Borromean-Entanglement-Driven Assembly of Porous Molecular Architectures with Anion-Modified Pore Space

A series of metal–organic frameworks based on a flexible, highly charged Bpybc ligand, namely 1⋅Mn⊃OH−, 2⋅Mn⊃SO42−, 3⋅Mn⊃bdc2−, 4⋅Eu⊃SO42− (H2BpybcCl2=1,1′‐bis(4‐carboxybenzyl)‐4,4′‐bipyridinium dichloride, H2bdc=1,4‐benzenedicarboxylic acid) have been obtained by a self‐assembly process. Single‐crystal X‐ray‐diffraction analysis revealed that all of these compounds contained the same n‐fold 2D→3D Borromean‐entangled topology with irregular butterfly‐like pore channels that were parallel to the Borromean sheets. These structures were highly tolerant towards various metal ions (from divalent transition metals to trivalent lanthanide ions) and anion species (from small inorganic anions to bulky organic anions), which demonstrated the superstability of these Borromean linkages. This non‐interpenetrated entanglement represents a new way of increasing the stability of the porous frameworks. The introduction of bipyridinium molecules into the porous frameworks led to the formation of cationic surface, which showed high affinities to methanol and water vapor. The distinct adsorption and desorption isotherms of methanol vapor in four complexes revealed that the accommodated anion species (of different size, shape, and location) provided a unique platform to tune the environment of the pore space. Measurements of the adsorption of various organic vapors onto framework 1⋅Mn⊃OH− further revealed that these pores have a high adsorption selectivity towards molecules with different sizes, polarities, or π‐conjugated structures. You're a Borromeanie: Borromean‐entangled porous frameworks (an example is shown here) that can accommodate different kinds of anions with various sizes, shapes, and locations demonstrate the superstability of Borromean linkages and their potential in constructing porous frameworks with tunable pore environments.