This review describes the kinetics at play in Cucurbituril (CB[n])/guest recognition within a very wide time frame, from picoseconds to days. We cover the kinetics of (1) radiative and non‐radiative decays of fluorophores inside and outside CB[n]s, (2) guest motions in the CB[n] cavity, and (3) ingression, egression and threading mechanisms into, out of and through the macrocycles. We then show that the kinetics of guest release or capture can be controlled using CB[n]‐capped mesoporous systems and micelles, or by coupling those processes to the kinetics of ancillary reactions. The last section is devoted to the latest examples of reactions catalyzed and inhibited by CB[n]s.

The self-assembly into dynamic oligomers of Cucurbit[8]uril (CB[8]), a positive ditopic Ir(III) bis-terpyridine complex, and a negative ditopic Fe(II) bis-terpyridine complex flanked by four butyrate side chains was assessed to answer a seemingly straightforward question: does CB[8] adopt a social self-sorting pattern by encapsulating both positive and negative units into a heteroternary complex? We showed that this is indeed the case, with CB[8] linking a positive Ir unit to a neighboring negative Fe unit whenever possible. Furthermore, the solubility of the dynamic oligomers was significantly affected by their sequence; upon addition of 0.6-1.2 equiv of positive Ir oligomer to its negative Fe counterpart, the predominant assembly present in solution was a mixed oligomer with a (Fe-Ir-Ir-) sequence. Weak interactions between the negative butyrate side chains and the partially positive outer wall of CB[7] were also identified by two-dimensional nuclear magnetic resonance techniques, and resulted in a negative p K shift (0.10 p K unit) for the terminal carboxylic groups.

To maximize Coulombic interactions, cucurbit[8]uril (CB[8]) typically forms ternary complexes that distribute the positive charges of the pair of guests (if any) over both carbonylated portals of the macrocycle. We present here the first exception to this recognition pattern. Platinum(II) acetylides flanked by 4'-substituted terpyridyl ligands (tpy) form 2:1 complexes with CB[8] in an exclusively stacked head-to-head orientation in a water/acetonitrile mixture. The host encapsulates the pair of tpy substituents, and both positive Pt centers sit on top of each other at the same CB[8] rim, leaving the other rim free of any interaction with the guests. This dramatic charge imbalance between the CB[8] rims would be electrostatically penalizing, were it not for allosteric π-π interactions between the stacked tpy ligands, and possible metal-metal interactions between both Pt centers. When both tpy and acetylides are substituted with aryl units, the metal-ligand complexes form 2:2 assemblies with CB[8] in aqueous medium, and the directionality of the assembly (head-to-head or head-to-tail) can be controlled, both kinetically and thermodynamically.

The geometry, arrangement, and orientation of a quaternary ammonium surfactant flanked by two methyl groups, a benzyl head, and an octyl tail were assessed at the air–water and air-deuterium oxide (D2O) interfaces using sum frequency generation vibrational spectroscopy. Remarkably, symmetric and asymmetric N–CH3 stretches (at ∼2979 and ∼3045 cm–1, respectively, in the SSP polarization combination) were visible in water but negligible in deuterium oxide. We concluded that D2O addition triggers the average reorientation of the dimethyl amino units parallel to the interface and possibly changes the overall conformation of the surfactant. A reduced number of gauche defects in the surfactant octyl chain is also observed in D2O. Tilt angles for the octyl chain (1.0–10.8°) are consistent with an ordered monolayer at the air–liquid interface.

The torsional barriers along the Caryl-Caryl axis of a pair of isosteric disubstituted biphenyls were determined by variable temperature 1H NMR spectroscopy in three solvents with contrasted hydrogen bond accepting...