SINGLE-CRYSTAL ELECTRON PARAMAGNETIC RESONANCE STUDIES OF COPPER DIETHYLDITHIOCARBAMATE

Single-crystal electron paramagnetic resonance studies have been carried out on copper(II) diethyldithiocarbamate doped into both the zinc and nickel diethyldithiocarbamate complexes. The crystal structures of all three complexes are known, and the orientation of the principal axes of the g and hyperfine tensors can be related to the molecular axes. The lowering of symmetry on going from the nickel to the zinc diethyldithiocarbamate host leads to significant changes in the isotropic as opposed to the anisotropic hyperfine interaction. These changes have been attributed to increased orbital mixing upon a lowering of symmetry about the metal ion. The epr results were used to obtain molecular orbital coefficients from standard expressions employing orbitals based on the metal ion and sulfur atoms. The coefficient values were tested for their sensi¬tivity to the various parameters in the expressions, in particular, ligand spin-orbit coupling. Molecular orbital coefficients obtained were compared with those from a Wolfsberg-Helmholtz calculation. © 1968, American Chemical Society. All rights reserved.