Iridium containing honeycomb Delafossites by topotactic cation exchange

We report the structure and magnetic properties of two new iridium-based honeycomb Delafossite compounds, Cu3NaIr2O6 and Cu3LiIr2O6, formed by a topotactic cation exchange reaction. The starting materials Na2IrO3 and Li2IrO3, which are based on layers of IrO6 octahedra in a honeycomb lattice separated by layers of alkali ions, are transformed to the title compounds by a topotactic exchange reaction through heating with CuCl below 450 °C; higher temperature reactions cause decomposition. The new compounds display dramatically different magnetic behavior from their parent compounds – Cu3NaIr2O6 has a ferromagnetic like magnetic transition at 10 K, while Cu3LiIr2O6 retains the antiferromagnetic transition temperature of its parent compound but displays significantly stronger dominance of antiferromagnetic coupling between spins. These results reveal that a surprising difference in the magnetic interactions between the magnetic Ir ions has been induced by a change in the non-magnetic interlayer species. A combination of neutron and X-ray powder diffraction is used for the structure refinement of Cu3NaIr2O6 and both compounds are compared to their parent materials.