Due to the scarcity of the artificial transition metal technetium, studies on the solid-state properties of its oxides have been rarely undertaken. We have prepared a new technetium metal oxide system that include the 4d metal in two separate oxidation states and have characterized the new phases' crystal structures and magnetic properties. One phase Cd2Tc2O7 was prepared through the vapor-phase reaction of the heptaoxide Tc2O7 with Cd metal; the other phase, CdTcO3, was prepared through the solid state reaction of TcO2 with CdO. High-resolution synchrotron X-ray diffraction was used to characterize the crystal structures and stoichiometries of the two new technetates. At room temperature, Cd2Tc2O7 takes on the pyrochlore structure with a = 10.18118(1) Å, space group, Fdm and Z = 8. CdTcO3 has the GdFeO3-type structure with space groupPbnm and a = 5.38881(1) Å, b = 5.46504(1) Å, and c = 7.71272(1)Å. The magnetic susceptibility behavior of Cd2Tc2O7 is strikingly similar to that observed in Cd2Re2O7, with a broad transition close to 200 K. The magnetic behavior of Cd2Tc2O7 is also compared with that of isomorphous Pb2Tc2O6 and Bi2Tc2O7, also presented in this study. The magnetic susceptibility of the distorted perovskite phase CdTcO3 is weakly temperature dependent, with no obvious signs of an ordering transition below 300 K. Electronic band structure calculations performed to simulate electronic densities of states indicate that the Fermi level is located in a ‘t2g’ band of the octahedrally coordinated Tc cations and therefore metallic conductivity in both CdTcO3 and Cd2Tc2O7.
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