Low-temperature synthesis of cation-ordered bulk Zn₃WN₄ semiconductor via heterovalent solid-state metathesis

Metathesis reactions are widely used in synthetic chemistry. While state-of-the-art organic metathesis involves highly controlled processes where specific bonds are broken and formed, inorganic metathesis reactions are often extremely exothermic and, consequently, poorly controlled. Ternary nitrides offer a technologically relevant platform for expanding synthetic control of inorganic metathesis reactions. Here, we show that energy-controlled metathesis reactions involving a heterovalent exchange are possible in inorganic nitrides. We synthesized Zn₃WN₄ by swapping Zn²⁺ and Li⁺ between Li₆WN₄ and ZnX₂ (X = Br, Cl, F) precursors. The in situ synchrotron powder X-ray diffraction and differential scanning calorimetry show that the reaction onset is correlated with the ZnX₂ melting point and that product purity is inversely correlated with the reaction's exothermicity. Therefore, careful choice of the halide counterion (i.e., ZnBr₂) allows the synthesis to proceed in a swift but controlled manner at a surprisingly low temperature for an inorganic nitride (300 °C). High resolution synchrotron powder X-ray diffraction and diffuse reflectance spectroscopy confirm the synthesis of a cation-ordered Zn₃WN₄ semiconducting material. We hypothesize that this synthesis strategy is generalizable because many Li-M-N phases are known (where M is a metal) and could therefore serve as precursors for metathesis reactions targeting new ternary nitrides. This work expands the synthetic control of inorganic metathesis reactions in a way that will accelerate the discovery of novel functional ternary nitrides and other currently inaccessible materials.