Complementarity and selectivity are the hallmarks of many supramolecular systems. We demonstrate herein the construction of a 3-nm macrocyclic structure with 24 Mo and 12 Fe metal centers, templated by a classical Keggin or Dawson-type polyoxoanion. The resulting supramolecular assemblies have been characterized by single-crystal X-ray diffraction. Driven and stabilized by extensive hydrogen bonding between the macrocyclic host and the anionic guests, the host-guest pairing also displays size and shape selectivity. While the macrocyclic host will not form in the absence of a guest, the anionic template is not removable upon ring closure due to steric hindrance imposed by the host.

Templated formation of a Mo<sub>24</sub>Fe<sub>12</sub> macrocycle with large polyoxometalate guests

245th National Meeting (2013)

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Templated formation of a Mo24Fe12 macrocycle with large polyoxometalate guests

Templated formation of a Mo₂₄Fe₁₂ macrocycle with large polyoxometalate guests