On the mechanism of action of gated molecular baskets: The synchronicity of the revolving motion of gates and in/out trafficking of guests.

We used dynamic (1)H NMR spectroscopic methods to examine the kinetics and thermodynamics of CH(3)CCl(3) (2) entering and leaving the gated molecular basket 1. We found that the encapsulation is first-order in basket 1 and guest 2, while the decomplexation is zeroth-order in the guest. Importantly, the interchange mechanism in which a molecule of CH(3)CCl(3) directly displaces the entrapped CH(3)CCl(3) was not observed.

Controlling the dynamics of molecular encapsulation and gating.

This critical review describes mechanisms by which guest molecules enter and depart molecular capsules. The discussion focuses on presenting gated molecular encapsulation, i.e.

Gated molecular recognition and dynamic discrimination of guests.

Some highly efficient enzymes, e.g., acetylcholinesterase, use gating as a tool for controlling the rate by which substrates access their active site to direct product formation.

Four-state switching characteristics of a gated molecular basket.

The development of working molecular devices relies on the ability to extrinsically modulate function via structure. We have found that gated molecular basket 1 can be reversibly interconverted among four unique structural states (see above). Controlling the relative population of these states, the recognition characteristics of the basket can be finely tuned.

Tuning the rate of molecular translocation.

Gated molecular baskets can be functionalized to tune the conformational dynamics of the gates, installed at their rim, and thereby to adjust the time that a guest molecule spends inside their cavity.

Molecular encapsulation via metal-to-ligand coordination in a Cu(I)-folded molecular basket.

A molecular basket, composed of a semirigid C3v symmetric tris-norbornadiene framework and three pyridine flaps at the rim, has been shown to coordinate to a Cu(I) cation and thereby fold in a multivalent fashion. The assembly was effective (Ka = 1.73 +/- 0.

Prospects in controlling morphology, dynamics and responsiveness of supramolecular polymers.

The programmed assembly of molecules into supramolecular polymers is of great interest for developing stimuli-responsive "smart" materials. Controlling the morphology, dynamics and responsiveness of such materials is essential for future applications. It, however, necessitates fundamental understanding of non-covalent forces that direct the ordering of molecules in complex environments.