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One striking feature of enzyme is its controllable ability to trap substrates via synergistic or cooperative binding in the enzymatic pocket, which renders the shape‐selectivity of product by the confined spatial environment. The success of shape‐selective catalysis relies on the ability of enzyme to tune the thermodynamics and kinetics for chemical reactions. In emulation of enzyme's ability, we showcase herein a targeting strategy with the substrate being anchored on the internal pore wall of metal‐organic frameworks (MOFs), taking full advantage of the sterically kinetic control to achieve shape‐selectivity for the reactions. For this purpose, a series of binding site‐accessible metal metalloporphyrin‐frameworks (MMPFs) have been investigated to shed light on the nature of enzyme‐mimic catalysis. They exhibit a different density of binding sites that are well arranged into the nanospace with corresponding distances of opposite binding sites. Such a structural specificity results in a facile switch in selectivity from an exclusive formation of the thermodynamically stable product to the kinetic product. Thus, the proposed targeting strategy, based on the combination of porous materials and binding events, paves a new way to develop highly efficient heterogeneous catalysts for shifting selectivity. [ABSTRACT FROM AUTHOR]

Herein, we show how the spatial environment in the functional pores of covalent organic frameworks (COFs) can be manipulated in order to exert control in catalysis. The underlying mechanism of this strategy relies on the placement of linear polymers in the pore channels that are anchored with catalytic species, analogous to outer‐sphere residue cooperativity within the active sites of enzymes. This approach benefits from the flexibility and enriched concentration of the functional moieties on the linear polymers, enabling the desired reaction environment in close proximity to the active sites, thereby impacting the reaction outcomes. Specifically, in the representative dehydration of fructose to produce 5‐hydroxymethylfurfural, dramatic activity and selectivity improvements have been achieved for the active center of sulfonic acid groups in COFs after encapsulation of polymeric solvent analogues 1‐methyl‐2‐pyrrolidinone and ionic liquid. [ABSTRACT FROM AUTHOR]