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Journal article
Electrostatically Dominated Pre-Organization in Cyclodextrin Metal-Organic Frameworks
Angewandte Chemie International Edition, Vol.64(3), e202415404
01/15/2025
PMID: 39415338
Web of Science ID: WOS:001365245700001
Abstract
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 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 their 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.
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Details
- Title
- Electrostatically Dominated Pre-Organization in Cyclodextrin Metal-Organic Frameworks
- Publication Details
- Angewandte Chemie International Edition, Vol.64(3), e202415404
- Resource Type
- Journal article
- Copyright
- © 2024 Wiley-VCH GmbH
- Identifiers
- WOS:001365245700001; 99380580136606600
- Academic Unit
- Hal Marcus College of Science and Engineering ; Chemistry
- Language
- English