title: Thermodynamically controlled synthesis of a chiral tetra-cavitand nanocapsule and mechanism of enantiomerization.
abstract: The dynamic covalent synthesis, structure and conformational dynamics of a chiral polyimine nanocapsule 1a are reported. Reaction of four tetraformyl cavitands and eight H(2)N(CH(2))(2)NH(2) yields quantitatively 1a, which has a compact, asymmetrically folded, pseudo-C(2)-symmetric structure, as determined by X-ray crystallography, and encapsulates four CHCl(3) and three CH(3)OH guests in the solid state. In solution, 1a enantiomerizes by passing over a barrier of ΔG(298)(double dagger) = 21.5 ± 0.7 kcal mol(-1) via a refolding process.
authors.affiliation: Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, Piscataway, New Jersey 08854, United States.
authors.forename: Junling
authors.initials: J
authors.lastname: Sun
authors.forename: James L
authors.initials: JL
authors.lastname: Bennett
authors.forename: Thomas J
authors.initials: TJ
authors.lastname: Emge
authors.forename: Ralf
authors.initials: R
authors.lastname: Warmuth