Two new isotypic d/f-heterometallic purely inorganic cationic materials, [AgM(TeO)]SO (M = Ce or Th), were synthesized using the metal oxides (MO and TeO), silver nitrate, and sulfuric acid under mild hydrothermal conditions. The prepared materials were characterized via single-crystal X-ray diffraction, which revealed that the materials possess a 3D framework of corner-sharing TeO units. The tellurite framework creates four unique pores, three of which are occupied by the M and Ag metal centers. The tellurite network, metal coordination, and total charge yield a cationic framework, which is charge-balanced by electrostatically bound sulfate anions residing in the largest of the four framework pores. These materials also possess Ag in a ligand-imposed linear geometry.
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