Exploring the Links between Structural Distortions, Orbital Ordering, and Multipolar Magnetic Ordering in Double Perovskites Containing Re(VI) and Os(VII)

A combination of high-resolution powder diffraction techniques and solid-state NMR has been employed to explore the links between crystal structure, orbital ordering, and magnetism in three isostructural double perovskites containing transition metal ions with a 5d1 configuration. In Ba2ZnReO6, both neutron and synchrotron X-ray powder diffraction data reveal a cubic-to-tetragonal transition at 23 K that breaks the degeneracy of the t2g orbitals and leads to a pattern of orbital ordering that stabilizes magnetic ordering when the sample is cooled below 16 K. Similar behavior is observed in Ba2MgReO6, with an orbital ordering temperature of 33 K and a magnetic ordering temperature of 18 K. Prior theoretical works suggest that the pattern of orbital order seen in the P42/mnm space group is needed to stabilize the heavily canted antiferromagnetism of these compounds. Unfortunately, powder diffraction data is not sensitive enough to differentiate between the I4/mmm and P42/mnm structural models, as the distortions are too subtle to be unambiguously identified from either neutron or synchrotron X-ray powder diffraction methods. In contrast, both diffraction and 7Li NMR data indicate that Ba2LiOsO6 retains the cubic structure down to 1.7 K. The antiferromagnetic ground state and lack of any sign of orbital ordering in Ba2LiOsO6 provide compelling evidence that the electronically driven tetragonal distortion seen in Ba2ZnReO6, and Ba2MgReO6 is intimately linked to the magnetic ordering seen in those compounds. The absence of magnetic reflections in high intensity neutron powder diffraction data collected on Ba2MgReO6 strongly suggests ordering of multipolar moments on Re­(VI), likely ferro-octupolar ordering.