Structural Modification of the Cation-Ordered Ruddlesden-Popper Phase YSr2Mn2O7 by Cation Exchange and Anion Insertion.

Calcium-for-strontium cation substitution of the a-b0c0/b0a-c0-distorted, cation-ordered, n = 2 Ruddlesden-Popper phase, YSr2Mn2O7, leads to separation into two phases, which both retain an a-b0c0/b0a-c0-distorted framework and have the same stoichiometry but exhibit different degrees of Y/Sr/Ca cation order. Increasing the calcium concentration to form YSr0.5Ca1.5Mn2O7 leads to a change in the cooperative tilting on the MnO6 units to a novel a-b-c-/b-a-c- arrangement described in space group P21/n11. Low-temperature, topochemical fluorination of YSr2Mn2O7 yields YSr2Mn2O5.5F3.5. In contrast to many other fluorinated n = 2 Ruddlesden-Popper oxide phases, YSr2Mn2O5.5F3.5 retains the a-b0c0/b0a-c0 lattice distortion and P42/mnm space group symmetry of the parent oxide phase. The resilience of the a-b0c0/b0a-c0-distorted framework of YSr2Mn2O7 to resist symmetry-changing deformations upon both cation substitution and anion insertion/exchange is discussed on the basis the A-site cation order of the lattice and the large change in the ionic radius of manganese upon oxidation from Mn3+ to Mn4+. The structure property relations observed in the Y-Sr-Ca-Mn-O-F system provide insight into assisting in the synthesis of n = 2 Ruddlesden-Popper phases, which adopt cooperative structural distortions that break the inversion symmetry of the extended lattice and therefore act as a route for the preparation of ferroelectric and multiferroic materials.