tetraazacyclotetradecane-1,4,8-triacetic acid (H(3)te3a) were synthesized, the former one for the first time. The syntheses of these ligands were achieved from reactions on 1,4,8,11-tetraazacyclotetradecane-1,4,8-tris( carbamoylmethyl) hydroiodide (te3am center dot HI), and compounds (Hte3am)(+), 1, and (H(7)te3a1p)(2+), 4, were characterized by X-ray diffraction. Structures of two other compounds resulting from side-reactions, (H(2)te2lac)(2+), 2, and (H(4)te2a2p(OEt2))(2+), 3, were also determined by X-ray diffraction. Potentiometric titrations of H(5)te3a1p and H(3)te3a were performed at 298.2 K and ionic strength 0.10 mol dm(-3) in NMe4NO3 to determine their protonation constants. H-1 and P-31 NMR titrations of H(5)te3a1p were carried out in order to determine the very high first protonation constant of this ligand and to elucidate the sequence of protonation. Potentiometric studies of the two ligands with Ca2+, Mn2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+ and Pb2+ metal ions performed in the same experimental conditions showed that the complexes of H5te3a1p present very high thermodynamic stability while complexes of H(3)te3a, particularly Co2+ and Zn2+, are even more stable. P-31 NMR spectra of the cadmium(II) complex of H(5)te3a1p showed that the phosphonate moiety was coordinated to the metal ion. The UV-vis-NIR spectroscopic data and magnetic moment values of Co2+ and Ni2+ complexes of H(5)te3a1p and H(3)te3a together with the EPR of the corresponding Cu2+ complexes indicated that all these complexes adopt distorted octahedral coordination geometries in solution. This was confirmed by the single crystal structure of [Cu-2(Hte3a)(H2O)(3)Cl]Cl-0.5(ClO4)(0.5) center dot 2H(2)O that showed two distorted octahedral copper centres bridged by a N-acetate pendant arm with a Cu center dot center dot center dot Cu distance of 4.890(1) angstrom. The first one is encapsulated into the macrocyclic cavity surrounded by four nitrogen and two oxygen donors from the macrocycle, whereas the second one is on the periphery of the macrocycle and is coordinated to two oxygen atoms of one acetate pendant arm in chelating fashion, one chloride and three water molecules.

Adsorption of frog foam nest proteins at the air-water interface

The surfactant properties of aqueous protein mixtures ( ranaspumins) from the foam nests of the tropical frog Physalaemus pustulosus have been investigated by surface tension, two-photon excitation. uorescence microscopy, specular neutron reflection, and related biophysical techniques. Ranaspumins lower the surface tension of water more rapidly and more effectively than standard globular proteins under similar conditions. Two- photon excitation. uorescence microscopy of nest foams treated with fluorescent marker ( anilinonaphthalene sulfonic acid) shows partitioning of hydrophobic proteins into the air-water interface and allows imaging of the foam structure. The surface excess of the adsorbed protein layers, determined from measurements of neutron reflection from the surface of water utilizing H2O/D2O mixtures, shows a persistent increase of surface excess and layer thickness with bulk concentration. At the highest concentration studied ( 0.5 mg ml(-1)), the adsorbed layer is characterized by three distinct regions: a protruding top layer of similar to20 Angstrom, a middle layer of similar to30 Angstrom, and a more diffuse submerged layer projecting some 25 Angstrom into bulk solution. This suggests a model involving self-assembly of protein aggregates at the air-water interface in which initial foam formation is facilitated by specific surfactant proteins in the mixture, further stabilized by subsequent aggregation and cross-linking into a multilayer surface complex.

Thermal decomposition of potassium hexanitronickelate(II) hydrate

The thermal decomposition of the complex K-4[Ni(NO2)6]center dot H2O has been investigated over the temperature range 25-600 degrees C by a combination of infrared spectroscopy, powder X-ray diffraction, FAB-mass spectrometry and elemental analysis. The first stage of reaction is loss of water and isomerisation of one of the coordinated nitro groups to form the complex K-4 [Ni(NO2)(4) (ONO)]center dot NO2. At temperatures around 200 degrees C the remaining nitro groups within the complex isomerise to the chelating nitrite form and this process acts as a precursor to the loss of NO2 gas at temperatures above 270 degrees C. The product, which is stable up to 600 degrees C, is the complex K-4[Ni(ONO)(4)]center dot NO2, where the nickel atom is formally in the +1 oxidation state. (c) 2005 Elsevier B.V. All rights reserved.

Experimental evidence for a partially dissociated water bilayer on Ru{0001}

Core-level photoelectron spectra, in excellent agreement with ab initio calculations, confirm that the stable wetting layer of water on Ru{0001} contains O-H and H2O in roughly 3:5 proportion, for OHx coverages between 0.25 and 0.7 ML, and T<170 K. Proton disorder explains why the wetting structure looks to low energy electron diffraction (LEED) to be an ordered p(root3xroot3)R30degrees adlayer, even though approximate to3/8 of its molecules are dissociated. Complete dissociation to atomic oxygen starts near 190 K. Low photon flux in the synchrotron experiments ensured that the diagnosis of the nature of the wetting structure quantified by LEED is free of beam-induced damage.

A refined LEED analysis of water on Ru{0001}: an experimental test of the partial dissociation model

Despite a number of earlier studies which seemed to confirm molecular adsorption of water on close-packed surfaces of late transition metals, new controversy has arisen over a recent theoretical work by Feibelman, according to which partial dissociation occurs on the Ru{0001} surface leading to a mixed (H2O + OH + H) superstructure. Here, we present a refined LEED-IV analysis of the (root3 x root3)R30degrees-D2O-Ru{0001} structure, testing explicitly this new model by Feibelman. Our results favour the model proposed earlier by Held and Menzel assuming intact water molecules with almost coplanar oxygen atoms and out-of-plane hydrogen atoms atop the slightly higher oxygen atoms. The partially dissociated model with an almost identical arrangement of oxygen atoms can, however, not unambiguously be excluded, especially when the single hydrogen atoms are not present in the surface unit cell. In contrast to the earlier LEED-IV analysis, we can, however, clearly exclude a buckled geometry of oxygen atoms.

Dimetallic complexes of macrocycles with two rigid dibenzofuran units as receptors for detection of anionic substrates

The hexaazamacrocycles [28](DBF)2N6 {cyclo[bis(4,6-dimethyldibenzo[b,d]furaniminoethyleneiminoethylene]} and [32](DBF)2N6 {cyclo[bis(4,6-dimethyldibenzo[b,d]furaniminopropyleneiminopropylene]} form stable dinuclear copper(II) complexes suitable to behave as receptors for several anionic substrates. These two receptors were used to study the binding interactions with several substrates, such as imidazole (Him) and some carboxylates [benzoate (bz−), oxalate (ox2−), malonate (mal2−), phthalate (ph2−), isophthalate (iph2−), and terephthalate (tph2−)] by spectrophotometric titrations and EPR spectroscopy in MeOH (or H2O):DMSO (1:1 v/v) solution. The largest association constant was found for ox2− with Cu2[32](DBF)2N64+, whereas for the aromatic dicarboxylate anions the binding constants follow the trend ph2− > iph2− > tph2−, i.e. decrease with the increase of the distance of the two binding sites of the substrate. On the other hand, the large blue shift of 68 nm observed by addition of Him to Cu2[32](DBF)2N64+ points out for the formation of the bridged CuimCu cascade complex, indicating this receptor as a potential sensor for the detection and determination of imidazole in solution. The X-band EPR spectra of the Cu2[28](DBF)2N64+ and Cu2[32](DBF)2N6]4+ complexes and the cascade complexes with the substrates, performed in H2O:DMSO (1:1 v/v) at 5 to 15 K, showed that the CuCu distance is slightly larger than the one found in crystal state and that this distance increases when the substrate is accommodated between the two copper centres. The crystal structure of [Cu2[28](DBF)2N6(ph)2]·CH3OH was determined by X-ray diffraction and revealed the two copper centres bridged by two ph2− anions at a Cu···Cu distance of 5.419(1) Å. Each copper centre is surrounded by three carboxylate oxygen atoms from two phthalate anions and three contiguous nitrogen atoms of the macrocycle in a pseudo octahedral coordination environment.