Dedicated to Professor Hermann NEELS on the occasion of his 65th birthday EPR investigations of Mnz+-doped solid solutions of TSCC and TSCB were performed between 4.2 K and 300 K. The Curie temperature vs. molar fraction of bromide x is nonlinear, for z 2 0.75 no ferroelectric EPR-line splitting occurs. The relation between the line widths and the molar fraction of bromide is discussed by means of a simple statistical model.An festen Losungen von Mn2+-dotiertem TSCC und TSCB wurden zwischen 4,2 K und 300 K EPR-Untersuchungen durchgeftihrt. Die Abhiingigkeit der Curie-Temperatur vom molaren Bromidgehalt z ist nichtlinear, fur z 2 0,75 tritt keine der spontanen Polarisation proportionale EPR-Linien-Aufspaltung mehr auf. Die Beziehung zwischen der Linienbreite und dem molaren Bromidgehalt wird mit Hilfe eines einfachen statistischen Modells diskutiert.
Copper(II) bis(di-n-butyldiselenocarbamate) is studied in single crystals, diamagnetically diluted by Ni(II) bis(di-n-butyldiselenocarbamate), in polycrystalline samples and in frozen solutions by means of EPR. The EPR spectra show that in the unit cell two magnetic nonequivalent Cu(dbsc)2 molecules are to be found and that 77Se ligand hyperfine splitting can be detected. The principal axes of the g and the copper-hfs tensor do not coincide. A spin Hamiltonian for this case is given. Contrary to the copper-hfs and the 77Se-hfs tensors, which were found to be in agreement with what is expected for a planar complex of approximately D2h symmetry, the behavior of the g tensor is significantly different with respect to analogous CuS4 compounds. This indicates that the electronic structure of the complex differs remarkably from the structure of planar Cu(II) complexes; consequently, the symmetry is C2h. The Se-hfs data were used to estimate the degree of covalency in the Cu–Se σ bond. This was compared with parameters for some analogous sulfur complexes. In the spectra of the polycrystalline samples the anomaly in the behavior of the tensors is obviously in accord with the single crystal EPR results.
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