Stabilizing the Extrinsic Porosity in Metal–Organic Cages-Based Supramolecular Framework by In Situ Catalytic Polymerization

Abstract

Porous supramolecular frameworks based on metal-organic cages (MOCs) usually have poor structural stability after activation. This issue narrows the scope of their potential applications, particularly for the inclusion of guest molecules that demand high porosity. Herein, the authors have reported the stabilization of a mesoporous zirconium MOC-based supramolecular framework with an in situ catalytic polymerization strategy. Due to the passivation effect imparted by this strategy, the introduced polymer is primarily distributed on the surface of the crystals, which results in the hybrid material retaining its crystallinity and permanent porosity. A preliminary application of this type of stabilized mesoporous supramolecular framework shows that among MOC-based supramolecular frameworks, it has the highest high-pressure methane uptake. Such a facile strategy may provide a general way to stabilize fragile porous materials and facilitate exploration of their potential applications.

Crystalline‐State Solvent: Metal‐Organic Frameworks as a Platform for Intercepting Aggregation‐Caused Quenching

“…Metal-organic frameworks (MOFs) are a promising class of crystalline inorganic-organic hybrid materials featuring uniform pores, high internal surface areas, and tailorable chemical structure and properties. [7][8] These advantages make MOFs unique hosts for adsorbing various functional guests, including metal ions, [9] organic molecules, [10] metal complexes, [11] polyoxometalate, [12] nanoparticles, [13] and proteins. [14] The resulting composite MOF materials offer opportunities for improved performances or emergent properties in comparison to the individual parent MOF and guest molecules separately.…”

Porous Pyrene Organic Cage with Unusual Absorption Bathochromic-Shift Enables Visible Light Photocatalysis

“…20,21 Porous organic cages (POCs) constructed from covalently linked molecular building blocks have emerged as new types of nanosized synthons for porous reticular frameworks. [22][23][24][25][26][27][28][29] In comparison with other porous materials, [30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46] POCs possess both intrinsic intracage cavity and intercage porosity upon assembly, in addition to their advantageous solution processability and regeneration through recrystallization. The unique porous nature of POCs can facilitate the mass transfer of reactants and products in heterogeneous catalysis.…”

Solvent‐Controlled Construction of Molecular Chains and Bowls/Sieves from a Bent Dipyridyl Ligand†

“…Self‐assembly of fascinating polymeric and discrete molecular architectures has attracted continuous research interests. [ 1‐10 ] While numerous porous coordination polymers have been constructed and widely used for guest storage and separation, [ 11‐15 ] discrete molecular containers are relatively few. [ 16‐18 ] Generally, metal/ligand building blocks with specific angularity are used to construct topologically simple structures such as rings and cages with high symmetries.…”