Search results for "Paramagnetic"
showing 10 items of 600 documents
Crystal and molecular structure and electronic properties of [Cu(phen)2(HL)] · (phen)0.5 · 7H2O (H3L = 1,3,5-triazine-2,4,6(1H,3H,5H)-trione), a nove…
1998
Abstract The crystal and molecular structure of [Cu(phen)2(HL) · (phen)0.5 · 7H2O (H2L = 1,3,5-triazine-2,4,6(1H,3H,5H)-trione) has been determined by X-ray diffraction methods. The structure is built up of neutral [Cu(phen)2(HL)] entities (which are associated to form dinuclear units through hydrogen bonds involving the cyanurate ions), uncoordinated phenanthroline and crystallisation water molecules. The copper atom is involved in a CuN5 chromophore, with an stereochemistry near to a compressed trigonal bipyramid (TBP) but with a significant degree of distortion towards the square pyramidal (SP) topology. The EPR spectrum is indicative of a mixed d z 2 d x 2 −y 2 ground state for the copp…
Oxidomolybdenum(IV), ‐(V), ‐(VI) Complexes with Relevance to Molybdenum Enzymes: Oxygen Atom Transfer, Redox Chemistry and EPR Spectroscopy
2010
The cis-dioxidomolybdenum(VI) complex Mo(NN′)2O2 (1) [(NN′) = N-(4-hydroxyphenyl)-2-pyrrolatocarbaldimine] transfers one oxygen atom to phosphanes PMenPh3–n (n = 0–3) to give quantitatively the respective phosphane oxides OPMenPh3–n (OAT, oxygen atom transfer). The kinetics of these OAT reactions has been investigated spectrophotometrically. When offering excess PMenPh3–n (n = 1–3), oxido(phoshane)molybdenum(IV) complexes Mo(NN′)2O(PMenPh3–n) 5a–5c are isolated and characterized by multinuclear NMR spectroscopy (1H, 13C, 31P, 15N), IR spectroscopy, UV/Vis spectroscopy and mass spectrometry. The redox chemistry of the molybdenum(IV) complexes 5a–5c and of molybdenum(VI) complex 1 has been pr…
Dicopper(II) Metallacyclophanes with Oligo(p-phenylene-ethynylene) Spacers: Experimental Foundations and Theoretical Predictions on Potential Molecul…
2013
Two novel double-stranded dicopper(II) metallacyclophanes of formula (nBu4N)4[Cu2(dpeba)2]·4MeOH·2Et2O (1) and (nBu4N)4[Cu2(tpeba)2]·12H2O (2) have been prepared by the Cu(II)-mediated self-assembly of the rigid ('rod-like') bridging ligands N,N'-4,4'-diphenylethynebis(oxamate) (dpeba) and N,N'-1,4-di(4-phenylethynyl)phenylenebis(oxamate) (tpeba), respectively. Single crystal X-ray diffraction analysis of 1 confirms the presence of a dicopper(II)tetraaza[3.3]4,4'-diphenylethynophane metallacyclic structure featuring a very long intermetallic distance between the two square planar Cu(II) ions [r = 14.95(1) Å]. The overall parallel-displaced π-stacked conformation of the two nearly planar par…
3D-transition metal mono-substituted Keggin polyoxotungstate with an antenna molecule: synthesis, structure and characterization
2008
Three new organic-inorganic hybrid complexes based on 3d-transition metal monosubstituted Keggin polyoxometalates (POMs) with imidazole (Im) as pendant ligands, formulated as (HIm)(6-)[SiW11O39NiIm]0.8[SiW11O39Ni(H2O)]0.2.7H2O (1), (Im)4Na6[SiW11O39MnIm]0.69[SiW11O39Mn(H2O)]0.31.7.5H2O (2) and (HIm)6[SiW11O39CoIm]0.63[SiW11O39Co(H2O)]0.37.7H2O (3), have been synthesized and characterized by IR spectroscopy, UV-visible spectroscopy, elemental analysis, TG analysis, cyclic voltammetry, magnetic properties, EPR and single-crystal/powder X-ray diffraction. The structural analyses indicate that the 3d metal atoms are incorporated into the vacancy of the alpha-[SiW11O39](8-) (SiW11). Complexes 1-…
Paramagnetic aluminium β-diketiminate
2012
The β-diketiminate ligand framework is shown to undergo reduction to form a neutral main group radical stabilized by spiroconjugation of the unpaired electron over the group 13 element centre. The synthesized paramagnetic complex was characterized by EPR spectroscopy and computational chemistry.
Preparative, structural, and electrochemical investigations on peralkylated niobocene dichlorides and difluorides
1994
CP(dagger)2NbCl2 (CP(dagger) = 175-C5Me4Et) (1b) was synthesized from NbCl5 and a slight excess of Cp(dagger)Li and NaBH4. Its electrochemical (2 e-, E1/2 = -1.6 V) and chemical reduction (2 equiv of Na/Hg) was studied showing that peralkylation of the Cp ligand facilitates two-electron reduction compared to less substituted CP2NbHal2 derivatives. The reduced solutions of CP*2NbCl2 (CP* = C5Me5) (1a) and of lb were shown by means of EPR spectroscopy to contain two new paramagnetic species 1A,B for which bent niobocene (A(Nb) = 100 G) and fulvene-like structures (A(Nb) = 55 G) are proposed. The high reduction potential of these species led in their reaction with HPF6 to the first stable difl…
Electron paramagnetic resonance and magnetic circular dichroism of Gd3+ ions in oxyfluoride glass–ceramics containing CaF2 nanocrystals
2015
Abstract Magnetic resonance investigations of the Gd3 + centre structure in the oxyfluoride glass and glass–ceramics (GCs) have been carried out. The electron paramagnetic resonance (EPR) measurements showed the presence of low symmetry Gd3 + centres in the glass sample. The cubic Gd3 + centre appeared in the glass–ceramics after heat treatment of the samples at temperatures above 650 °C. The magnetic circular dichroism (MCD) measurements of both glass and glass–ceramics showed wide absorption band around 310 nm. In the GC samples MCD–EPR of the cubic Gd3 + centre has been detected.
Purely Spectroscopic Determination of the Spin Hamiltonian Parameters in High-Spin Six-Coordinated Cobalt(II) Complexes with Large Zero-Field Splitti…
2019
Accurate determination of the spin Hamiltonian parameters in transition-metal complexes with large zero-field splitting (ZFS) is an actual challenge in studying magnetic and spectroscopic properties of high-spin transition metal complexes. Recent critical papers have convincingly shown that previous determinations of these parameters, based only on the magnetic data, have low accuracy and reliability. A combination of X-band electron paramagnetic resonance (EPR) spectroscopy and SQUID magnetometry seems to be a more convincing and accurate approach. However, even in this case, the accuracy of the determination of the spin Hamiltonian parameters is strongly limited. In this work, we propose …
Magnetic LB films based upon polyoxometalate clusters and single molecule nanomagnets
1999
Abstract By using the adsorption properties of polyoxometalates such as the ferromagnetic cluster [Co 4 (H 2 O) 2 (PW 9 O 34 ] 10− ) along a positively charged monolayer, we have prepared well organized monolayers of the magnetic polyanions. A similar procedure allowed us to obtain Langmuir-Blodgett films (LB films) based on Mn 12 clusters which show a marked hysteresis
Computer simulations of electron paramagnetic resonance spectra of P2O5Li2WO4Li2O glasses
1992
Abstract P2O5Li2WO4Li2O glasses have been synthesized and studied over a wide range of compositions. The glasses were characterized mainly by thermodifferential analysis and electron paramagnetic resonance (EPR). The EPR spectra are characterized by the presence of two signals with very different intensities, associated with the Wv (major signal) and Mov (minor signal) paramagnetic centres. The signals have been satisfactorily reproduced by computer simulation, assuming anisotropy in the g values as well as the hyperfine parameters and linewidths. EPR parameters have been extracted and indicate metallic ions located in environments close to square pyramidal.