Electrostatically cooperative host-in-host of metal cluster ⊂ ionic organic cages in nanopores for enhanced catalysis

• Published in: Nature communications Vol. 13; no. 1; pp. 1471 - 8
• Main Authors: Tan, Liangxiao, Zhou, Jun-Hao, Sun, Jian-Ke, Yuan, Jiayin
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 18.03.2022; Nature Publishing Group; Nature Portfolio
• Subjects: 119/118; 140/131; 147/137; 639/638/263; 639/638/541; 639/638/77; Cages; Cascade chemical reactions; Catalysis; Catalysts; Catalytic activity; Cations; Composite materials; Encapsulation; Humanities and Social Sciences; Ion pairs; Ionic liquids; Ions; Metal clusters; multidisciplinary; Porous materials; Science; Science (multidisciplinary); Substrates
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-022-29031-y

The construction of hierarchically nanoporous composite for high-performance catalytic application is still challenging. In this work, a series of host-in-host ionic porous materials are crafted by encapsulating ionic organic cages into a hyper-crosslinked, oppositely charged porous poly(ionic liquid) (PoPIL) through an ion pair-directed assembly strategy. Specifically, the cationic cage (C-Cage) as the inner host can spatially accommodate a functional Au cluster, forming a [Au⊂C-Cage + ]⊂PoPIL − supramolecular composite. This dual-host molecular hierarchy enables a charge-selective substrate sorting effect to the Au clusters, which amplifies their catalytic activity by at least one order of magnitude as compared to Au confined only by C-Cage as the mono-host (Au⊂C-Cage + ). Moreover, we demonstrate that such dual-host porous system can advantageously immobilize electrostatically repulsive Au⊂C-Cage + and cationic ferrocene co-catalyst (Fer + ) together into the same microcompartments, and synergistically speed up the enzyme-like tandem reactions by channelling the substrate to the catalytic centers via nanoconfinement. The encapsulation of catalysts within hosts is a strategy to tune their reactivity. Here, the authors encapsulate a gold cluster within a porous cage and study its reactivity.