A nitronyl nitro­xide complex of ­nickel(II) with nitrate as a ligand

The complex cation in [4,5-di­hydro-4,4,5,5-tetra­methyl-2-(2-pyridyl-κN)­imidazol-1-oxyl 3-oxide-κO³](nitrato-κ²O,O′)(N,N,N′,N′-tetra­methyl-1,2-ethanedi­am­ine-κ²N,N′)­nickel(II) hexafluorophosphate dichloromethane solvate, [Ni(NO₃)(C₆H₁₆N₂)(C₁₂H₁₆N₃O₂)]PF₆·CH₂Cl₂, is the first example of a nitro­nyl nitro­xide complex of a transition metal ion having d electrons in which nitrate is coordinated as a bidentate ligand. Owing to the smaller steric requirement of NO₃⁻, the Ni—­O(nitro­xide) bond length [2.014 (2) Å] is remarkably shorter than that in the corresponding ­β-­diketonate complexes [2.052 (4)–2.056 (2) Å].     

Luminescence of cesium dicyanoaurate(I). Evidence for extended Au(I)Au(I) interactions in two dimensions

The luminescence of microcrystalline samples of Cs[Au(CN)₂] is reported and ascribed to planar AuAu interactions. Low-temperature measurements from 1.6 to 100 K of the luminescence decay rate of Cs[Au(CN)₂] for the band centered at 458 nm reveal the presence of at least two emitting levels separated by 46 cm⁻¹. A simple orbital model is proposed to account for the luminescence, and spin—orbit coupling is invoked to explain the splitting of the two lowest states. The analogies and differences between this luminescence and that observed for salts of Pt(CN)₄²⁻ are briefly discussed.     

Ferromagnetic copper(II)–copper(II) interaction in a single chlorido and dicyanamido bridged mixed–valence copper(I/II) 2-D polymer generated by in situ partial reduction of copper(II)

A mixed-valence 2-D Cu(I/II) complex, [{Cu(II)(dmen)(μ-Cl)(μ_1,5-dca)}{Cu(I)(μ_1,5-dca)}]_n (1) (dmen = N,N-dimethylethylenediamine, dca = dicyanamide = [N(CN)₂]^?), has been synthesized by in situ partial reduction of Cu(II) to Cu(I) using benzoin (2-hydroxy-1,2-di(phenyl)ethanone) as reductant. Complex 1 was characterized by spectroscopic techniques, single crystal X-ray diffraction, and low temperature magnetic measurements. Structural investigation reveals that 1 represents a mixed-valence 2-D coordination polymer formed by parallel 1-D [Cu(II)(dmen)(Cl)Cu(I)(μ_1,5-dca)₂]_n chains running along the b axis, where chloride bridges Cu(II) ions of adjacent polymers through long connections (2.8401(1) Å) to form a 2-D network. The metal centers have two different geometrical environments (distorted square pyramidal and distorted trigonal planar geometries for Cu(II) and Cu(I), respectively). The Cu(II) ions in [Cu(II)(dmen)(μ-Cl)(dca)]_n are interconnected through single chloride bridges while within the [Cu(I)(μ_1,5-dca)]_n units, the dca connects adjacent Cu(I) ions through μ_1,5-dca bridges. Magnetic susceptibility measurements reveal weak ferromagnetic interactions (J = +0.3 cm^?1) within the chlorido-bridged Cu(II) regular chain present in 1. Simultaneous presence of μ_1,5-dca and single chlorido bridges with ferromagnetic coupling is believed to be unique in mixed-valence Cu(I)/Cu(II) complexes.     

Chiral induction from ligands to metal centres. A copper(II)–nitroxide complex

Copper(II) complexes of a racemic mixture of a chiral nitronyl-nitroxide are characterised. One, A, is a centro-symmetrical species where two enantiomers are coordinated to a metal centre. The second, B, is a 1D compound comprising bridging ligands through the oxyl and pyridyl donor sites. One observes that, although the crystals are racemic, within a chain, all ligands and metal centres have respectively the same chirality. Possibilities of obtaining optically active extended structures through chiral induction from nitroxide ligands to metal ions are discussed in relation with molecular spin transition species.     

Very long-distance magnetic coupling in a dicopper(II) metallacyclophane with extended π-conjugated diphenylethyne bridges

Self-assembly of the rigid rodlike ligand N,N'-4,4'-diphenylethynebis(oxamate) (dpeba) and Cu(2+) ions affords a novel dinuclear copper(II) metallacyclophane (nBu(4)N)(4)[Cu(2)(dpeba)(2)]·4MeOH·2Et(2)O (1) featuring a very long intermetallic distance (r = 15.0 ?). Magnetic susceptibility measurements for 1 reveal a moderately weak but nonnegligible intramolecular antiferromagnetic coupling between the two metal centers across the double para-substituted diphenylethynediamidate bridge (J = -3.9 cm(-1); H = -JS(1)S(2), where S(1) = S(2) = S(Cu) = (1)/(2)). Density functional electronic structure calculations on 1 support the occurrence of a spin polarization mechanism.     

Multichannel recognition of hydrogen sulphate anion by a Zn(II)–triazole–pyridine complex bearing a ferrocenyl pendant

Receptors ferrocene–triazole–pyridine triads assembled with Zn(II) or Cd(II) metal cations behave as chemosensor molecules for HSO₄ ^?  anions through electrochemical and optical channels: the redox peak of the ferrocene/ferrocenium redox couple is shifted cathodically by 72–53 mV, and a new absorption band appeared in the UV–vis spectrum upon complexation with the HSO₄ ^?  anion. Association constants, detection limits and stoichiometries of the recognition processes have been determined, whereas ¹H NMR experiments and density functional theory calculations are used to suggest the plausible binding mode taking place in the new supramolecular assembly formed.     

Synthesis,structure and magnetism of a hydrogen-bond-linked three-dimensional network of a novel nickel(II)–cobalt(II)–nickel(II) complex containing a new macrocyclic mononuclear complex ligand

A novel trinuclear complex, [Co(NiL)₂(H₂O)₂](ClO₄)₂ · 2C₂H₅OH, was prepared by self-assembly using [NiL] as a new complex ligand; L is the dianion of dimethyl 5,6,7,8,15,16-hexahydro-6,7-dioxodibenzo[1,4,8,11]tetraazacyclotetradecine-13,18-dicarboxylate. The structure of the trinuclear complex was determined by X-ray crystallography. The Co^II ion is at the center of the trinuclear complex cation and occupies a distorted octahedral O₆ environment, approximating to O _h with a ⁴ T _1g ground state for Co^II that has an unquenched spin–orbit coupling reflected in the magnetic properties. Two Ni^II ions reside in completely same and slightly distorted square-planar N₄ coordination geometries. Co^II and each Ni^II are bridged by an oxamido group from one of the two macrocyclic ligands (L). O—H...O and ... interactions link the trinuclear fragments, perchlorate ions and C₂H₅OH molecules to form a three-dimensional supramolecular architecture.     

Stimuli-responsive,thixotropic bicomponent hydrogel of melamine–Zn(II)-orotate complex

Zinc(II)-orotate complex (ZnOA) has been synthesised, and it is used to produce supramolecular complex with melamine (M) at 1:1 molar ratio. During sonication for 5–6 min, the supramolecular complex is transformed into a bi-component hydrogel (S-gel). The spectroscopic tools such as FTIR and UV–vis spectra suggest that the H-bonding interaction between M and ZnOA produces a supramolecular complex which further forms J-aggregates during gelation. The circular dichroism spectra indicate the change in ellipticity with temperature that arises from the molecular dissymmetry during stacking of the ZnOAM complexes. The microscopic images indicate that the hydrogel network is formed with short helical nano-fibres. The energy-minimised structure of ZnOAM complex exhibits a well-defined d value of 11.3 Å obtained from X-ray scattering of the xerogel. The frequency-dependent rheological experiment (storage modulus (G′) is greater than loss modulus (G″)) characterises it as a gel. The gel shows thixotropic and stimuli-responsive behaviour.     

Electroreduction of Dy(III) assisted by Zn and its co-deposition with Zn(II) in LiCl–KCl molten salt

To recover dysprosium (Dy) from LiCl–KCl molten salt, the electrochemical mechanism of Dy(III) on liquid Zn electrode and co-deposition of Dy(III) and Zn(II) on W electrode were studied using electrochemical methods. Cyclic voltammetry results demonstrated that the redox process of Dy on liquid Zn electrode is reversible and controlled by diffusion. Reverse chronopotentiograms showed that the transition time ratio of reduction and oxidation is ~3:1, revealing the redox of Dy on liquid Zn electrode is a kind of soluble–soluble system: Dy(III) + 3e⁻ = (Dy–Zn)_solution. The half-wave potential of Dy(III) was almost constant with the increase in scanning rate. The electrochemical separation of metallic Dy from the molten salt was performed using constant potential electrolysis, and the product characterized using X-ray diffraction and scanning electron microscopy–energy-dispersive X-ray spectroscopy was the thermodynamic unstable compound DyZn₅. Also, the co-deposition mechanism of Dy(III) and Zn(II) was explored, indicating that Dy(III) could deposit on pre-deposited Zn and form Dy–Zn compounds: Zn(II) + 2e⁻ = Zn and xDy(III) + yZn + 3xe⁻ = Dy_xZn_y. Moreover, the effect of Dy(III) concentration on the formation of Dy–Zn compounds was investigated. The redox peak currents corresponding to different Dy–Zn compounds changed with the increase in Dy(III) concentration. The co-deposition of Dy(III) and Zn(II) was performed using constant current electrolysis at diverse Dy(III) concentrations. The different Dy–Zn compounds were produced by controlling Dy(III) concentration.     

A density functional study on magnetic exchange interaction between Mn(II) ion and nitronyl nitroxide radical in trans- and cis-metal-radical complexes

In the recent few years, transition metal complexeswith radical ligands have received much attentionaiming at a so-called metal-radical approach for novelmolecular magnet design[1]. One of the more popularfamilies is concerned in nitronyl nitroxide radica…     

Hetero-trinuclear Zn(II)-M(II) (M = Sr,Ba) complexes based on a mononuclear Zn(II) complex metallohost: syntheses,structures and fluorescence properties

A new mononuclear Zn(II) complex, [ZnL(HOAc)] (1) (H₂L = 6,6′-diethoxy-2,2′-[1,2-ethylenedioxybis(nitrilomethylidyne)]diphenol), was synthesized by reaction of H₂L and Zn(II) acetate under solvothermal conditions. Complex 1 acts as a metallohost possessing a pentadentate O₅ donor. Complex 1 molecules bonded to one Sr(II) or Ba(II) form two new hetero-trinuclear complexes, [(ZnL)₂M(OAc)₂] (M = Sr (2), Ba (3)). In 2 and 3, Zn(II) ions are 5-coordinate, but the Sr(II) or Ba(II) ion is 10-coordinate by four μ-phenolic oxygens from two L^2? units, four oxygens from four ethoxy groups and two oxygens from two μ-acetato ligands. Furthermore, 1–3 exhibit blue emissions with the maximum emission wavelengths λ_max = 477, 500, and 471 nm when excited at 360 nm.     

Modulation of luminescence by subtle anion-cation and anion-π interactions in a trigonal Au(I)···Cu(I) complex

The trigonally coordinated [AuCu(PPh(2)py)(3)](BF(4))(2) (1) crystallizes in two polymorphs and a pseudopolymorph, each of which contains a trigonally coordinated cation with short Au(I)-Cu(I) separations of ～2.7 ?. Under UV illumination, these crystals luminesce different colors ranging from blue to yellow. The structures of these cations are nearly superimposable, and the primary difference resides in the relative placement of the anions and solvate molecules. As confirmed by time-dependent density functional theory calculations, it is these interactions that are responsible for the differential emission properties.     

Weak interactions in imidazole-containing zinc(II)-based metal–organic frameworks

The self-assembly of the two zinc(II) metal–organic frameworks, [Zn₂(L)(bdc)₂]·3MeOH·4H₂O}_n ( 1 , L = 2-(pyridin-4-yl)-3H-imidazo[4,5-c]pyridine, H₂bdc = 1,4-benzenedicarboxylic acid) and [Zn₂(L)(bdc)₂]·2DMF·H₂O}_n ( 2 ), was achieved under mild reaction conditions. Both compounds 1 and 2 were structurally characterized by single-crystal X-ray diffraction analysis. Interestingly, the coordination modes of the ligand L in two structures are entirely different. Compounds 1 and 2 were made up of paddle wheel-shaped {Zn₂(O₂C)₄} secondary building unit (SBU) clusters, which adopted three-dimensional structures with a pcu topology. Rich weak interactions were observed in the structures of both 1 and 2 . The uncoordinated imidazole and pyridine moieties exhibited electron donor–acceptor interactions, π–π stacking, hydrogen bonding, and CH–π interactions. These interactions also facilitated the abilities of the framework to adsorb CO₂ molecules. Gas adsorption studies revealed that compound 1 selectively adsorbed CO₂ (131.1 cm³/g) over N₂ (23.5 cm³/g) and H₂ (36.5 cm³/g) at a pressure of 1 atm.     

Soft template synthesis in copper(II)–dithiooxamide–methanal,copper(II)–dithiooxamide–ethanal and copper(II)–dithiooxamide–propanone triple systems in a copper(II)hexacyanoferrate(II) gelatin-immobilized matrix

Novel complexing processes in the Cu^II–dithiooxamide–methanal, Cu^II–dithiooxamide–ethanal and Cu^II–dithiooxamide–propanone triple systems proceeding under specific conditions, to copper(II)hexacyanoferrate(II) gelatin-immobilized matrix systems in contact with aqueous-alkaline (pH 12) solutions containing dithiooxamide and methanal, ethanal or propanone, have been studied. It has been shown that template synthesis leading to the formation of macrocyclic coordination compounds (2,8-dithio-3,7-diaza-5-oxanonandithioamide-1,9)copper(II), (2,8-dithio-3,7-diaza-4,6-dimethyl-5-oxanonandithio-amide-1,9)copper(II) and (4,4,6-trimethyl-2,8-dithio-3,7-diazanonen-6-dithioamide-1,9)copper(II), respectively, takes place under such conditions. Dithiooxamide, methanal, ethanal and propanone act as ligand synthons in these processes.     

Alkyne–azide cycloaddition catalyzed by a dinuclear copper(I) complex

A novel dinuclear copper complex Cu^I₂(pip)₂ was used as a catalyst for alkyne–azide cycloaddition (CuAAC) reaction. High yields (95–99%) were obtained for various substrates at a low loading of 0.2 mol %. The unique structure, high stability of the dinuclear structure in solution, and easy preparation make this complex not only a high-efficiency catalyst but also a model for understanding the mechanism of the CuAAC reaction.     

The Thermal Analysis of Binary Zn(II)–Sr(II) Cyclo-tetraphosphates

Binary Zn(II)–Sr(II) cyclo-tetraphosphates have been synthesised as new binary compounds. The synthesis is based on a thermal procedure making use of the reversible transformation of cyclo- tetraphosphates to higher linear phosphates. With respect to the proposed application of these products as special inorganic pigments some properties (thermal stability, structural parameters, anticorrosion activity) have been determined. This revised version was published online in August 2006 with corrections to the Cover Date.     

Melamine-mediated self-assembly of a Cu(II)–methylmalonate complex assisted by π+–π+ and anti-electrostatic H-bonding interactions

A Cu(II)-methylmalonate complex, (C₃H₇N₆)₄[Cu(II)(C₄H₄O₄)₂](H₂O)₄Cl₂ (1) (where C₃H₇N₆ = protonated melamine, C₄H₄O₄ = methylmalonic acid), has been synthesized from aqueous media and its crystal structure was determined by single-crystal X-ray diffraction. The anionic Cu(II)-methylmalonate complex mediated formation of interesting supramolecular assemblies in the solid state by means of ionic interactions with protonated melamine. Moreover, other forces such as antielectrostatic H-bonding and π⁺–π⁺ interactions also play a crucial role in defining the final 3-D architecture of 1. An interesting stacking among protonated melamine molecules is studied by DFT calculations. Lattice water molecules and chlorides form various hydrogen bonds to take part in the self-assembly processes.