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

Huang, Jia-Hong; Liu, Li-Ying; Wang, Zhao-Yang; Zang, Shuang-Quan; Mak, Thomas C W · ACS Nano · 2022

basic_science · Level V

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Abstract

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, Cu<sub>14</sub>(C<sub>2</sub>B<sub>10</sub>H<sub>10</sub>S<sub>2</sub>)<sub>6</sub>(CH<sub>3</sub>CN)<sub>6</sub> (Cu<sub>14</sub>) and Cu<sub>16</sub>(C<sub>2</sub>B<sub>10</sub>H<sub>10</sub>S<sub>2</sub>)<sub>8</sub> (Cu<sub>16</sub>), which adopt matched surface patterns by host-guest chemistry. The Cu<sub>14</sub>·Cu<sub>16</sub> cocrystals show integrated UV-vis adsorption and dual emission stemming from the Cu<sub>14</sub> and Cu<sub>16</sub> 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.