No abstract

Polyfluorinated aliphatic compounds were encapsulated by a self-assembled M6L4 coordination host in aqueous media. NMR titration and X-ray crystallographic analyses clearly revealed that the aggregation of the fluorinated moieties of the guests in the host cavity plays a significant role in the binding. Polyfluorinated aromatics did not show such aggregation in the cavity because of their "nonfluorous" nature.

Even flexible linear substrates are conformationally fixed within the hydrophobic confined cavities of enzymes. This enables preorganization of the substrates and their positioning in close proximity to the active center to facilitate stereo- and site-selective reactions. Here, we demonstrate the site-selective electrophilic addition of linear diterpenoids within a self-assembled coordination cage. The reactions proceed through folding of the linear substrates into a U-shaped conformation, which results in noncovalent protection of internal CC bonds to enhance the site selectivity.

This is the author manuscript accepted for publication and has undergone full peer review but has not been through the copyediting, typesetting, pagination and proofreading process, which may lead to differences between this version and the Version of Record.

We synthesized a double-walled knotted cage from a flexible tripodal ligand. The characteristic double-walled structure provided a unique adaptive behavior of the cavity upon inclusion of organic molecules, which was evidenced by NMR and X-ray measurements. The semiflexible host framework, restricted by the knotted topology, enabled kinetic molecular recognition revealing the sequential binding of two different guests from their mixture.