Metal Complexes with Nitronyl Nitroxide Substituted Phenolate Ligands Providing New Magnetic Exchange Interaction Pathways − Synthesis, Structures, Magnetic Dilution Studies, and Ab Initio Calculations

The synthesis and magnetic properties of seven new nitronyl nitroxide substituted phenolates with chelating amine groups are reported. Copper(II) and nickel(II) complexes prepared with these ligands are structurally and magnetically characterized, showing exchange interactions between the metal and the radical ligands through the phenolate oxygen. Magnetically diluted samples are prepared by embedding the compounds in a poly(vinyl chloride) film to suppress intermolecular exchange interactions. This method is used for the first time in a quantitative way to separate intra- and intermolecular exchange interactions in radical-metal systems. The experimentally determined ground states are further confirmed by DFT calculations.