Single molecule solvation and its effects on tautomeric equilibria in a self-assembled capsule.
A self-assembled cylindrical capsule provides a nanoscale environment that affects keto-enol equilibria. The equilibrium constants for encapsulated beta-ketoesters show values that differ by an order of magnitude from that of the free tautomers in solution. For complexes with a single, large encapsulated guest, the inner surfaces of the capsule and the seam of the hydrogen bonds influence the equilibrium between the encapsulated keto and enol forms. For complexes of smaller beta-ketoesters, the coencapsulated solvent influences the equilibria. The solvent reduces the space available and affects the positioning of the ester in the capsule.
Scarso
Alessandro
A
Skaggs Institute for Chemical Biology and Department of Chemistry, The Scripps Research Institute, MB-26, 10550 North Torrey Pines Road, La Jolla, California 92037, USA.
Rebek
Julius
J
D000438:Alcohols / Q000737:chemistry*; D004952:Esters / Q000737:chemistry; D007659:Ketones / Q000737:chemistry*; D007700:Kinetics; D046911:Macromolecular Substances; D008958:Models, Molecular; D012996:Solutions
D000438:Alcohols; D004952:Esters; D007659:Ketones; D046911:Macromolecular Substances; D012996:Solutions