Self-assembly with postmodification: Kinetically stabilized metalla-supramolecular rectangles

Interaction of a predesigned molecular clip (4) with rigid dipyridyl bridging ligands, in acetone/ water mixtures, leads to the formation of molecular rectangles (5-8) in 92-97% isolated yields via spontaneous self-assembly. Characterization was accomplished with multinuclear NMR and UV-vis spectroscopy, FAB mass spectrometry, and X-ray crystallography. The length of these metallamacrocycles ranges from 2 to 3 nm. Postmodification via non-nucleophilic counterion exchange results in enhanced structural integrity for the assemblies.