Guest exchange in an encapsulation complex: a supramolecular substitution reaction.
Encapsulation complexes are reversibly formed assemblies in which small molecule guests are completely surrounded by large molecule hosts. The assemblies are held together by weak intermolecular forces and are dynamic: they form and dissipate on time scales ranging from milliseconds to days-long enough for many interactions, even reactions, to take place within them. Little information is available on the exchange process, how guests get in and out of these complexes. Here we report that these events can be slow enough for conventional kinetic studies, and reactive intermediates can be detected. Guest exchange has much in common with familiar chemical substitution reactions, but differs in some respects: no covalent bonds are made or broken, the substrate is an assembly rather than a single molecule, and at least four molecules are involved in multiple rate-determining steps.
The Skaggs Institute for Chemical Biology and Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037, USA.
J
J
Santamaría
T
T
Martín
G
G
Hilmersson
S L
SL
Craig
J
J
Rebek
D000218:Adamantane / Q000737:chemistry; D000480:Alkynes; D006571:Heterocyclic Compounds / Q000737:chemistry*; D006860:Hydrogen Bonding; D007093:Imidazoles; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy; D012997:Solvents; D013237:Stereoisomerism; D014992:Xylenes; D006574:Heterocyclic Compounds, 2-Ring; D048289:Imidazolidines
D000218:Adamantane; D000480:Alkynes; D006571:Heterocyclic Compounds; D007093:Imidazoles; D012997:Solvents; D014992:Xylenes; C114652:4-n-heptylphenyl compound; C031286:4-xylene; C092018:glycoluril; D006574:Heterocyclic Compounds, 2-Ring; D048289:Imidazolidines