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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. [ABSTRACT FROM AUTHOR]

Imparting mesopores to organic cages of an intrinsic microporous nature to build up hierarchically porous cage soft materials is a grand challenge and will reshape the property and application scope of traditional organic cage molecules. Herein, we discovered how to engineer mesopores into microporous organic cages via their host–guest interactions with long chain ionic surfactants. Equally important, the ionic head of surfactants equips the supramolecularly assembled porous structures with charge‐selective uptake and release function in solution. Interestingly, such hierarchically porous organic cage can serve as a nanoreactor once trapping enzymes within the cavity, which show 5‐fold enhanced activity of enzymatic catalysis when compared with the free enzymes. [ABSTRACT FROM AUTHOR]

The past decade has witnessed rapid progress in the synthesis of nanoporous organic networks or polymer frameworks for various potential applications. Generally speaking, functionalization of porous networks to add extra properties and enhance materials performance could be achieved either during the pore formation (thus a concurrent approach) or by post-synthetic modification (a sequential approach). Nanoporous organic networks which include ion pairs bound in a covalent manner are of special importance and possess extreme application profiles. Within these nanoporous ionic organic networks (NIONs), here with a pore size in the range from sub-1 nm to 100 nm, we observe a synergistic coupling of the electrostatic interaction of charges, the nanoconfinement within pores and the addressable functional units in soft matter resulting in a wide variety of functions and applications, above all catalysis, energy storage and conversion, as well as environment-related operations. This review aims to highlight the recent progress in this area, and seeks to raise original perspectives that will stimulate future advancements at both the fundamental and applied level. [ABSTRACT FROM AUTHOR]