Collect. Czech. Chem. Commun. 2005, 70, 1493-1576

Exploring Dynamics and Stereochemistry in Mechanically-Interlocked Compounds

Scott A. Vignon and J. Fraser Stoddart*

California NanoSystems Institute and Department of Chemistry and Biochemistry, University of California, Los Angeles, 405 Hilgard Avenue, Los Angeles, CA 90095-1569, U.S.A.


The advent of self-assembly and template-directed synthetic protocols has led to a tremendous surge in the number of mechanically-interlocked compounds being prepared and studied. As these investigations are being carried out, it is becoming increasingly apparent that many of these compounds, known as catenanes and rotaxanes, possess unique dynamic and stereochemical properties. In addition, the drive to create molecular switches and machines for nanotechnological applications has generated a need to understand how to control those properties in condensed phases. Here, we present an overview of the field with regard to the solution dynamics and stereochemistry of mechanically-interlocked compounds - as well as to some related structural types - and review the recent results from our own research in some detail. 1H NMR spectroscopy has proven to be a powerful tool for probing both degenerate and nondegenerate dynamic processes in these compounds, as well as for identifying stereoisomers if they are present in solution. The results of several variable temperature NMR investigations on the effects of structural changes upon the dynamic processes and stimulated relative motions of components in catenanes and rotaxanes, as well as in some self-complexes and pretzelanes, are discussed. A review with 90 references.

Keywords: Catenanes; Donor-acceptor; Dynamic stereochemistry; Molecular machines; NMR dynamics; Pretzelanes; Rotaxanes; Self-complexing; Tetrathiafulvalenes; Macrocycles.

References: 184 live references.