A Strategy for the Preparation of Thioantimonates Based on the Concept of Weak Acids and Corresponding Strong Bases

By following a new synthetic approach, which is based on the in situ formation of a basic medium by the reaction between the strong base Sb(V)S₄^3? and the weak acid H₂O, it was possible to prepare three layered thioantimonate(III) compounds of composition [TM(2,2′‐bipyridine)₃][Sb₆S₁₀] (TM=Ni, Fe) and [Ni(4,4′‐dimethyl‐2,2′‐bipyridine)₃][Sb₆S₁₀] under hydrothermal conditions featuring two different thioantimonate(III) network topologies. The antimony source, Na₃SbS₄ ? 9 H₂O, undergoes several decomposition reactions and produces the Sb^IIIS₃ species, which condenses to generate the layered anion. The application of transition‐metal complexes avoids crystallization of dense phases. The reactions are very fast compared to conventional hydrothermal/solvothermal syntheses and are much less sensitive to changes of the reaction parameters.