Home About us Contact
|
Home About us Contact | ||
|
|
||
Polynuclear Complexes (polynuclear + complex)
Selected AbstractsAssembly of Dinuclear CuII Rigid Blocks by Bridging Azido or Poly(thiocyanato)chromates: Synthesis, Structures and Magnetic Properties of Coordination Polymers and Polynuclear ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 8 2010Sergey V. Kolotilov Abstract Reaction of a dinuclear cationic copper(II) complex of 4,4,-[2-(3-hydroxyiminobutyl)imino]biphenyl [CuII2(LH)2]2+ with N3, resulted in the formation of a dinuclear azido [CuII2(LH)2(N3)2(H2O)2] complex or a 2D coordination polymer [CuII2(LH)2(N3)2]n. Reaction of the dinuclear complex with [CrIII(NCS)6]3, or [CrIII(NCS)4(NH3)2], produced a 2D polymer {[CuII2(LH)2(CH3CN)2]3[CrIII(NCS)6]2}n or a 1D chain, constructed from tetranuclear units {[CuII2(LH)2][CrIII(NCS)4(NH3)2]2}n. Structures of the compounds were determined by X-ray crystallography and complexes were characterised by the temperature dependency of the magnetic susceptibility and by ESR spectroscopy. Magnetic properties of homometallic compounds were fit with the model of a dimer with the Hamiltonian , = ,J,1·,2. For heterometallic complexes ,MT curves were fit as the superposition of magnetism resulting from both [CuII2(LH)2]2+ and the adjacent CrIII -containing anion. J values for the complexes lie in the range from ,12.74(4) to ,17.77(8) cm,1. It was shown that the 4,4,-biphenyl bridge efficiently mediates exchange interactions. [source] Intermetallic Interactions Within Solvated Polynuclear Complexes: A Misunderstood Concept,ANGEWANDTE CHEMIE, Issue 1 2010Favera, Natalia Dalla Einzug der Gladiatoren: Zwei Arten von Effekten konkurrieren um die Kontrolle der intermetallischen Wechselwirkungen in mehrkernigen (supra)molekularen Helicaten in Lösung (siehe Bild): Coulomb-Wechselwirkungen erzeugen eine starke intermetallische Abstoßung bei kleinen Abständen, und Solvatisierungseffekte resultieren in einer starken intermetallischen Anziehung für kleine pseudosphärische Ionen mit kleinen Metall-Metall-Abständen d. [source] An Energy Dispersive X-ray Diffraction Study of Dioxouranium(VI) in 1 M Lithium CitrateEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 13 2004Ermanno Vasca Abstract An Energy Dispersive X-ray Diffraction (EDXD) study of 0.3 M dioxouranium(VI) in 1 M lithium citrate at pH = 5 is reported. The data are in accordance with the existence of a predominately polynuclear complex containing four U atoms, concluded from potentiometric measurements. The uranium atoms lie at the corners of two triangles sharing one edge. Five O atoms surround each uranyl group, the uranium coordination polyhedron being a pentagonal bipyramid; four U atoms are linked through double or single O bridges. The U,U distances are 3.95 Å and 4.65 Å. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Nucleophilic Addition of Water and Alcohols to Dicyanonitrosomethanide: Ligands with Diverse Bonding Modes in Magnetically Coupled d-Block ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 1 2010Anthony S. R. Chesman Abstract Ligands resulting from the transition-metal-promoted nucleophilic addition of water or an alcohol to dicyanonitrosomethanide ions (dcnm) have been utilised in the formation of a large series of polynuclear complexes. Addition of water to dcnm results in formation of carbamoylcyanonitrosomethanide (ccnm); deprotonation of this ligand gives amidocarbonyl(cyano)nitrosomethanide (acnm), which has been incorporated into the trinuclear complex [Cu3(acnm)2(dmae)2(H2O)2] [dmae = 2-(dimethylamino)ethoxide] (1) which shows strong antiferromagnetic coupling with an exchange coupling constant, J = ,500 cm,1. [Cu(acnm)(NH3)2], (2) marks the first instance of acnm facilitating the formation of a coordination polymer, namely a 1D chain with intramolecular hydrogen bonding. Attempts to synthesise 2 through different reaction conditions instead resulted in the mononuclear [Cu(acnm)(NH3)2(py)] (py = pyridine) (3). The addition of ethanol to dcnm results in cyano[imino(ethoxy)methyl]nitrosomethanide (cenm) which features in the mononuclear [Cu(cenm)2(H2O)2] (4) and polymeric {[Cu(cenm)2]2·H2O}, (5). The latter is the first example of the cenm ligand in a coordination polymer and has a highly unusual coordination mode through the nitrile groups and extremely weak antiferromagnetic coupling. {[Mn3(ccnm)2(EtOH)2(OAc)4]·2EtOH}, (6) and (Et4N)2[Cu(ccnm)4] (7) contain previously unobserved coordination modes of the ccnm ligand while the complex [Mn(cmnm)3Mn(bipy)(MeOH)](ClO4) (8) {cmnm = cyano[imino(methoxy)methyl]nitrosomethanide, bipy = 2,2,-bipyridine} displays weak antiferromagnetic coupling between manganese atoms with J = ,1.44 cm,1. A change in the solvent systems used in the synthesis of 7 results in the formation of the mononuclear complexes [Mn(bipy)2(dcnm)2] (9) or [Mn(bipy)2(H2O)(dcnm)](dcnm)·H2O (10) and [Mn(bipy)2(dcnm)(H2O)](dcnm) (11). The addition of ethlyene glycol monomethyl ether to dcnm gives cyano[imino(2-methoxyethoxy)methyl]nitrosomethanide (cgnm) and the formation of [Cu(cgnm)2(H2O)2] (12). [source] How to Build Molecules with Large Magnetic AnisotropyCHEMISTRY - A EUROPEAN JOURNAL, Issue 16 2009Jordi Cirera Dr. Abstract Predicting single-molecule magnets? Magnetic anisotropy, a property that plays a key role in single-molecule magnets (SMMs), has been analyzed by using theoretical methods. Mononuclear complexes and the dependence of the magnetic anisotropy on their geometrical and electronic structure, as well as how such mononuclear complexes must be combined as building blocks to obtain polynuclear complexes with large anisotropy (see figure) are considered. The magnetic anisotropy of mononuclear transition-metal complexes has been studied by means of electronic structure calculations based on density functional theory. The variation of the zero-field splitting (ZFS) parameters has been analyzed for the following characteristic distortions: a tetragonal Jahn,Teller distortion, the Bailar twist, the Berry pseudorotation, and the planarization of tetrahedral complexes. Finally, the coupling of mononuclear building blocks in polynuclear complexes to obtain a large negative magnetic anisotropy necessary to improve their single-molecule-magnet (SMM) behavior has been studied. [source] | ||||||||||