Inorganic Chemistry, Vol.58, No.13, 8835-8840, 2019
CaMn0.5Ir0.5O2.5: An Anion-Deficient Perovskite Oxide Containing Ir3+
Reaction between CaMn0.5Ir0.5O3 and NaH, either through solid-solid contact or via a gas mediated reaction process, yields the topochemically reduced phase CaMn0.5Ir0.5O2.5 in which Mn3+ and Ir3+ cations are located within a partially anion-vacancy disordered lattice. Magnetization data from CaMn0.5Ir0.5O2.5 can be fit by the Curie-Weiss law to yield C = 1.586 cm(3) K mot(-1) and theta = -86.9 K, consistent with a combination of S = 2, Mn3+ and S = 0, Ir3+. On cooling below T similar to 110 K, the system undergoes a transition to a spin-glass state, consistent with the observed Mn/Ir cation disorder and frustration between Mn-O-Mn and Mn-O-Ir-O-Mn magnetic couplings. The degree of reduction and the observed anion-vacancy disorder are discussed on the basis of the d-orbital filling of the transition-metal cations.