Na$_2$Ir$^\text{IV}$Cl$_6$: The Missing Member of the Perfectly Cubic Vacancy Ordered $A_2$IrCl$_6$ Family, Another Potential $J_{eff}$ = $\frac{1}{2}$ Ground State Candidate

Abstract

Vacancy ordered double perovskites (VODPs) have been known for more than 100 years, but their exact crystal structures and magnetic ground state remained controversial till date. Anhydrous VODP iridates ($A_2$Ir$X_6$; $A$ = K$^+$, (NH$_4$)$^+$, Cs$^+$, Rb$^+$, and $X$ = F$^-$, Cl$^-$, Br$^-$), having $face-centered~cubic$ (fcc) antiferromagnetic ground state, offer a chemically well-defined platform to investigate the influence of on-site Coulomb repulsion, crystal field, spin-orbit coupling, and competing Heisenberg and Kitaev interactions. Interestingly, among these, the Na-based VODP iridates seem to possess an unusual hydration dependent structural and magnetic uncertainty. As a result, a cubic Na$_2$IrCl$_6$ system having fcc antiferromagnetism could not be stabilized ever. Here, for the first time, we report the synthesis and comprehensive characterization of anhydrous Na$_2$IrCl$_6$ single crystals having fcc structure with antiferromagnetic transition temperature of 1.91 K. Thermogravimetric analysis establishes the absence of lattice water and also demonstrates thermal stability of the crystals up to 453 K. The cubic phase reported here contrasts with previously described 'anhydrous' monoclinic Na$_2$IrCl$_6$ and highlights the strong structural and physical property relationship in Na-based VODP iridates. This new material offers an exciting playing ground for exploring another potential perfect $J_{eff}$ = $\frac{1}{2}$ octahedra and the consequent strong Kitaev interaction within the nearest-neighbor (nn) pairs of Ir ions.