Symmetry breaking in self-assembled M 4 L 6 cage complexes

Abstract

Here we describe the phenomenon of symmetry breaking within a series of M4L6 container molecules. These containers were synthesized using planar rigid bis-bidentate ligands based on 2,6-substituted naphthalene, anthracene, or anthraquinone spacers and Fe(II) ions. The planarity of the ligand spacer favors a stereochemical configuration in which each cage contains two metal centers of opposite handedness to the other two, which would ordinarily result in an S4-symmetric, achiral configuration. Reduction of symmetry from S4 to C1 is achieved by the spatial offset between each ligand's pair of binding sites, which breaks the S4 symmetry axis. Using larger Cd(II) or Co(II) ions instead of Fe(II) resulted, in some cases, in the observation of dynamic motion of the symmetry-breaking ligands in solution. NMR spectra of these dynamic complexes thus reflected apparent S4 symmetry owing to rapid interconversion between energetically degenerate, enantiomeric C1-symmetric conformations.