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

Abstract

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, we report the design and synthesis of a series of stable {Cu3} cluster based tetrahedral MOCs with varied packing structures. These MOCs, as homogeneous catalysts, not only show high catalytic activity and selectivity regardless of substrates 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.This article is protected by copyright. All rights reserved

Metal ion attachment in cavities of metal organic polyhedra to enhance framework robustness and catalytic performance

“…[1][2][3] Moreover, MOPs have the unique advantage of being processed in solution, 4 which differentiates them from extended materials such as metalorganic frameworks (MOFs). These features enable MOPs to be applied in various fields, such as sensing, [5][6][7][8] catalysis, [9][10][11] drug delivery, [12][13][14] gas separation [15][16][17] and gas storage. [18][19][20] To better meet the needs of various applications, MOPs can be functionalized by two methods.…”