Supramolecular Coordination Compounds (SCCs) represent the power of Coordination Chemistry methodologies to self-assemble discrete architectures with targeted properties. SCCs are generally synthesised 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 PdII SCCs within the confined space of a preformed MOF (SCCs@MOF) and its post-assembly metalation to give a PdII-AuIII supramolecular assembly, crystallography underpinned. These SCCs@MOF catalyse the coupling of boronic acids and/or alkynes, representative multisite metallic-catalysed reactions in which traditional SCCs tend to decompose, and retain its structural integrity as consequence of the synergetic hybridization between SCCs and MOF. These results open new avenues in both the synthesis of novel SCCs and their use on heterogeneous metal-based Supramolecular Catalysis.
Adam Ortiz, Rosa Mon Conejero, Marta Greco, Rossella Kalinke, Lucas H. G. Vidal-Moya, Alejandro Fernandez, Antonio Winpenny, Richard E. P. Doménech Carbó, Antonio Leyva-Pérez, Antonio Armentano, Donatella Pardo Marín, Emilio Ferrando Soria, Jesús 2019 Self-Assembly of Catalytically-Active Supramolecular Coordination Compounds within Metal-Organic Frameworks Journal of the American Chemical Society 141 26 10350 10360