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 in situ 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.