Self-Assembly of Catalytically Active Supramolecular Coordination Compounds within Metal–Organic Frameworks Rosa Adam Marta Mon Rossella Greco Lucas H. G. Kalinke Alejandro Vidal-Moya Antonio Fernandez Richard E. P. Winpenny Antonio Doménech-Carbó Antonio Leyva-Pérez Donatella Armentano Emilio Pardo Jesús Ferrando-Soria 10.1021/jacs.9b03914.s003 https://acs.figshare.com/articles/dataset/Self-Assembly_of_Catalytically_Active_Supramolecular_Coordination_Compounds_within_Metal_Organic_Frameworks/8320916 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<sup>II</sup> SCCs within the confined space of a pre-formed MOF (SCCs@MOF) and its post-assembly metalation to give a Pd<sup>II</sup>–Au<sup>III</sup> 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. 2019-06-13 00:00:00 post-assembly metalation novel SCCs chemical nanoreactors pre-formed MOF synergetic hybridization metal-based supramolecular catalysis III supramolecular assembly coordination chemistry methodologies metal atoms boronic acids metal-based catalysts Supramolecular Coordination Compounds Pd II SCCs representative multi-site metal-catalyzed reactions