Modular Cocrystallization of Customized Carboranylthiolate-Protected Copper Nanoclusters via Host–Guest Interactions

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.