Search results for " Paramagnetic resonance"
showing 10 items of 567 documents
Fullerene as a Platform for Recyclable TEMPO Organocatalysts for the Oxidation of Alcohols
2014
[60]Fullerene has been employed successfully as a molecular platform to anchor 12 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) moieties. Such an octahedrally substituted C60-derivative has been employed as an organocatalyst for the oxidation of primary and secondary alcohols using the Anelli protocol. The reaction showed a general applicability to various alcohols, and the catalyst was recovered easily and could be recycled for at least seven cycles with no loss in catalytic activity. EPR spectroscopy studies revealed that the amount of radicals decreases during the catalytic cycles, even if the recovered material still displays unchanged catalytic activity. This new approach paves the way …
A tetranuclear organorhenium(i) complex of the 2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-p-quinodimethane radical anion, TCNQF4˙−
2008
The radical complex {(mu(4)-TCNQF4)[Re(CO)(3)(bpy)](4)}(PF(6))(3), as prepared and isolated from the reaction between TCNQF4 and [Re(CO)(3)(bpy)(MeOH)](PF(6)), was studied electrochemically and by IR vibrational spectroscopy, UV-Vis-NIR absorption spectroscopy, and by EPR at 9.5, 190 and 285 GHz. The isotropic g factor of 2.0058, the detectable g anisotropy, and the (185,187)Re EPR hyperfine coupling of 0.95 mT for four equivalent metal nuclei support predominant, but not exclusive, spin localisation at the bridging ligand. Nitrile and metal carbonyl stretching frequencies as well as the typically structured near infrared absorption band lend further support to (TCNQF4 (-))(Re(I))(4) as the…
How Hydrogen Bonds Affect Reactivity and Intervalence Charge Transfer in Ferrocenium‐Phenolate Radicals
2016
The ferrocenyl-phenol 2,4-di-tert-butyl-6-(ferrocenylcarbamoyl)phenol (H-1) forms intramolecular hydrogen bonds which are absent in its constitutional isomer 2,6-di-tert-butyl-4-(ferrocenylcarbamoyl)phenol (H-2). Their corresponding bases 1– and 2– show intra- and intermolecular NH···O hydrogen bonds, respectively. The phenolate 1– is reversibly oxidized to 1·, whereas 2– only undergoes a quasi-reversible oxidation to 2·, which suggests a higher reactivity. The radical pools of 1· and 2· formed by the oxidation/deprotonation of H-1 and H-2 have been probed by (rapid-freeze) electron paramagnetic resonance (EPR) spectroscopy and by spin-trapping techniques to elucidate the types of radicals …
Layered ferromagnets hosting tetraalkylammonium-substituted nitronyl nitroxide free radicals
2008
This paper describes the structural, magnetic and EPR properties of hybrid organic/inorganic magnets formed by anionic heterometallic oxalato-based layers and cationic nitronyl nitroxide (NN) free radicals of the tetraalkylammonium type. A series of compounds of formula nBu3NCH2NN[MCr(ox)3] (M = Mn (1), Ni (2), Zn (3)) has been prepared and studied by AC and DC magnetic susceptibility measurements and EPR spectroscopy. Magnetic order with critical temperatures ranging from 5 K to 15 K was confirmed. EPR measurements show that the organic spin carriers interact significantly with the inorganic network.
Nitronyl Nitroxide Radicals Linked to Exchange‐Coupled Metal Dimers – Studies Using X‐ray Crystallography, Magnetic Susceptibility Measurements, EPR …
2009
To study long-range magnetic interactions between exchange-coupled metal centers and a radical moiety coordinated through a peripheral group, three new homodimetallic complexes with MnII, CoII, and ZnII bridged by a nitronyl nitroxide (NIT) substituted benzoate ligand with the structure [(NIT-C6H4-COO)M2(LR)](ClO4)2 {M = MnII, CoII, and ZnII; NIT = nitronyl nitroxide and LR = N,N,N′,N′-tetrakis(2-benzimidazolylalkyl)-2-hydroxy-1,3-diaminopropane} have been prepared and studied by X-ray crystallography, magnetic susceptibility measurements, EPR spectroscopy, and density functional theory calculations. For comparison, related complexes with MnII and CoII bridged by a diamagnetic nitrobenzoate…
Hybrid Magnetic Materials Based on Nitroxide Free Radicals and Extended Oxalato‐Bridged Bimetallic Networks
2005
A series of hybrid organic-inorganic magnets of formula p-rad[MIICr(ox)3] [M = Mn (1), Co (2), Ni (3), Zn (4)] and m-rad[MIICr(ox)3] [M = Mn (5), Co (6)], in which N-methylpyridinium cations bearing a nitronyl nitroxide moiety in positions 3 (m-rad) or 4 (p-rad) of the pyridine ring coexist with the 2D honeycomb-like oxalato-bridged bimetallic lattice, has been prepared and studied by AC and DC magnetic susceptibility measurements and EPR spectroscopy. In general, the physical properties of these magnets are not altered significantly by the insertion of the nitronyl nitroxide radicals although these paramagnetic molecules seem to interact weakly with the inorganic network as demonstrated by…
Heparin–polynitroxides: Synthesis and preliminary evaluation as cardiovascular EPR/MR imaging probes and extracellular space-targeted antioxidants
2011
We report here the synthesis of heparin-polynitroxide derivatives (HPNs) in which nitroxide moieties are linked either to uronic acid or glycosamine residues of the heparin macromolecule. HPNs have low anticoagulant activity, possess superoxide scavenging properties, bind to the vascular endothelium/extra-cellular matrix and can be detected by EPR and MRI techniques. As the vascular wall-targeted redox-active paramagnetic compounds, HPNs may have both diagnostic (molecular MRI) and therapeutic (ecSOD mimics) applications.
Magneto-structural and theoretical study of the weak interactions in a Mn(II) complex with a very unusual N,O-chelating coordination mode of 2-aminot…
2017
International audience; The Mn(II) complex {[Mn(atpa)(H2O)2]·H2O}n (1),with the dicarboxylate ligand 2-aminoterephthalic acid (H2atpa), has been synthesized and crystallographically, spectroscopically and magnetically characterized. Complex 1 shows a very unusual 1κ2N,O coordination mode of the aminoterephthalate dianion with the Mn(II) ion. One of the carboxylate groups shows a syn-anti-μ2-η1:η1 binding mode to form a 2D square grid. The magnetic properties of this compound can be very well reproduced with a regular S = 5/2 chain model with a very weak antiferromagnetic coupling constant of J = −0.2 cm−1 through the single syn-anti carboxylate bridges. EPR measurement also supports the exp…
Alanine films for EPR dosimetry of low-energy (1–30 keV) X-ray photons
2019
Abstract L- α -alanine has aroused considerable interest for use in radiation EPR dosimetry and has been formally accepted as a secondary standard for high-dose (kGy) and transfer dosimetry of high-energy photons and electrons. In this work, we extended the investigation of the energy response of alanine EPR films in the low energy range for X-photons (1–30 keV). Electron Paramagnetic Resonance (EPR) measurements were performed on Kodak BioMax alanine films exposed to low-energy X-rays from a Cu-, W- and Mo-targets tube operating at voltages up to 30 kV. Films were chosen because of the low penetration of the soft X-rays used. The response of alanine to low-energy X-rays was characterized e…
Magnetic resonance investigations of oxygen-related luminescence centres in AlN ceramics
2001
Abstract The structure of oxygen-related luminescence centres in nominally undoped and Y2O3-doped AIN ceramics were investigated by electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR) and optically-detected EPR. The photoluminescence-detected EPR lines having g values of 1.990 and 2.008 were attributed to neighbouring donor and acceptor pairs causing the recombination luminescence excited in the ultraviolet. The two EPR lines at g = 1.987 and g = 2.003, detected via the recombination luminescence in the afterglow, are thought to be due to a recombination between the same, but more distant donor and acceptor pairs. The donor is supposed to be an electron trapped …