The efficient separation of metals from ores and secondary sources such as electronic waste is necessary to realising circularity in metal supply. Precipitation processes are increasingly popular and are reliant on designing and understanding chemical recognition to achieve selectivity. Here we show that a simple tertiary diamide precipitates gold selectively from aqueous acidic solutions, including from aqua regia solutions of electronic waste. The X-ray crystal structure of the precipitate displays an infinite chain of diamide cations interleaved with tetrachloridoaurate. Gold is released from the precipitate on contact with water, enabling ligand recycling. The diamide is highly selective, with its addition to 29 metals in 2 M HCl resulting in 70% gold uptake and minimal removal of other metals. At 6 M HCl, complete collection of gold, iron, tin, and platinum occurs, demonstrating that adaptable selective metal precipitation is controlled by just one variable. This discovery could be exploited in metal refining and recycling processes due to its tuneable selectivity under different leaching conditions, the avoidance of organic solvents inherent to biphasic extraction, and the straightforward recycling of the precipitant.

Supramolecular chemical strategies for Rare Earth (RE) element separations are emerging which amplify the small changes in properties across the series to bias selectivity in extraction or precipitation. These advances are important as the REs are crucial to modern technologies yet their extraction, separation, and recycling using conventional techniques remain challenging. We report here a pre-organised triamidoarene platform which, under acidic, biphasic conditions, uniquely and selectively precipitates light RE nitratometalates as supramolecular capsules. The capsules exhibit both intra- and intermolecular hydrogen bonds that dictate selectivity, promote precipitation, and facilitate the straightforward release of the RE and recycling of the receptor. This work provides a self-assembly route to metal separations that exploits size and shape complementarity and has the potential to integrate into conventional processes due to its compatibility with acidic metal feed streams.