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“Breathing” Motion of a Modulable Molecular Cavity
Author(s) -
Zhang Dawei,
Cochrane James Robert,
Di Pietro Sebastiano,
Guy Laure,
Gornitzka Heinz,
Dutasta JeanPierre,
Martinez Alexandre
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201700395
Subject(s) - crystallography , chemistry , vanadium , ligand (biochemistry) , nuclear magnetic resonance spectroscopy , stereochemistry , inorganic chemistry , biochemistry , receptor
A class of hemicryptophane cages that adopt imploded conformations in solution and in the solid state has been described and studied by NMR spectroscopy and X‐ray crystallography. It is reported that the degree of collapse of the molecular cavity can be controlled by changing the stereochemistry of the chiral elements of the hemicryptophanes, leading to a modulation of their physical and chemical properties. Upon the binding of an oxidovanadium unit, the collapsed molecular cavity can inflate to give an expanded conformation. Removal of the vanadium core by an ancillary complexing ligand restores the initial folded structure. Thus, coordination/de‐coordination of the metal ion controls the dynamic motions of the cage, leading to a reversible nanomechanical process. This controlled motion between a collapsed and expanded cavity can be seen as that of a breathable molecular cage.