Alkali-Metal-Ion-Directed Self-Assembly of Redox-Active Manganese(III) Supramolecular Boxes

The ability to organize functional
molecules into higher dimensional arrays with well-defined spatial
relationships between the components is one of the major goals in
supramolecular chemistry. We report here a new route for the preparation
of supramolecular boxes, incorporating two types of metal ions: (i)
alkali-metal ions, which induce the supramolecular architecture and
essentially play a structural role in the final compounds; (ii) manganese­(III)
ions, which are redox-active systems and give functionality to the
new cages. Our results evidence that the size of the cavity inside
the box can be tuned depending on the alkali metal used, a characteristic
that gives this new family of compounds the potential to act selectively
against different substrates. These compounds behave as active catalysts
for disproportionation of H2O2 or for water
photolysis, but they catalyze neither catecholase reaction nor peroxidase
action upon using bulky organic substrates.