Self-Assembly\nof Catalytically Active Supramolecular\nCoordination Compounds within Metal–Organic Frameworks

Abstract

Supramolecular\ncoordination compounds (SCCs) represent the power\nof coordination chemistry methodologies to self-assemble discrete\narchitectures with targeted properties. SCCs are generally synthesized\nin solution, with isolated fully coordinated metal atoms as structural\nnodes, thus severely limited as metal-based catalysts. Metal–organic\nframeworks (MOFs) show unique features to act as chemical nanoreactors\nfor the <i>in situ</i> synthesis and stabilization of otherwise\nnot accessible functional species. Here, we present the self-assembly\nof Pd^II SCCs within the confined space of a pre-formed\nMOF (SCCs@MOF) and its post-assembly metalation to give a Pd^II–Au^III supramolecular assembly, crystallography\nunderpinned. These SCCs@MOFs catalyze the coupling of boronic acids\nand/or alkynes, representative multi-site metal-catalyzed reactions\nin which traditional SCCs tend to decompose, and retain their structural\nintegrity as a consequence of the synergetic hybridization between\nSCCs and MOFs. These results open new avenues in both the synthesis\nof novel SCCs and their use in heterogeneous metal-based supramolecular\ncatalysis.