Search results for "Paramagnetic resonance"
showing 10 items of 567 documents
New dinuclear copper complexes incorporating bis(imidazolyl) based ligands and bidentate–monodentate oxalate bridges. Crystal structure and magnetic …
2016
Abstract This paper reports the synthesis, X-ray crystal structure and magnetic characterization of two novel copper(II) dinuclear compounds including bis(imidazolyl) ligands and oxalate anions, [Cu2(BIM)2(C2O4)2]·4H2O (1) (BIM = bis(2-imidazolyl)methane) and [Cu2(BIK)2(C2O4)2] (2) (BIK = bis(2-imidazolyl)ketone). The oxalate anion acts as bidentate–monodentate in both cases, although it exhibits different coordination bridging modes: whereas in compound 1 a μ1,1,2-oxalato is observed, a μ1,2,3-oxalato is found in compound 2. In both cases, the 3D framework is held together by a combination of H-bonding and aromatic-aromatic interactions provided by the convenient structural features of BIM…
Growth and characterization of GdxHg1−xSe crystals
2008
Abstract The growth of GdxHg1−xSe crystals by the vertical Bridgman method was studied in the composition range 0⩽x⩽0.1. The structural and electronic properties of GdxHg1−xSe crystals were investigated as a function of composition. It was found that an increase in gadolinium content up to x=0.01 results in a decrease of structural defects and an increase in electron mobility up to the maximum value of μ77≈2.8×105 cm2/V s. Structural defects start to increase at x>0.01, and the formation of Gd2Se3 amorphous phase takes place at x>0.03. On the base of the electron-spin resonance investigation, it was shown that the Gd incorporates into the HgSe host in Gd3+ charge state at the concentration …
Elaboration and characterization of organic/inorganic hybrid nanoporous material incorporating Keggin-type Mo-Si polyanions
2007
A novel nanoporous (pore size of 11 nm in average, BET surface area of 30 m2/g, pore volume of 300 mm3/g) hybrid inorganic-organic material was synthesized using the solid-phase interaction at room temperature of plant-originated phenylpropanoid polymer lignin and a Keggin-type heteropolyanion [SiMo12O40]4-. The partly reduction of Mo(VI) to Mo(V) and complexes formation between lignin and polyanion have been established by EPR, FT-IR and Raman spectroscopy. The XRD pattern and FT-IR spectrum of the hybrid material and indicates that [SiMo12O40]4- anion maintains the Keggin structure.
An Unusual Geometry of Five-Coordinate Copper(II): The Structure of Cu(terpy)I2 and Spectroscopic Investigations of Complexes Cu(terpy)X2 (X: I, NCS)
1991
The structure of the compound Cu(terpy)I2 (terpy 2,2′: 6′, 2″ terpyridine) was determined at room temperature. It is monoclinic, space group I2/c with a = 13.689(3), b = 9.510(2), c = 11.605(3) Å, β = 97.59(4)° and Ζ = 4. The copper(II) ions are five-coordinated by the three nitrogen atoms from the terpy ligand and the two iodine atoms. The CuN3I2 polyhedron exhibits the same unusual “reverse” geometry as is observed for Cu(terpy)(NCS)2. Single crystal EPR measurements of the iodide and the isothio-cyanate complexes confirmed the structural results, excluding the possibility of a dynamically averaged geometry.
Comparison of spin density calculation methods for various alkyl-substituted 9,10-anthraquinone anion radicals in the solution phase
1996
EPR and ENDOR spectra were recorded for 2-methyl-9,10-anthraquinone (2-methylAQ), 2-ethylAQ, 2-tertbutylAQ and 2,3-dimethylAQ anion radicals in the solution phase. The EPR spectra were simulated with the help of ENDOR data. The experimental isotropic hyperfine coupling constants (IHFCs) were compared with calculated values from semi-empirical INDO, spin-restricted AM1/CI and B3PW91 density-functional methods. The best computational methods for the IHFCs were the semi-empirical AM1/CI method and the B3PW91 density-functional method with a large basis set.
Structural and magnetic properties of polynuclear oximate copper complexes with different topologies
2017
Abstract Two new copper(II) complexes containing the methyl(2-pyridyl)ketone oxime ligand (mpkoH) [Cu3(OH)(ClO4)2(mpko)3]·CH3OH (1) and [Cu(ClO4)(mpko)(mpkoH)]n (2) have been prepared from Cu(ClO4)2 and mpkoH in different metal-to-ligand molar ratios. In addition, the compound [Cu{(mpko)2BF2}(H2O)](BF4) (3) [(mpko)2BF2 is the fluoroboration product of the oxime] has been obtained when replacing Cu(ClO4)2 by Cu(BF4)2. Compound 1 is an isolated triangle with a {Cu3(µ3-OH)}5+ core, whereas 2 is a chain of CuII ions linked by anionic mpko− bridges. 1 exhibits strong antiferromagnetic competing interactions, as well as antisymmetric exchange. On the other hand, very weak ferromagnetic interactio…
Redox active polymers with phenothiazine moieties for nanoscale patterning via conductive scanning force microscopy
2011
Redox active polymers with phenothiazine moieties have been synthesized by Atomic Transfer Radical Polymerization (ATRP). These novel polymers reveal bistable behaviour upon application of a bias potential above the oxidation threshold value. Using conductive Scanning Force Microscopy, two distinguishable conductivity levels were induced on a nanoscale level. These levels were related to a high conducting “On” and a low conducting “Off” state. The “On” state is generated by the oxidation of the phenothiazine side chains to form stable phenothiazine radical cations. The formation and stability of the radical sites was examined by cyclic voltammetry, electron spin resonance and optical spectr…
Grafting of polymer chains on the surface of carbon nanotubes via nitroxide radical coupling reaction
2015
Poly(butylene succinate) (PBS) was grafted on the surface of TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) modified multi-walled carbon nanotubes (MWCNTs) via a nitroxide radical coupling reaction. TEMPO functionalized MWCNTs (MWCNTs-g-TEMPO) were synthesized using the Cu(I)-catalyzed azide/alkyne click chemistry approach and the covalent bond of the nitroxide moieties onto the MWCNTs was confirmed via electron paramagnetic resonance (EPR) spectroscopy. The PBS grafting on the sidewalls of MWCNTs was carried out in solution via peroxide-induced formation of macroradicals and it was confirmed by EPR and attenuated total reflectance Fourier transform infrared analysis. Preliminary rheological …
Functionalization of aliphatic polyesters by nitroxide radical coupling
2014
Functionalized poly(butylene succinate) (PBS) samples were prepared by a post-polymerization method based on the coupling reaction between TEMPO derivatives bearing different functionalities and PBS macroradicals generated by H-abstraction using a peroxide. 4-Benzoyloxy-2,2,6,6-tetramethylpiperidine-1- oxyl (BzO-TEMPO) and 4-(1-naphthoate)-2,2,6,6-tetramethylpiperidine-1-oxyl (NfO-TEMPO), a pro-fluorescent nitroxide, were successfully grafted on PBS, as revealed by MALDI TOF MS and UV-Vis spectroscopy. The functionalization degrees were accurately determined by UV-Vis analysis and confirmed by 1H-NMR spectroscopy. The grafting site was identified by combining theoretical calculations with e…
How Structure-Related Collapse Mechanisms Determine Nanoscale Inhomogeneities in Thermoresponsive Polymers
2012
Continuous wave electron paramagnetic resonance (CW EPR) spectroscopy on the amphiphilic spin probe TEMPO in solutions of selectively chosen functional, thermoresponsive poly(propylene oxide) (PPO)- and poly(ethylene oxide) (PEO)-based copolymers of both linear and branched structure is used to elucidate their host–guest interactions and inverse phase transitions. Three different fundamental types of host–guest interactions between probes and polymers could be correlated to the phase transition mechanisms (supported by MD simulations), evidencing that these proceed via nanoscale inhomogeneities of the polymers. Because of their ability to host small amphiphilic guest molecules, thermorespon…