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Journal of the American Chemical Society, Vol.135, No.47, 17999-18006, 2013
High-Fidelity Stereochemical Memory in a (Fe4L4)-L-II Tetrahedral Capsule
A new class of (Fe4L4)-L-II capsules, based upon a tritopic trialdehyde subcomponent, is reported. One such capsule was prepared diastereoselectively through the incorporation of a chiral amine residue. This amine was displaced by an achiral one, while maintaining the stereochemistry of the cage framework (99% ee); this cage retained its stereochemistry even after 4 days at 90 degrees C. Mechanistic studies indicate the memory displayed by this capsule to be the result of effective stereochemical communication between the metal centers mediated by the rigid 3-fold-symmetric faces, in combination with a stepwise substitution mechanism.