Search results for "Paramagnetic resonance"
showing 10 items of 567 documents
Spin Frustration in Triangular Cu 3 II Complexes with 6‐Methyl‐2‐pyridyloxime as Ligand – Synthesis, Structural, and Magnetic Characterization
2013
In the present work, new examples of μ3-OH/oximato Cu3 triangles have been obtained by treatment of different copper salts with 6-methyl-2-pyridylaldoxime [6-MepyC(H)NOH, 6-mepaoH]. Depending on the anion, the compounds [Cu3(OH)(6-mepao)3(O2CPh)2] (1), [Cu6(OH)2(6-mepao)6(NO3)3](NO3)·H2O (2·H2O) and [Cu6(OH)2(6-mepao)6(ClO4)3](ClO4) (3) formed and were characterized. Complex 1 is an isolated triangle, whereas 2 and 3 are hexanuclear compounds with two triangular subunits linked by anionic bridges. Susceptibility measurements show very strong antiferromagnetic interactions and the presence of antisymmetric exchange at low temperature. The magnetic properties of these frustrated triangles hav…
Over-Oxidation as the Key Step in the Mechanism of the MoCl5-Mediated Dehydrogenative Coupling of Arenes.
2015
Molybdenum pentachloride is an unusually powerful reagent for the dehydrogenative coupling of arenes. Owing to the high reaction rate using MoCl5, several labile moieties are tolerated in this transformation. The mechanistic course of the reaction was controversially discussed although indications for a single electron transfer as the initial step were found recently. Herein, based on a combined study including synthetic investigations, electrochemical measurements, EPR spectroscopy, DFT calculations, and mass spectrometry, we deduct a highly consistent mechanistic scenario: MoCl5 acts as a one-electron oxidant in the absence of TiCl4 and as two-electron oxidant in the presence of TiCl4, bu…
Stabilities and coordination modes of histidine in copper(II) mixed-ligand complexes with ethylenediamine, diethylenetriamine or N,N,N′,N″,N″-pentame…
2008
Abstract Solution equilibrium studies on the Cu(II)–polyamine–methionine ternary systems (polyamine: ethylenediamine (en), diethylenetriamine (dien), N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (Me5dien)) have been performed by pH-potentiometry, UV–Vis spectrophotometry and EPR methods. The obtained results suggest the formation of the mixed-ligand complexes with [Cu(A)(Met)]+ stoichiometry in all studied systems. Our spectroscopic results indicate the tetragonal geometry for [Cu(en)(Met)]+, the geometry slightly deviated from square pyramidal for [Cu(dien)(Met)]+ and strongly deviated from square pyramidal towards trigonal bipyramidal for the [Cu(Me5dien)(Met)]+ species. The coordination …
Stabilities and Coordination Modes of α-Alaninephosphonic Acid in Copper(II) Heteroligand Complexes with Ethylenediamine, Diethylenetriamine or N,N,N…
2011
Solution equilibrium studies on Cu2+–L1–L2 ternary systems have been performed by pH-potentiometry, UV–Vis spectrophotometry and EPR methods (L1 corresponds to polyamines such as ethylenediamine (en), diethylenetriamine (dien), or N,N,N′,N′,N″-pentamethyldiethylenetriamine (Me5dien) and L2 represents 1-aminoethylphosphonic acid (α-alaninephosphonic acid)). The obtained results suggest the formation of heteroligand complexes with [Cu(L1)(α-Ala(P))] stoichiometry in all studied systems. Additionally, in the system with en the [Cu(en)(α-Ala(P))H−1]− species is formed in basic solution. Our spectroscopic results indicate tetragonal geometry for the [Cu(en)(α-Ala(P))] species, geometry slightly …
ChemInform Abstract: Synthesis and Magnetic Properties of Bis(μ-hydroxo)bis((2,2′-bipyridyl)copper(II)) Squarate. Crystal Structure of Bis(μ-hydroxo)…
1990
Abstract The compound [Cu2(bipy)2(OH)2](C4O4)·5.5H2O, where bipy and C4O42− correspond to 2,2′-bipyridyl and squarate (dianion of 3,4-dihydroxy-3-cyclo- butene-1,3-dione) respectively, has been synthesized. Its magnetic properties have been investigated in the 2–300 K temperature range. The ground state is a spin-triplet state, with a singlet-triplet separation of 145 cm−1. The EPR powder spectrum confirms the nature of the ground state. Well-formed single crystals of the tetrahydrate, [Cu2(bipy)2(OH)2](C4O4)·4H2O, were grown from aqueous solutions and characterized by X-ray diffraction. The system is triclinic, space group P 1 , with a = 9.022(2), b = 9.040(2), c = 8.409(2) A, α = 103.51(2…
Rotation of methyl radicals in a solid krypton matrix
2009
Electron spin resonance (ESR) measurements were carried out to study the rotation of methyl radicals (CH(3)) in a solid krypton matrix at 17-31 K temperature range. The radicals were produced by dissociating methane by plasma bursts generated by a focused 193 nm excimer laser radiation during the krypton gas condensation on the substrate. The ESR spectrum exhibits only isotropic features at the temperature range examined, and the intensity ratio between the symmetric (A) and antisymmetric (E) spin state lines exhibits weaker temperature dependence than in a solid argon matrix. However, the general appearance of the methyl radical spectrum depends strongly on temperature due to the pronounce…
DNA condensation with spermine dendrimers: interactions in solution, charge inversion, and morphology control
2011
In this report, we characterize the formation of structured condensates of 884 base pair, double stranded DNA and spin-labeled, second generation dendrons (SL-G2) that are spermine-based and cationic using continuous wave electron paramagnetic resonance spectroscopy (CW EPR) and transmission electron microscopy (TEM). The electrostatic interaction between DNA and SL-G2 in solution leads to condensation of DNA into densely packed structures. At a particular charge ratio of 2.3 (cationic charges/anionic charges), the structures appear as thick rod-like condensates of parallelly ordered, stretched DNA and SL-G2. Depending on the concentration of DNA, the charge ratio and the ionic strength, wh…
The decomposition of 1-phenyl-3-chloro-nortricyclene and 1-phenylnortricyclene on reduction in 1,2-dimethoxyethane. The EPR spectra of the radical io…
1972
Radical anions of 1-phenyl-3-chloronortricyclene and 1-phenylnortricyclene were produced by reduction with potassium in 1,2-dimethoxyethane under a high vacuum. The initially formed radical anion of 1-phenyl-3-chloronortricyclene was very unstable, and decomposed finally to the anions of naphthalene and biphenyl. The only product of the reduction of 1-phenylnortricyclene was the biphenyl anion. The EPR spectra of the reaction mixtures were measured at temperatures from —80°C to room temperature.
Influence of metal ions on the structures of Keggin polyoxometalate-based solids: Hydrothermal syntheses, crystal structures and magnetic properties
2006
Abstract Three new Keggin polyoxometalate (POM)-based compounds linked to 3d metal complexes have been synthesized under hydrothermal conditions: [Cu(phen)2]2{[Cu(phen)]2 [SiMo12O40(VO)2]} (1), {[Zn(phen)2]2[GeMo12O40(VO)2]}{[Zn(phen)2(H2O)]2 [GeMo12O40(VO)2]}·3H2O (2) and {[Co(phen)2]2[PMo12O40(VO)2]}{[Co(phen)2(OH)]2 [PMo12O40(VO)2]}·2.5H2O (3) (phen=1,10-phenanthroline). These three compounds present, as building blocks, the bicapped Keggin anions [XMo12O40(VO)2] (X=Si, Ge and P). Compound 1 consists of a bicapped Keggin anion [SiMo12O40(VO)2]2− linked to two [Cu(phen)]+ complexes with two [Cu(phen)2]+ countercations. Compound 2 contains two bicapped Keggin anions [GeMo12O40(VO)2]4−, one…
Pulse EPR methods for studying chemical and biological samples containing transition metals
2006
This review discusses the application of pulse EPR to the characterization of disordered systems, with an emphasis on samples containing transition metals. Electron nuclear double-resonance (ENDOR), electron-spin-echo envelope-modulation (ESEEM), and double electron-electron resonance (DEER) methodologies are outlined. The theory of field modulation is outlined, and its application is illustrated with DEER experiments. The simulation of powder spectra in EPR is discussed, and strategies for optimization are given. The implementation of this armory of techniques is demonstrated on a rich variety of chemical systems: several porphyrin derivatives that are found in proteins and used as model s…