E.S.R. studies of the solute-solute interactions between copper(II) and nickel(II) thiosemicarbazone chelates in non-aqueous solutions

Abstract

The X-band e.s.r. spectra due to the copper(II) chelates of the thiosemicarbazones salicylaldehyde thiosemicarbazone (stsc), salicylaldehyde 4-methyl(thiosemicarbazone) (smtc), salicylaldehyde 4- ethyl-(thiosemicarbazone) (setc), salicylaldehyde 4- phenyl(thiosemicarbazone) (sptc), 2-hydroxyacetophen- one 4- ethyl(thiosemicarbazone) (aetc) and 2-hydroxypropiophenone 4- ethyl(thiosemicarbazone) (petc) dissolved in various organic solvents have been studied at room temperature and down to 77 K. The e.s.r. spectra show evidence of hyperfine structure due to the ¹⁴N nucleus of the ligand. Addition of the nickel(II) chelate of the thiosemicarbazone ligands to organic solvent solutions of the corresponding copper(II) chelate brings about a profound change in the e.s.r. spectrum of the copper(II) chelate in frozen solution. These changes are interpreted as arising from a change in the ground state of the copper(II) ion from essentially d_x2-y2 to d_3z2-r2, which arises as a result of specific solute- solute interactions between the copper(II) and nickel(II) chelates.