Cocrystals containing distinct atom-precise metal nanoclusters (NCs) provide an opportunity to elucidate the crystallization process, architectural complexity, and newly emerging properties of condensed-state metal NC-assembled materials. However, the controllable preparation of such cocrystals is still challenging. Herein, we present a modular strategy to cocrystallize two customized carboranylthiolate-protected copper NCs, Cu14(C2B10H10S2)6(CH3CN)6 (Cu14) and Cu16(C2B10H10S2)8 (Cu16), which adopt matched surface patterns by host-guest chemistry. The Cu14·Cu16 cocrystals show integrated UV-vis adsorption and dual emission stemming from the Cu14 and Cu16 NCs. Moreover, the component NCs are selectively doped by gold atoms, which is a promising way to incorporate diverse properties of metal cluster-based cocrystals. This work not only provides a copper NC-based cocrystal for a profound study on a condensed-state copper nanomaterial but also develops a modular strategy for the cocrystallization of metal NCs.
Keywords: carborane; cocrystallization; copper nanoclusters; host−guest assembly; modular strategy.