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.