RESUMEN
A rapid screening method based on traveling-wave ion-mobility spectrometry (TWIMS) combined with tandem mass spectrometry provides insight into the topology of interlocked and knotted molecules, even when they exist in complex mixtures, such as interconverting dynamic combinatorial libraries. A TWIMS characterization of structure-indicative fragments generated by collision-induced dissociation (CID) together with a floppiness parameter defined based on parent- and fragment-ion arrival times provide a straightforward topology identification. To demonstrate its broad applicability, this approach is applied here to six Hopf and two Solomon links, a trefoil knot, and a [3]catenate.
RESUMEN
Reversible oxidation reactions in electrochemically switchable oligorotaxanes with tetrathiafulvalene (TTF) decorated 24-crown-8 ether wheels generate intramolecular mixed-valence and radical-cation interactions between the wheels. This induces shuttling of the wheels and a contraction of inter-wheel distances. Further oxidation generates repulsive forces between the TTFs and maximizes the inter-wheel distances instead. These interactions and co-conformational changes were not observed for structurally similar controls in which acetyl groups along the axle prevent translational motion of the wheels. This operation mode of oligorotaxanes, which is reminiscent of an accordion-like motion, is promising for functional materials and nanodevices such as piston-type rotaxane motors.
RESUMEN
Two new BINOL-based chiral crown ether/ammonium complexes are studied by travelling-wave ion-mobility spectrometry. Homo- and heterochiral crown ether/ammonium complexes differ in their collision cross sections, and these differences go along with changes in hydrogen bonding as revealed by gas phase H/D-exchange experiments. Applications for the determination of enantiomeric excess are discussed.
RESUMEN
London dispersion forces are the weakest interactions between molecules. Because of this, their influence on chemical processes is often low, but can definitely not be ignored, and even becomes important in cases of molecules with large contact surfaces. Hierarchically assembled dinuclear titanium(IV) helicates represent a rare example in which the direct observation of London dispersion forces is possible in solution even in the presence of strong cohesive solvent effects. Hereby, the dispersion forces do not unlimitedly support the formation of the dimeric complexes. Although they have some favorable enthalpic contribution to the dimerization of the monomeric complex units, large flexible substituents become conformationally restricted by the interactions leading to an entropic disadvantage. The dimeric helicates are entropically destabilized.
RESUMEN
The self-inclusion behavior of a tetrathiafulvalene-containing lasso-type pseudo[1]rotaxane can be reversibly switched between threaded and non-threaded states by redox-stimuli. The switching mechanism was investigated by cyclic voltammetry in solution and monitored by ion mobility mass spectrometry in the gas phase.