New Honeycomb Iridium (V) Oxides: NaIrO₃ and Sr₃CaIr₂O₉

We report the structures and physical properties of two new iridates, NaIrO$_3$ and Sr$_3$CaIr$_2$O$_9$, both of which contain continuous two-dimensional honeycomb connectivity. NaIrO3 is produced by room temperature oxidative deintercalation of sodium from Na$_2$IrO$_3$, and contains edge-sharing IrO6 octahedra that form a planar honeycomb lattice. Sr$_3$CaIr$_2$O$_9$, produced via conventional solid-state synthesis, hosts a buckled honeycomb lattice with novel corner-sharing connectivity between IrO6 octahedra. Both of these new compounds are comprised of Ir$^{5+}$ (5$d^4$) and exhibit negligible magnetic susceptibility. They are thus platforms to investigate the origin of the nonmagnetic behavior exhibited by Ir$^{5+}$ oxides, and provide the first examples of a $J$ = 0 state on a honeycomb lattice.