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Spin state transitions and intermetallic charge transfers can essentially change material structural and physical properties while excluding external chemical doping. However, these two effects have rarely been found to occur sequentially in a specific material. In this article, we show the realization of these two phenomena in a perovskite oxide PbCoO 3 with a simple ABO 3 composition under high pressure. PbCoO 3 possesses a peculiar A- and B-site ordered charge distribution Pb 2+ Pb 4+ 3 Co 2+ 2 Co 3+ 2 O 12 with insulating behavior at ambient conditions. The high spin Co 2+ gradually changes to low spin with increasing pressure up to about 15 GPa, leading to an anomalous increase of resistance magnitude. Between 15 and 30 GPa, the intermetallic charge transfer occurs between Pb 4+ and Co 2+ cations. The accumulated charge-transfer effect triggers a metal-insulator transition as well as a first-order structural phase transition toward a Tetra.-I phase at the onset of ∼20 GPa near room temperature. On further compression over 30 GPa, the charge transfer completes, giving rise to another first-order structural transformation toward a Tetra.-II phase and the reentrant electrical insulating behavior.

In this study, advanced control of crystallographic orientations and magnetic properties of self-assembled nanostructures via rational selections of substrates is demonstrated. We show that in the perovskite-spinel BiFeO(3)-CoFe(2)O(4) model system the crystal orientation of self-assembled CoFe(2)O(4) nanopillars can be tuned among (001), (011), and (111), while that of the BiFeO(3) matrix is fixed in (001). Moreover, the resultant CoFe(2)O(4) nanopillars appear in various shapes: pyramid, roof, and triangular platform, respectively. The tunable nanostructures through this approach enable the control of material functionality such as the magnetic anisotropy of CoFe(2)O(4). This study opens a new pathway for the engineering of self-assembled heteroepitaxial nanostructures.