Self-Assembly of Catalytically Active Supramolecular Coordination Compounds within Metal–Organic Frameworks

Supramolecular coordination compounds (SCCs) represent the power of coordination chemistry methodologies to self-assemble discrete architectures with targeted properties. SCCs are generally synthesized in solution, with isolated fully coordinated metal atoms as structural nodes, thus severely limited as metal-based catalysts. Metal–organic frameworks (MOFs) show unique features to act as chemical nanoreactors for the <i>in situ</i> synthesis and stabilization of otherwise not accessible functional species. Here, we present the self-assembly of Pd^II SCCs within the confined space of a pre-formed MOF (SCCs@MOF) and its post-assembly metalation to give a Pd^II–Au^III supramolecular assembly, crystallography underpinned. These SCCs@MOFs catalyze the coupling of boronic acids and/or alkynes, representative multi-site metal-catalyzed reactions in which traditional SCCs tend to decompose, and retain their structural integrity as a consequence of the synergetic hybridization between SCCs and MOFs. These results open new avenues in both the synthesis of novel SCCs and their use in heterogeneous metal-based supramolecular catalysis.