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

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 c a r b o r a n y l t h i o l a t e -p r o t e c t e d c o p p e r N C s , Cu 14 (C 2 B 10 H 10 S 2 ) 6 (CH 3 CN) 6 (Cu 14 ) and Cu 16 (C 2 B 10 H 10 S 2 ) 8 (Cu 16 ), which adopt matched surface patterns by host−guest chemistry. The Cu 14 •Cu 16 cocrystals show integrated UV−vis adsorption and dual emission stemming from the Cu 14 and Cu 16 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.

Parasitism in Metal Nanoclusters: A Case Study of (AuAg)25·(AuAg)27

“…In recent years, cocrystals have emerged as attractive nanomaterials with aesthetic structures, fascinating properties, and diverse potential applications. − Cocrystallization represents the long-range ordered arrangement of two or more components in the same crystallization system, and the special noncovalent interactions between/among these components often lead to various intriguing properties that are different from any single component. Nanocluster cocrystallization provides an ideal platform to explore the intermolecular interactions between and among multiple nanoparticles.…”

Carborane-Cluster-Wrapped Copper Cluster with Cyclodextrin-like Cavities for Chiral Recognition

“…Carboranes (dicarba- closo -dodecaboranes) are icosahedral clusters and have multiple directional hydridic sites, C–H and B–H vertices . Owing to their unique three-dimensional architectures and hydridic sites, carborane analogues have a uniqueness in the field of host–guest chemistry and supramolecular chemistry. − A series of metal clusters stabilized by carborane-based thiolate ligands demonstrated distinguished performances in stability and optical properties. − Because of the unique steric of carboranes and intracluster C–H···π, B–H···π, and unique C–H···B–H hydrogen bonding interactions, which restrain the arrangement of the ligands and subsequently influence the pattern of interface or metal core, carborane-protected metal clusters readily form chiral products. − Therefore, the appropriate structure of the metal cluster can create a chiral environment, encompassed by the hydrogen-rich surfaces of carborane clusters, for chirality recognition.…”

Cocrystallization of Two Negatively Charged Dimercaptomaleonitrile-Stabilized Silver Nanoclusters

“…On the other hand, studies on the assembly of atomically precise metal NCs are of great significance in the nanomaterial field, which has attracted increasing interest in the last few decades. − The tunable size, shape, and surface chemistry of metal NCs make them fair building blocks in cluster-assembled materials. Recently, a series of metal NC-based cocrystals have been reported, − which shed some light on the assembly of distinct NCs. Notably, the component NCs in these cocrystals are usually electroneutral or ion pairs.…”