Electrostatically Dominated Pre‐Organization in Cyclodextrin Metal–Organic Frameworks

Electrostatic interactions between oppositely charged entities play a key role in pre-organizing substrates and stabilizing transition states of reactions in enzymes. The use of electrostatic interactions to pre-organize ions in nanoconfined pores, however, has not been investigated to its full potential. Herein, we describe how carboxylate anions can be pre-organized at the behest of their electrostatic interactions with K⁺ cations in nanoconfined tunnels present in γ-cyclodextrin metal-organic frameworks, i.e., CD-MOFs. Several carboxylate anions, which are all much smaller than the cavities of the tunnels, were visualized by X-ray crystallography when nanoconfined in CD-MOFs, despite the large voids present in the tunnels. These anions were found to be aligned within a planar array defined by four K⁺ cations, positioned around the periphery of the tunnels. The strong electrostatic interactions between the carboxylate anions and the K⁺ cations dictate the orientation of the anions and override the influence of all other possible noncovalent bonding interactions between them and the tunnels. Consequently, the aligned pairs of γ-cyclodextrin rings constituting the tunnels become distorted, resulting in them having lower symmetry and fewer disordered carboxylate anions in the solid state. Our findings offer a transformative strategy for controlling the packing and orientation of ions in nanoconfined environments.