EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 22 2010
Dipankar Maity
Abstract A novel hexacoordinating non-Schiff base ligand (H4L) with N2O4 donor atoms has been synthesized by simple Mannich reactions. The use of this ligand with Cu(ClO4)2·6H2O in different molar ratios as well as pH leads to the formation of a mononuclear species and a tetranuclear CuII complex possessing a cubane [Cu4L2] core with almost equal Cu···Cu separation. In the presence of an excess amount of copper(II) ions and triethylamine at reflux, the mononuclear [CuH2L] species can be converted into the tetranuclear one, whereas the reverse process was not observed even after prolonged reaction time. Both the complexes have been characterized by single-crystal X-ray diffraction and magnetic measurements. Magnetic studies reveal that complex 1 displays a paramagnetic Curie-type behavior whereas 2 displays a singlet-spin ground state induced by strong intramolecular antiferromagnetic interactions. [source]

A CuIINiII Complex with Ethylenediamine: Crystal Structure and Ferromagnetic Behaviour of an Aqua-Bridged Heterometallic Chain Containing Ambidentate Ni(OAc)42, Blocks

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 22 2010
Oksana V. Nesterova
Abstract A one-pot reaction of copper powder and nickel and ammonium acetates in a CH3OH solution of ethylenediamine (en) yields a unique 1D aqua-bridged polymer [Cu(en)2(,2 -H2O)2Ni(OAc)4]n·4nH2O (1) with an ambidentate Ni(OAc)42, fragment that has not been previously characterized. The basic structural motif of 1 contains a previously unreported heterometallic M(,2 -H2O)M, aqua-bridge chain with alternating metal atoms. A complex system of N/O,H···O hydrogen bonds strengthens the polymeric chains and links them into a supramolecular three-dimensional network. Variable-temperature magnetic susceptibility measurements of 1 revealed a weak ferromagnetic coupling (J = 1.1 cm,1) between the paramagnetic copper(II) and nickel(II) ions, which is transmitted through the oxygen bridges. [source]

Cubane-Like Bismuth-Iron Cluster: Synthesis, X-ray Crystal Structure and Theoretical Characterization of the [Bi4Fe8(CO)28]4, Anion

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 20 2010
Kirill Yu.
Abstract The reaction of cyclo -Bi4[Si(SiMe3)3]4 (1) with Na2[Fe(CO)4] in the presence of nBu4NCl leads to the formation of the cage compound [nBu4N]4[Bi4Fe8(CO)28] (2). According to X-ray single-crystal structure analysis, the faces of the tetrahedral Bi4 core are capped by Fe(CO)3 moieties in a ,3 fashion to give a cubanoid Bi4Fe4 framework. The four Fe(CO)4 fragments are ,1 -coordinated to bismuth, each. With 12 skeletal electron pairs the [Bi4Fe8(CO)28]4, anion (2a) is a Bi4Fe4 cubane. The negative charge is localized within cluster 2a according to the NBO analysis of its derivatives. The strength of metal,ligand interactions Bi,,3 -Fe(CO)3 is responsible for the size of the cluster's cubic core. NICS computations at the cage centers of considered molecules show that 2a has paratropic character, whereas removal of four ,1 -Fe(CO)4 fragments from latter causes spherical aromaticity of the modified clusters [Bi4Fe4(CO)12]4, (2aa) and [Bi4Fe4(CO)12]2+ (2ab), mediated by a Bi4 cluster , orbital. [source]

The Effect of Surface Area and Crystal Structure on the Catalytic Efficiency of Iron(III) Oxide Nanoparticles in Hydrogen Peroxide Decomposition

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 16 2010
Cenek Gregor
Abstract Iron(II) oxalate dihydrate has been used as a readily decomposable substance for the controlled synthesis of nanosized iron(III) oxides. The polymorphous composition, particle size and surface area of these iron oxide nanoparticles were controlled by varying the reaction temperature between 185 and 500 °C. As-prepared samples were characterized by XRD, low-temperature and in-field Mössbauer spectroscopy, BET surface area and the TEM technique. They were also tested as heterogeneous catalysts in hydrogen peroxide decomposition. At the selected temperatures, the formed nanomaterials did not contain any traces of amorphous phase, which is known to considerably reduce the catalytic efficiency of iron(III) oxide catalysts. As the thickness of the sample (, 2 mm) was above the critical value, a temporary temperature increase ("exo effect") was observed during all quasi-isothermal decompositions studied, irrespective of the reaction temperature. Increasing the reaction temperature resulted in a shift of the exo effect towards shorter times and an increased content of maghemite phase. The maghemite content decreases above 350 °C as a result of a thermally induced polymorphous transition into hematite. The catalytic data demonstrate that the crystal structure of iron(III) oxide (i.e. the relative contents of maghemite and hematite) does not influence the rate of hydrogen peroxide decomposition. However, the rate constant increases monotonously with increasing sample surface area (and decreasing thermolysis temperature), reaching a maximum of 27,×,10,3 min,1(g/L),1 for the sample with a surface area of 285 m2,g,1. This rate constant is currently the highest reported value of all known iron oxide catalytic systems and is even slightly higher than that observed for the most efficient catalyst reported to date, which has a significantly larger surface area of 337 m2,g,1. This surprisingly high catalytic activity at relatively low surface area can be ascribed to the absence of a amorphous phase in the samples prepared in this study. Taking into account these new findings, the contributions of the key factors highlighted above (surface area, particle size, crystal structure, crystallinity) to the overall activity of iron oxides forhydrogen peroxide decomposition are discussed. [source]

Synthesis, Crystal Structure, and Catalytic Properties of Novel Dioxidomolybdenum(VI) Complexes with Tridentate Schiff Base Ligands in the Biomimetic and Highly Selective Oxygenation of Alkenes and Sulfides

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 5 2010
Abdolreza Rezaeifard
Abstract Four novel dioxidomolybdenum(VI) complexes [MoO2(Lx)(CH3OH)] have been synthesized, using 2[(E)-(2-hydroxy-2-phenylethylimino)methyl]phenol derivatives as tridentate ONO donor Schiff base ligands (H2Lx) and MoO2(acac)2. A monoclinic space group was determined by X-ray crystallography from single-crystal data of a sample of these new complexes. The epoxidation of alkenes by using tert -butyl hydroperoxide and oxidation of sulfides to sulfoxides by urea hydrogen peroxide were efficiently enhanced with excellent selectivity under the catalytic influence these new MoVI complexes. The high efficiency and relative stability of the catalysts have been observed by turnover numbers and UV/Vis investigations. The electron-poor and bulky ligands promoted the effectiveness of the catalysts. [source]

An Unusual Anion,, Interaction in an ;rido Organometallic Assembly: Synthesis, First Crystal Structure, and Computational Study

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 25 2009
Jamal Moussa
Abstract The organometallic assembly [Cp*Ir(,6 -C6H2O4)(BF2)2(CF3SO3)][Cp*Ir(,-Cl)3IrCp*] (3) was prepared from [Cp*Ir(solvent)3][OTf]2 (2) and 1,2,4,5 tetrahydroxybenzene (THB, 1) in acetone, in the presence of an excess amount of BF3·2H2O. Assembly 3 was fully characterized by multinuclear NMR spectroscopy. Remarkably, the X-ray molecular structure of 3 shows that an anion,, interaction occurs between the neutral component Cp*Ir(,6 -C6H2O4)(BF2)2 of the assembly and the CF3SO3 anion of the cationic species [Cp*Ir(,-Cl)3IrCp*]. Computational analysis was carried out on 3 to unravel the nature of this noncovalent interaction. Such an example could serve as a model to explain the important role of anions in organometallic chemistry and asymmetric catalysis. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source]

Reactivity of Cationic Lanthanide(III) Monoporphyrinates towards Anionic Cyanometallates , Preparation, Crystal Structure, and Luminescence Properties of Cyanido-Bridged Di- and Trinuclear d,f Complexes

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 22 2008
Xunjin Zhu
Abstract The metathesis reaction between two equivalents of [Ln(tpp)(H2O)3]Cl (Ln = Yb, Er; tpp2, = tetraphenylporphyrinate dianion) and one equivalent of cyanometallate in dmf at room temperature under nitrogen for 24 hours gave the cyanido-bridged d,f trinuclear complexes [{Ln(tpp)(dmf)n}2{(,-NC)2M(CN)2}] (Ln = Yb, n = 2, M = Ni, 1; Ln = Er, n = 3, M = Ni, 2; Ln = Yb, n = 2, M = Pt, 3; Ln = Er, n = 3, M = Pt, 4), a trinuclear complex [{Er(tpp)(dmf)2}{(,-NC)2Fe(CN)4}{Er(Htpp)(dmf)2}] (5), and a dinuclear complex [{Er(tpp)(dmf)(H2O)}(,-NC)Ag(CN)] (6) when the cyanometallate used was the dianion [M(CN)4]2, (M = Ni, Pt), the trianion [Fe(CN)6]3,, and monoanion [Ag(CN)2],, respectively. The solid-state structures of these complexes were ascertained by X-ray crystallography. Photoluminescence studies of complexes 1,4 showed that these complexes displayed photophysical properties characteristic of normal metal,porphyrinato complexes. Their absorption bands and emission peaks in the visible region are typical of the intraligand ,,,* transitions of the porphyrinato ligand. Furthermore, these complexes also exhibited emission characteristic of the lanthanide(III) ion in the near-infrared (NIR) region, which was quenched by the cyanometallates. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source]

Synthesis and Crystal Structure of Mercury-Substituted Type-I Clathrates A8Hg4Sn42 (A = K, Rb, Cs)

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 4 2008
Andreas Kaltzoglou
Abstract The mercury-substituted type-I clathrates A8Hg4Sn42,with A = K, Rb or Cs, were obtained by fusion of the pure elements at high temperatures. The crystal structures of the compounds were refined from single-crystal X-ray diffraction data. They crystallize in the space group Pmn (No. 223), Z = 1 with a = 12.1255(4) Å for K8Hg4Sn42 (1), a = 12.1838(4) Å for Rb8Hg4Sn42 (2) and a = 12.2130(4) Å for Cs8Hg4Sn42 (3). The 3D framework of four-bonded atoms defines two types of polyhedral cages of different size that are fully occupied by the alkali-metal atoms. All three compounds are considered as formally charge-balanced Zintl phases without any homogeneity range. Differential thermal analysis (DTA) indicates that the stability of the clathrates significantly depends on the size of the encaged cations. The thermal stability of the title compounds and the binary phases A8Sn44 (A = K, Rb, Cs) is discussed. Temperature-dependent magnetic measurements for compound 3 show also the expected diamagnetic behaviour. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source]

A New Donor-Stabilized Ditungsten Amido Alkoxido Species: Synthesis, Crystal Structure, Fluxionality, and Grafting onto Silica

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 35 2007
Olivier Coutelier
Abstract A new dimeric tungsten(III) complex containing amidoand chelating pyridine,alkoxido ligands was synthesized through protonolysis of [W2(NMe2)6] by 2-(2-pyridyl)propan-2-ol and fully characterized by X-ray diffraction and infrared and NMR spectroscopy. Intramolecular exchange processes were studied by variable-temperature NMR spectroscopy. The compound was grafted onto dehydroxylated silica by protonolysis of an amido,tungsten bond, and the structure of the supported species was investigated by infrared and solid-state (bidimensional) NMR spectroscopy. The reactivity of the molecular and grafted species toward alkynes was probed. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]

[(Pyridylcarbonyl)pyridyl]triazolopyridines, Useful Ligands for the Construction of Polynuclear Coordination Compounds , Synthesis, Crystal Structure and Magnetic Properties of a Novel Tetranuclear Copper(II) Cubane,

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 29 2007
Belén Abarca
Abstract A new tetranuclear cubane Cu4O4 complex has been synthesised from assembly of CuII ions and the polydentate ligand (pyridin-2-yl){6-([1,2,3]triazolo[1,5- a]pyridin-3-yl)pyridin-2-yl}methanone. Crystallographic analysis indicates that the Cu4O4 unit has an S4 symmetry. The magnetic properties have been analysed using the H = ,2,i,jJijSiSj spin Hamiltonian. Two distinct coupling constants, 2J1,3 = ,37.4 cm,1 and 2J1,2 = ,2.6 cm,1, obtained from the fitting of the experimental data have been rationalised on the basis of a density functional study of magnetostructural correlations in cubane complexes containing the Cu4O4 core. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]

Crystal Structure and Surface Photovoltage Properties of MnII Coordination Supramolecules

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 24 2007
Li-Ping Sun
Abstract Three MnII coordination supramolecular complexes [Mn(pdc)(H2O)]n1, {[Mn(pdc) (phen)(H2O)]·3H2O}n2, and {[Mn(cyan)2(H2O)4]·2HCl·2(Hcyan)} 3 (H2pdc = pyridine-2,3-dicarboxylic acid, Hcyan = cyanuric acid, phen = 1,10-phenanthroline) were hydrothermally synthesized and their structures determined by single-crystal X-ray diffraction. The pdc group in complex 1 bridges the MnII ions to form an infinite 3D structure. In complex 2, the MnII ion is bridged to a 1D infinite chain by pdc groups and the chain is further connected to a 2D structure by hydrogen bonds. The 3D structure of complex 3 is formed by hydrogen bonds and O···Cl weak interactions. Surface photovoltage spectroscopy (SPS) of complexes 1,3 indicate that they all possess positive SPV response in the range of 300,800 nm and show p -type semiconductor characteristic. The intensities of the SPV responses are obviously different, and this can mainly be attributed to the differences in their structures. Field-induced surface photovoltage spectroscopy (FISPS) of complexes 1,3 confirms their p -type semiconductor characteristic.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]

Synthesis and Crystal Structure of a Heptanuclear and an Octanuclear Copper(II) Complex Derived from ,- D -Glucofuranoses

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 23 2007
Michael Gottschaldt
Abstract CuII complexes of different 6-(,-keto-enamino)-6-deoxy-1,2- O -isopropylidene-,- D -glucofuranoses 3a,f have a high tendency to build up oligonuclear clusters. Two new oligonuclear copper(II) complexes could be synthesised, crystallised and their structures determined. The complex Cu(3a) was found to consist of a heptanuclear cluster in which two ,-cubane like substructures share one copper ion. The structure is highly asymmetric and in the cluster every CuII ion has a different coordination geometry. Variation of the residues of the ,-ketoenaminic unit leads to the formation of the octanuclear copper(II) complex Cu(3e). Similarly, this has two ,-cubane subunits consisting of a heptanuclear structure with an additionally attached copper ion. In the crystal, two Cu8 cluster molecules are found differing in their geometries due to intermolecular interactions responsible for the formation of a supramolecular network. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]

Aiding Factors in the Formation of Azaplatinacyclobutane Rings , X-ray and Crystal Structure of [Pt{CH(Ph)CH2NEt2 -,C,,N}(N,N,N,,N, -tetramethylethylenediamine)]+ and of Its Open-Chain Precursor

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2007
Giuseppe Lorusso
Abstract The addition products 2 of a secondary amine to a coordinated olefin, in the cationic complexes [PtCl(,2 -CH2=CHR)(tmeda)]+ (tmeda = N,N,N,,N, -tetramethylethylenediamine; R = Me, 1a; Ph, 1b, H, 1c), undergo in basic medium an intramolecular nucleophilic substitution with elimination of the chlorido ligand and formation of an azaplatinacyclobutane ring 3. The ring-closing process occurs notwithstanding the absence of a labilizing ligand trans to the leaving chlorido ligand and of bulky substituents on the amino,ethanide chain. If the addition product 2 is a mixture of Markovnikov and anti-Markovnikov isomers, the ring-closing reaction is faster for the anti-Markovnikov form, and this leads to an increase of the relative amount of the anti-Markovnikov isomer in the cyclized species 3. The difference in the rate of formation of the azaplatinacyclobutane ring between the two isomers has been interpreted on the basis of a more favorable stereochemistry in the case of the anti-Markovnikov form. The X-ray crystal structures of [Pt{CH(Ph)CH2NEt2 -,C,,N}(tmeda)]+ (3bn) and of its open-chain precursor, [PtCl{CH(Ph)CH2NHEt2}(tmeda)]+ (2bn) fully support this hypothesis.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]

Synthesis, Crystal Structure, and Magnetic Properties of Two Manganese(II) Polymers Bearing Ferrocenecarboxylato Ligands

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 14 2007
Zilu Chen
Abstract Reactions of Mn(ClO4)2·6H2O with FcCO2Na [Fc = (,5 -C5H4)Fe(,5 -C5H5)] in methanol solution gave [Mn3(FcCO2)6(CH3OH)4]n (1), and, in the presence of 4,4,-bipyridine (4,4,-bpy), [Mn3(FcCO2)6(H2O)2(4,4,-bpy)]n (2). Both complexes have the similar chains with a sequence of ,Mn,(,2 -COO)n,Mn,(,2 -COO),Mn,(,2 -COO),Mn,(,2 -COO)n,Mn, (n = 4 and 2 for complex 1 and 2, respectively), which are constructed alternatively from mononuclear [MnII] units and dinuclear [Mn2(FcCO2)4] units by ,2 -ferrocenecarboxylato- O,O, bridging. The two MnII ions in the dinuclear [Mn2(FcCO2)4] units of complex 1 are connected by four ferrocenecarboxylato ligands to form a swastika-like shaped skeleton, which is rare in metallocenecarboxylato complexes. However, the two MnII ions in the dinuclear [Mn2(FcCO2)4] units of complex 2 are bridged only by two carboxylato ligands, and the other two ferrocenecarboxylato ligands in this unit bind in a chelating mode. The chains in complex 2 are further interconnected by the coordinated 4,4,-bipyridine molecules to form two-dimensional coordination sheets. Magnetic susceptibility measurements revealed a weak antiferromagnetic coupling for both complexes. A model Heisenberg chain comprising classical spins coupled through alternating exchange interactions J1,J1,J2 (AF1,AF1,AF2) is proposed to describe the magnetic behavior. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]

A Trinuclear Aqua Cyano-Bridged Ruthenium Complex [{(,5 -C5H5)(PPh3)2Ru(,-CN)}2RuCl2(PPh3)(H2O)]PF6: Synthesis, Characterization and Crystal Structure

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 13 2007
Viatcheslav Vertlib
Abstract The organometallic trinuclear aqua cyano-bridged complex [{(,5 -C5H5)(PPh3)2Ru(,-CN)}2RuCl2(PPh3)(H2O)]PF6 (1), in which the fragment [RuCl2(PPh3)(H2O)] acts as a bridge and an acceptor group between the two terminal cyclopentadienyl ruthenium cyano moieties, was isolated in moderate yield from the reaction of [(,5 -C5H5)(PPh3)2RuCN] with [RuCl2(PPh3)3] in THF. To the best of our knowledge, compound 1 is one of the few examples of a trinuclear array of ruthenium fragments bridged by the nitrogen atom of the,C,N, group (Ru,C,N,Ru,,N,C,Ru) with a Ru-coordinated water molecule. The new aqua complex was structurally characterized by FTIR, 1H, 13C, and 31P NMR spectroscopy, mass spectrometry, elemental analysis, single-crystal X-ray diffraction, and cyclic voltammetry. The title complex crystallizes in a triclinic unit cell a = 17.3477(6) Å, b = 17.8551(5) Å, c = 18.2460(7) Å, , = 95.693(2)°, , = 111.648(2)°, and , = 97.839(2)° in the space group P with Z = 2.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]

Solvothermal Synthesis, Crystal Structure, and Thermal Stability of Three-Layered Thioantimonate(III) Complexes: [Ni(C3H10N2)3]Sb4S7, [C4H14N2]Sb8S13·H2O, and [C6H18N2]Sb10S16·H2O

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 11 2007
Meng Zhang
Abstract Three new thioantimonate(III) complexes [Ni(1,2-PDA)3]Sb4S7 (1) (1,2-PDA = 1,2-propanediamine), [dmenH22+]Sb8S13·H2O (2) (dmen = N,N -dimethylethylenediamine), and [deenH22+]Sb10S16·H2O (3) (deen = N,N -diethylethylenediamine), prepared under solvothermal conditions, have been characterized by single-crystal X-ray diffraction, elemental analysis, and DTA-TG measurements. In compound 1, a rectangle-like Sb16S16 heteroring whose dimensions are about 8.1,×,14.7 Å is observed, this is the largest reported pore in layered thioantimonates to date. Further condensation of the Sb16S16 heterorings resulted in an unprecedented framework of the five-atom thick SbxSyn, layer. In 2, a new member of SbnSn (n = 2, 3, 4, 8, 16, 30, 31, 32) heterocycles Sb15S15 heteroring has been obtained as the first example. In compound 3, the most particular feature is that when the secondary Sb,S bonds are considered the Sb2 atom becomes sevenfold coordinated.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]

Control of Intramolecular Ether-Oxygen Coordination in the Crystal Structure of Copper(II) Complexes With Dipicolylamine-Based Ligands

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 8 2007
Yuji Mikata
Abstract Thirteen crystal structures of copper(II) complexes with a series of dipicolylamine (DPA)-derived ligands, N -(2-methoxyethyl)- N,N -bis(2-pyridylmethyl)amine (L1), N -[2-(2-hydroxyethyloxy)ethyl]- N,N -bis(2-pyridylmethyl)amine (L2) and N -(3-methoxypropyl)- N,N -bis(2-pyridylmethyl)amine (L3), have been determined and the factors that control the coordination of the ether-oxygen atom of these ligands to the copper centre are discussed. Complexes that have +1 or +2 charges exhibit coordination of the ether-oxygen atom, whereas neutral complexes in which two anions are bound to the copper(II) centre tend to lose the oxygen coordination. Upon chelation of the oxygen atom, L3 forms a six-membered chelate ring with respect to the 3-aminopropyl ether moiety whereas L1 and L2 form a five-membered chelate. This difference, especially in the nitrate and bromide complexes, determines whether the ether-oxygen atom chelates to the metal centre to give a monocationic complex, or the second anion coordinates to the metal centre to form the ether-free, neutral complex. The terminal anchor hydroxy group of L2 facilitates the ether-oxygen coordination via a hydrogen bond interaction to the donor atom located trans to the aliphatic nitrogen atom in the basal plane. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]

Crystal Structure, Solid-State NMR Spectroscopic and Photoluminescence Studies of Organic-Inorganic Hybrid Materials (HL)6[Ge6(OH)6(hedp)6]·2(L)·nH2O, L = hqn or phen,

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 23 2006
Luís Mafra
Abstract Two germanium,hedp4, solids with heteroaromatic amines 8-hydroxyquinoline (hqn) and 1,10-phenanthroline (phen), (HL)6[Ge6(OH)6(hedp)6]·2(L)·nH2O (L = hqn or phen), in I and II respectively, have been prepared and characterised by single-crystal XRD, thermogravimetry, FTIR and UV/Vis spectroscopy. The complex hydrogen-bond networks, particularly in compound I, have been studied by advanced high-resolution solid-state NMR spectroscopy that combines homonuclear recoupling techniques (two-dimensional 1H- 1H DQF and 1H- 1H RFDR MAS NMR) and combined rotation and multiple-pulse spectroscopy (two-dimensional 1H- 1H FS-LG, 1H- 31P FS-LG). The fine details of the crystal structure of I have been elucidated, mainly those involving the ,,, stacking of 8-hydroxyquinoline and the relative orientation of adjacent such molecules. Compound II exhibits an emission from the lowest triplet-state energy (,,,* 0-phonon transition) of the aromatic rings at 320 nm (31250 cm,1) from 14 K to room temperature. In contrast, the triplet emission of I at 530 nm (18868 cm,1) is only detected at low temperature, because of thermally activated non-radiative mechanisms. The emission spectra of I and II display a lower-energy component with a larger life time, which results from the formation of an excimer state that originated from the ,,, phenanthroline and hydroxyquinoline interactions, respectively. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source]

Synthesis, Crystal Structure, and Second-Order Nonlinear Optical Properties of Ruthenium(II) Complexes with Substituted Bipyridine and Phenylpyridine Ligands

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2006
Laurence Labat
Abstract Two new ruthenium(II) complexes of formula [Ru(bpy)2(L1)][PF6] and [Ru(bpy)2(L2)][PF6]2 are reported. HL1 is a (nitrophenyl)ethenyl-substituted phenylpyridine ligand, and L2 is the bipyridine analogue of HL1. The X-ray crystal structure of [Ru(bpy)2(L1)][PF6] has been solved, and the compound is found to crystallize in the monoclinic C2/c space group. The electronic spectrum of the cyclometalated derivative [Ru(bpy)2(L1)][PF6] exhibits a low-lying transition that is red-shifted from 454 to 546 nm relative to that of the parent bipyridine-based complex, which reveals an important charge-transfer character. To support this assumption, the nonlinear optical properties were investigated by the hyper-Rayleigh scattering technique and indicate a molecular static hyperpolarizability (,0) equal to 230,×,10,30 cm5,esu,1. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source]

X-ray Crystal Structure and Characterization in Aqueous Solution of{N,N,-Ethylenebis(pyridoxylaminato)}zinc(II)

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 3 2006
Isabel Correia
Abstract The complexation of ZnII with H2Rpyr2en [H2Rpyr2en = N,N,-ethylenebis(pyridoxylaminato)] in aqueous solution has been studied by pH potentiometry and 1H NMR spectroscopy. Complex formation constants are determined and binding modes proposed. Complex formation starts at around pH 4, and several species with a 1:1 ligand-to-metal ratio with different protonation states form up to pH 12. Only above pH 10 does a hydrolytic species [ZnLH,1], become important. The crystal and molecular structures of [ZnCl(H2Rpyr2en)]+Cl,·1.5H2O (1) have been determined by X-ray diffraction. The coordination of the H2Rpyr2en ligand involves the two phenolate-O and two amine-N atoms in a distorted square-pyramidal geometry. The two pyridine-N atoms are protonated, and a Cl, atom completes the coordination sphere. Upon coordination, both N-amine atoms of H2Rpyr2en become stereogenic centres, and in both molecules of the unit cell of 1 one of the N-amine donors has an (R)-configuration, and the other an (S)-configuration. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source]

Synthesis and Investigations of the Crystal Structure of aDinuclear Diazadiene Molybdenum Oxo-Imido Complex with a Unique N3Mo(,-O)2MoN3 Core

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 24 2005
Alexei Merkoulov
Abstract Ligand metathesis of the diimido and dioxo precursor complexes [Mo(X)2Cl2(DME)] (X = O, NtBu) leads to the mixed oxo-imido derivative [Mo(NtBu)(O)Cl2(DME)] (1). By treatment with Li2DAD (DAD = 1,4-di- tert -butyl-1,4-diazabuta-1,3-diene), 1 is converted into the complex [Mo(NtBu)(O)(DAD)]2 (2). The crystal structure determination on a nonmerohedral twin of 2 reveals a dinuclear molecular structure with nearly symmetrical bridging oxygen atoms. The smaller oxo ligand tends to be a better bridging functionality than the imido ligand; the unprecedented N3Mo(,-O)2MoN3 configuration is favored over a ON2Mo(,-N)2MoN2O core. Compared to other known molybdenum DAD complexes, 2 reveals some degree of pyramidalization at the nitrogen atoms of the DAD ligand. In accord with the Mo,N, N,C, and C,C bond lengths, complex 2 is best described as an ene-diamido complex of formally six-valent molybdenum. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source]

Synthesis, Crystal Structure and Characterisation of a Novel Chiral Mixed-Valence Vanadium Oxide Hybrid, [V5O11(dien)3]

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2005
Ming-Lai Fu
Abstract The novel chiral mixed-valence vanadium oxide hybrid [V5O11(dien)3] (1) (dien = NH2C2H4NHC2H4NH2) has been synthesised by a hydrothermal reaction of V2O5 and dien in aqueous solution and characterised by elemental analysis, IR spectroscopy, TG-DSC analysis, magnetism, EPR spectroscopy, single-crystal X-ray diffraction and powder XRD. The X-ray diffraction analysis revealed that the structure of 1 can be regarded as being constructed from two [VVO4]3, groups bicapping three [VIVO(dien)]2+ units to form a discrete asymmetric pentanuclear vanadium complex with the dien ligands coordinating directly to the vanadium(IV) centres. Compound 1 exhibits an interesting tube-like 3D supramolecular structure due to abundant hydrogen-bonding interactions between the oxygen atoms of the inorganic backbone and the hydrogen atoms of the dien ligands from adjacent molecules. The variable-temperature magnetic susceptibility data of 1 suggest a weak ferromagnetic interaction among V4+ ions in the cluster. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source]

Synthesis and Physicochemical Characterization of Bis(macrocycles) Involving a Porphyrin and a meso -Substituted Corrole , X-ray Crystal Structure of a [(Free-base porphyrin),corrole]bis(pyridine)cobalt Complex

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 6 2005
Jean-Michel Barbe
Abstract A very efficient, simple synthesis of face-to-face porphyrin,corrole free-bases bearing substituents at the meso positions of the corrole ring is reported. Starting from the (porphyrin,aldehyde)zinc species 1Zn, porphyrin,corrole free-bases (3M, 3C) are obtained in two steps, in fairly good yields (40,43,%), compared to 11 steps for their corrole ,-pyrrole-substituted counterparts. Moreover, the possibility to directly synthesize the free-base (porphyrin,corrole)cobalt complex (5M or 5C) allows for the further preparation of heterodimetallic derivatives. Crystals of the bis(pyridine) adduct of 5M have been grown; the molecular structure clearly shows that the two pyridine molecules are coordinated to the cobalt ion in endo and exo positions, leading to an open-mouth geometry of the bis(macrocycle). The structure of 5M(py)2also shows intermolecular ,,, interactions along the [1,0,0] direction, leading to stacking of the complexes. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source]

Experimental and Theoretical Studies of Homoleptic Tellurium Cyanides Te(CN)x: Crystal Structure of Te(CN)2

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 24 2004
Thomas M. Klapötke
Abstract The labile tellurium cyanide species Te(CN)2 and Te(CN)4 have been prepared by treatment of tellurium(IV) tetrahalides with cyanide. Both are thermosensitive solids and, in addition, the tetracyanide was found to be pyrophoric. The crystal structure of Te(CN)2 has been determined. The structures of Te(CN)2, Te(CN)4, and Te(CN)6 have been calculated at various levels of theory. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source]

A New Trinuclear Linear Copper(II) Complex: Unusual Crystal Structure with Semi-Coordinated Thiophene Moieties and Weak Antiferromagnetic Coupling Through the Bridging Imidazolate Rings

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 23 2004
Yufei F. Song
Abstract A trinuclear copper(II) complex, [Cu3(imthio)2(NO3)4(MeOH)2] [where Himthio is 1,1-bis(imidazol-2-yl)-3-(thiophen-2-yl)-2-azapropane], has been synthesized by the reaction of Himthio with Cu(NO3)2·3H2O in MeOH. The structure of the copper complex is centrosymmetric and contains a linear trinuclear array of copper atoms. The central copper(II) ion, Cu1, which lies on an inversion centre, is equatorially coordinated by four nitrogen atoms from two anionic imthio ligands and axially by two semicoordinated thiophene sulfur atoms to give an octahedral environment (Cu1,S1 3.136 Å). The Himthio ligand bridges Cu1 and the terminal copper(II) ions through imidazole nitrogen atoms. The coordination around the external ions is completed by the oxygen atoms from two nitrate groups and by a methanol molecule in a distorted square-pyramidal geometry. The two terminal copper(II) complexes can be considered to be chelating ligands for the central CuII ion. The EPR spectrum of the complex in MeOH at 77 K shows two mononuclear species, as is fully confirmed by EPR simulation. Magnetic susceptibility of the complex shows weak antiferromagnetic behaviour (J = ,71.37 cm,1) caused by the overlapping of the magnetic orbitals of the copper atoms and the bridging imidazolate rings. (© Wiley-VCH Verlag GmbH & Co.. KGaA, 69451 Weinheim, Germany, 2004) [source]

NMR Study of L-Shaped (Quinoxaline)platinum(II) Complexes , Crystal Structure of [Pt(DMeDPQ)(bipy)](PF6)2

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 23 2004
Enrico Rotondo
Abstract A 1H and 13C NMR study of nine PtII complexes of DMeDPQ [6,7-dimethyl-2,3-bis(2-pyridyl)quinoxaline] and BDPQ [2,3-bis(2-pyridyl)benzo[g]quinoxaline], and the crystal structure of one of them, are reported. The results are consistent with Cs symmetry of "L-shaped square-planar complexes". The rigid seven-membered chelated quinoxaline ligand holds the fused aromatic rings nearly perpendicular to the PtII coordination plane, generating the peculiar L-shaped structure. Ancillary ligands in the residual coordination sites are: a) bidentate flexible-planar 2,2,-bipyridine (bipy; complexes 1 and 2); b) bidentate rigid-planar dipyrido[3,2- a:2,3,- c]phenazine (dppz) or benzo[b]dipyrido[3,2- h:2,,3,- j]phenazine (bdppz; complexes 3,6); or c) 3-substituted monodentate pyridines (3-Rpy; complexes 7,9). The L-shaped geometry has been exploited to gain insight into the steric and dynamic features that regulate the noncovalent interactions of these square-planar complexes with DNA. We have shown previously, for [Pt(bipy)(n -Rpy)2]2+, that bipy twisting can be frozen out on the NMR timescale below 260 K. Preservation of the Cs symmetry at low temperature indicates a lack of bipy fluxionality within these L-shaped structures. The static butterfly-like symmetric orientation of the quinoxaline pyridyl rings accounts for the hampered twisting of Pt(bipy), which is otherwise assisted by the synchronous "windscreen wiper" conrotatory rocking of the ancillary pyridine rings. The L-geometry can also be used to monitor the ancillary n -Rpy rotation by NMR spectroscopy. The quasi-vertical quinoxaline pyridyl rings alignment leave room in the coordination plane for the crossing of the opposite pyridine rings, thereby reducing their rotational barriers about the Pt,N bond. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source]

Synthesis, Crystal Structure, and Magnetic Properties of Mn2(OH)2SO4: A Novel Layered Hydroxide

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 11 2004
Mohsen Ben Salah
Abstract Mn2(OH)2SO4, obtained as pink prismatic crystals by the hydrothermal reaction of MnSO4·H2O and NaOH at 240 °C for 24 h, consists of layers of Mn hydroxide connected to each other through µ6 -sulfate ions. Each layer exhibits vacancies, and each vacant space is capped at the top and bottom by the sulfate groups. The compound is paramagnetic above 50 K (C = 4.36 emu K mol,1, µeff = 5.91 µB, , = ,100 K). Below 45 K, the magnetization increases slightly, indicating canted-antiferromagnetic (TNéel = 42±1 K) behavior consistent with the linear dependence of the magnetization as a function of the field at 2 K, which reaches only 0.4 µB at 50 kOe, and the lack of any imaginary component of the ac-susceptibilities (ac = alternating current). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source]

Template Synthesis, Crystal Structure and Luminescent Properties of Neutral N4O3 Tripodal LnIIIL Complexes (LnIII = La3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+ or Lu3+; H3L = Tris{[3,-(2,,-pyridyl)-5,- tert -butyl-2,-hydroxybenzylidene-2-imino]ethyl}amine)

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 4 2004
Wai-Kwok Wong
Abstract In the presence of Ln3+ (Ln = La, Eu, Gd, Tb, Dy, Ho, Er, Tm or Lu), tris(2-aminoethyl)amine condensed with three equivalents of 3-(2,-pyridyl)-5- tert -butyl-2-hydroxybenzaldehyde in methanol to give the neutral Schiff-base complex LnIIIL (Ln = La 1, Eu 2, Gd 3, Tb 4, Dy 5, Ho 6, Er 7, Tm 8 and Lu 9; H3L = tris{[3,-(2,,-pyridyl)-5,- tert -butyl-2,-hydroxybenzylidene-2-imino]ethyl}amine). The structures of compounds 4,7 were determined by X-ray crystallography. The crystal structure analyses revealed that the Schiff base behaves as a tri-deprotonated heptadentate ligand encapsulating the lanthanide metal ion within the N4O3 cavity, with all the pyridyl groups being pendant. Solution spectroscopic data suggest that the LnIIIL complexes remain intact in methanol and exist as nine-coordinate non-electrolytes with the lanthanide metal ions coordinated to the N4O3 cavity of the tripodal Schiff base and two solvent molecules. The solution photoluminescent properties of these lanthanide Schiff-base complexes were also examined. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source]

X-ray Crystal Structure of a Sodium Salt of [Gd(DOTP)]5,: Implications for Its Second-Sphere Relaxivity and the 23Na NMR Hyperfine Shift Effects of [Tm(DOTP)]5,

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 23 2003
Fernando Avecilla
Abstract The X-ray structure of the sodium salt of [Gd(DOTP)]5, shows two different chelates, [Gd(1)(DOTP)]5, and [Gd(2)(DOTP)]5,, bound at either surface of a sheet formed by a cluster of hydrated Na+ ions. Each [Gd(1)(DOTP)]5, anion binds directly to four Na+ ions of this cluster through the free oxygen atoms of the phosphonate groups of the adjacent ligand, while each [Gd(2)(DOTP)]5, unit is connected to the cluster via hydrogen bonds only. The Gd3+ ions in the two moieties do not have any inner-sphere water molecules, and are eight-coordinate. Their coordination polyhedra are twisted square antiprisms, with slightly different twist angles. These m, isomers are found in the crystal structure as racemic mixtures of enantiomers. Only one set of NMR resonances is observed in aqueous solution, corresponding to an averaged m, isomer. In this crystal structure, the Na+ ions bind the phosphonate oxygen atoms of the [Gd(1)(DOTP)]5, anion at positions far removed from the main symmetry axis. This is significantly different from the binding mode(s) previously proposed to be occurring in solution between Na+ and [Tm(DOTP)]5,, based on the interpretation of solution paramagnetic 23Na NMR shifts. This could arise as a result of the effects of the cluster of hydrated Na+ ions that are present, which may hinder axial binding modes and distort lateral binding modes. Further, in the crystal structure, both types of Gd3+ centers have four second-sphere water molecules that are located at distances (4.2,4.5 Å) significantly longer than those previously proposed from the analysis of the NMRD data of [Gd(1)(DOTP)]5,. This is a result of the coordination of Na+ by these water molecules, thus preventing their direct interaction with the phosphonate oxygen atoms. However, in solution such second-sphere water molecules can interact strongly with the phosphonate ligand oxygen atoms, resulting in efficient relaxation if their binding has relatively long lifetimes (> 50 ps). Rotational immobilization will amplify this contribution, thus making it similar to outer-sphere relaxation. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source]

Synthesis, Crystal Structure, and Optical Properties of a New Molecular Complex of C60 with a Covalently Linked (FeIIITPP)2O Dimer

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 21 2003
Aleksey L. Litvinov
Abstract A new molecular complex of C60 with covalently linked ,-oxo dimer (FeIIITPP)2O are (TPP = tetraphenylporphyrin) was obtained. The complex has a neutral ground state and is formed mainly by van der Waals forces. The X-ray analysis of the crystal structure of the complex showed it to have isolated packing of fullerenes in which each fullerene molecule is embraced in a pocket built by porphyrins. Optical properties and EPR behavior of the complex are described. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source]