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Reversible Property Switching, Thermoelectric Performance, and d 10 -d 10 Interactions in Ag5Te2Cl. -Between 303 and 333 K the title compound crystallizes in the monoclinic space group P21/n with Z = 8 and between 348 and 393 K in the tetragonal space group I4/mcm with Z = 4. The phase transition at 334 K is characterized by a jump in the total electric conductivity by two orders of magnitude directly affecting the electric and thermoelectric properties. Ag 5 Te 2 Cl is the first example where mobile d 10 ions interact to create low-dimensional partially covalent-bonded subunits in a solid, which then leads to a switching of thermoelectric and electronic properties. -(NILGES*, T.; OSTERS, O.; BAWOHL, M.; BOBET, J.-L.; CHEVALIER, B.; DECOURT, R.; WEIHRICH, R.; Chem. Mater.