The isotropic hyperfine interaction in ternary complexes of copper(II) with 8-hydroxyquinoline and various salicylic acids

1983 ◽  
Vol 61 (9) ◽  
pp. 2154-2158 ◽  
Author(s):  
Y. Anjaneyulu ◽  
N. V. S. Rao ◽  
R. Y. Swamy ◽  
R. P. Rao ◽  
V. G. K. M. Pisipati

Electron spin resonance and optical absorption studies are carried out on bis(8-hydroxyquinolinato)copper(II) and seven ternary copper(II) complexes with 8-hydroxyquinoline and salicylic acid or substituted salicylic acids. Electron spin resonance spectra of all these complexes give well-resolved lines. An unusual splitting of the parallel lines in frozen solution spectra and four line fluid (DMF) solution spectra at room temperature are observed. It is explained on the basis of either partial dissociation of 8-hydroxyquinoline ligand or the solvation effect of DMF which solvates some copper chelate molecules even at room temperature. This is more prominent on the parallel lines in frozen solution spectra of all the ternary complexes. The molecular orbital coefficients are estimated assuming an axial symmetry and these indicate that the in-plane π bonding is weak compared to σ-bond in the ternary complexes. The value of χ, which is proportional to hyperfine constants, indicates that it is quite independent of either ligand substitutions or substitutions in the ligand, but purely depends upon the immediate environment which constitutes the coordination around the paramagnetic ion.

1970 ◽  
Vol 23 (11) ◽  
pp. 2287 ◽  
Author(s):  
JR Pilbrow ◽  
TD Smith ◽  
AD Toy

Electron spin resonance measurements have been made on the copper(II) chelates of o-methylmercaptobenzoic acid, S-carboxydiethyldithiocarbamic acid, thiazolidine-4-carboxylic acid, 5-hydroxy-1,3-benzoxathiol-2-one and diacetyl bisthiosemicarbazone. The e.s.r. spectra of dimethylformamide solutions of the chelates have been interpreted in terms of dimeric species which are believed to exist at room temperature, as well as in frozen solutions in the case of o-methyl-mercaptobenzoic acid, S-carboxydiethyldithiocarbamic acid, and 5-hydroxy-1,3-benzoxathiol-2-one, whereas the dimeric forms of the remaining chelates are formed solely in frozen solution. The results have been interpreted as arising from dipole-dipole coupling between the copper(II) ions in their dimeric forms, and a line simulation procedure employed to extract the distance between the copper(II) dipoles. This information has been used to suggest the possible structures of the dimeric species. The effect of the introduction of zinc(II) ions during the formation of the copper(II) chelates has been assessed in each case.


1971 ◽  
Vol 24 (1) ◽  
pp. 59 ◽  
Author(s):  
PDW Boyd ◽  
JR Pilbrow ◽  
TD Smith

The electron spin resonance spectra of copper(II)- tris(hydroxymethyl)amino-methane complexes in aqueous solution provides evidence of the formation of dimeric species. These species are found to be different from those postulated by previous investigations. In dimethylformamide dimeric species are formed at room temperature and frozen solution in 1 : 1 and 1 : 2 metal-to-ligand mole ratios, though the formation of the dimer is critically dependent on the addition of base. Low field, ΔM = 2, signals observed for these systems have been interpreted in terms of dipole-dipole coupling between pairs of copper(II) ions. Structures for the copper(II) dimers have been proposed which are compatible with the copper-copper separation estimated by computer simulation of the spectra.


2021 ◽  
Vol 118 (2) ◽  
pp. 022407
Author(s):  
Hideyuki Takahashi ◽  
Yuya Ishikawa ◽  
Tsubasa Okamoto ◽  
Daiki Hachiya ◽  
Kazuki Dono ◽  
...  

The electron spin resonance method was employed to study the nature, concentration and kinetics of the disappearance under varying conditions of radicals produced in polyethylene by fast electron irradiation at 77°K. The predominant radical species at 77°K is the alkyl radical —CH 2 —ĊH—CH 2 —. On being warmed to room temperature it disappears rapidly, revealing a more stable un­identified radical. The kinetics of the decay at room temperature of both radicals was observed. Their stabilities were found to vary in polyethylene samples of differing physical and chemical properties. G values for these radicals are given. Comparison was made with spectra obtained under similar conditions with two pure paraffins and a pure olefin to evaluate the effect of crystallinity branching, molecular weight and unsaturation. In the olefin there is evidence for a build-up of allyl radicals due to the encounter of an alkyl radical with main chain unsaturation. This supports the view that alkyl radicals are mobile, and cross-linking occurs when two such radicals meet.


1982 ◽  
Vol 60 (18) ◽  
pp. 2340-2341 ◽  
Author(s):  
K. C. Khulbe ◽  
R. S. Mann

The intensity of the Cu2+ esr signal increased significantly on the addition of CO or SO2, especially with SO2, at room temperature to the preheated (at 400 °C) and evacuated CuO–alumina catalyst. When the CO or SO2 treated sample was evacuated at room temperature, the shape and intensity of the Cu2+ esr line returned to their original values. The intensity of the Cu2+ esr line decreased, but not to zero, on heating CuO–alumina either with CO or SO2. In the case of SO2, a new line appeared for the [Formula: see text] ion which was not affected on evacuation. It seems that the [Formula: see text] do not take part in the reduction of SO2 with CO over the CuO–alumina catalyst.


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