Bridging the Homogeneous and Heterogeneous Catalysis by Supramolecular Metal‐Organic Cages with Varied Packing Modes

• Published in: Advanced materials (Weinheim) Vol. 36; no. 15; pp. e2310061 - n/a
• Main Authors: Kan, Liang, Zhang, Lei, Dong, Long‐Zhang, Wang, Xiao‐Han, Li, Run‐Han, Guo, Chenxing, Li, Xiaopeng, Yan, Yong, Li, Shun‐Li, Lan, Ya‐Qian
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 01-04-2024
• Subjects: Cages; Carbonates; Catalysis; Catalysts; Catalytic activity; Cycloaddition; cycloaddition of CO2; heterogeneous separation; homogeneous catalysis; metal‐organic cages; Recoverability; self‐assembly; Solvents; Substrates; metal‐organic cages; homogeneous catalysis; heterogeneous separation; cycloaddition of CO2; self‐assembly
• ISSN: 0935-9648; 1521-4095
• DOI: 10.1002/adma.202310061

Integrating the advantages of homogeneous and heterogeneous catalysis has proved to be an optimal strategy for developing catalytic systems with high efficiency, selectivity, and recoverability. Supramolecular metal‐organic cages (MOCs), assembled by the coordination of metal ions with organic linkers into discrete molecules, have performed solvent processability due to their tunable packing modes, endowing them with the potential to act as homogeneous or heterogeneous catalysts in different solvent systems. Here, the design and synthesis of a series of stable {Cu3} cluster‐based tetrahedral MOCs with varied packing structures are reported. These MOCs, as homogeneous catalysts, not only show high catalytic activity and selectivity regardless of substrate size during the CO2 cycloaddition reaction, but also can be easily recovered from the reaction media through separating products and co‐catalysts by one‐step work‐up. This is because that these MOCs have varied solubilities in different solvents due to the tunable packing of MOCs in the solid state. Moreover, the entire catalytic reaction system is very clean, and the purity of cyclic carbonates is as high as 97% without further purification. This work provides a unique strategy for developing novel supramolecular catalysts that can be used for homogeneous catalysis and recycled in a heterogeneous manner.
A series of {Cu12} based tetrahedral (Td) metal‐organic cages (MOCs) with varied packing modes are self‐assembled, which act as highly active homogeneous catalysts for CO2 cycloaddition with epoxides. The varied packing of Td cages from hexagonal to cubic mode in the MOC enables one‐step heterogenous separation of the catalyst, co‐catalyst, and product, which perfectly bridges the homogeneous and heterogeneous catalysis.