Self-Templating and InSitu Assembly of a Cubic Cluster-of-Clusters Architecture Based on a {Mo24Fe12} Inorganic Macrocycle

Engineering self-templating inorganic architectures is critical for the development of bottom-up approaches to nanoscience, but systems with a hierarchy of templates are elusive. Herein we describe that the cluster-anion-templated (CAT) assembly of a {CAT}< subset of>{Mo24Fe12} macrocycle forms a giant ca. 220nm(3) unit cell containing 16macrocycles clustered into eight face-shared tetrahedral cluster-of-clusters assemblies. We show that {CAT}< subset of>{Mo24Fe12} with different CATs gives the compounds 1-4 for CAT=Anderson {FeMo6} (1), Keggin {PMo12} (2), Dawson {P2W18} (3), and {Mo12O36(HPO3)(2)} (4) polyoxometalates. Template-free assembly can be achieved, whereby the macrocycle components can also form a template insitu allowing template to macrocycle to superstructure formation and the ability to exchange the templates. Furthermore, the transformation of template clusters within the inorganic macrocycle {Mo24Fe12} allows the self-generation of an uncapped {Mo12O36(HPO3)(2)} in compound 4.