Excess antimony induced 12R Ba4Sb0.85Mn3.15O12 phase and Mn3O4 exsolution from 10H Ba5Sb0.7Mn4.3O15: crystal structure and magnetic properties

Hexagonal perovskite manganite has attracted much attention due to its rich structural chemistry and magnetic properties. The transformation between BaMxMn1−xO3 polymorphs can be caused by the change in substitution level or oxygen vacancies. In this study, we find a new polymorph change from 10H Ba5Sb0.7Mn4.3O15 (P63/mmc) to 12R Ba4Sb0.85Mn3.15O12 (R 3¯ m) via a ‘topochemical’ reaction with excess Sb2O3. The 10H Ba5Sb0.7Mn4.3O15 structure contains BaO3 layers in a (cchhh)2 sequence and face-shared MnO6 tetramers (Mn4 clusters), while the 12R Ba4Sb0.85Mn3.15O12 structure consists of BaO3 layers in a (cchh)3 stacking and face-shared MnO6 trimers (Mn3 clusters). The 10H → 12R phase conversion accompanies the exsolution of the Mn3O4 phase in trace amounts. For both 10H Ba5Sb0.71Mn4.29O15 and 12R Ba4Sb0.85Mn3.15O12, the Mn3+ cation on the corner-shared octahedra at M1 sites mediated competing ferromagnetic and antiferromagnetic exchanges between the magnetic Mn3 and Mn4 clusters, leading to spin-freezing transition at TF ≈ 11–15 K. The 10H → 12R phase change leads to an abrupt change of 2 K saturation moment from Ms ≈ 0.1 μB of 10H Ba5Sb0.71Mn4.29O15 to Ms ≈ 1.75 μB of 12R Ba4Sb0.85Mn3.15O12.