Chemical Pressure-Induced Anion Order-Disorder Transition in LnHO Enabled by Hydride Size Flexibility

While cation order-disorder transitions have been achieved in a wide range of materials and provide crucial effects in various physical and chemical properties, anion analogues are scarce. Here we have expanded the number of known lanthanide oxyhydrides, LnHO (Ln = La, Ce, Pr, Nd), to include Ln = Sm, Gd, Tb, Dy, Ho, and Er, which has allowed the observation of an anion order-disorder transition from the anion-ordered fluorite structure ( P4/ nmm) for larger Ln³⁺ ions (La-Nd) to a disordered arrangement ( Fm3̅ m) for smaller Ln³⁺ (Sm-Er). Structural analysis reveals that with the increase of Ln³⁺ radius (application of negative chemical pressure), the oxide anion in the disordered phase becomes too under-bonded, which drives a change to an anion-ordered structure, with smaller OLn₄ and larger HLn₄ tetrahedra, demonstrating that the size flexibility of hydride anions drives this transition. Such anion ordering control is crucial regarding applications that involve hydride diffusion such as catalysis and electrochemical solid devices.