Under high-pressure and high-temperature conditions, doped Bi3Re3O11 and Bi3Os3O11 with Fe up to 29 atomic % were synthesized. The crystal structures and chemical compositions of Bi3Os2.45Fe0.55O11 and Bi3Re2.13Fe0.87O11 were determined by synchrotron powder X-ray diffraction and electron probe microanalysis. Both crystal structures were explained by a KSbO3-type model with the space group Pn3̅. Magnetic and electronic transport property measurements showed that Bi3Os2.45Fe0.55O11 exhibited a ferrimagnetic transition at the highest magnetic ordering temperature of 490 K in the KSbO3-type, while Bi3Re2.13Fe0.87O11 exhibited a spin glassy behavior below 22 K. The magnetoresistance at 5 K and 90 kOe was almost zero for Bi3Os2.45Fe0.55O11, but −10% for Bi3Re2.13Fe0.87O11. These results suggest that KSbO3- type 5d oxides, which exhibit only weak temperature-dependent paramagnetism to date, are a group of compounds that can be converted into spintronic materials by doping with 3d elements, leading to the development of new KSbO3-type materials with both theoretical and practical significance.

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