Robotic Stepwise Synthesis of Hetero-Multinuclear Metal Oxo Clusters as Single-Molecule Magnets

An efficient stepwise synthesis method for discovering new heteromultinuclear metal clusters using a robotic workflow is developed where numerous reaction conditions constructing oxo in polyoxometalates (POMs) were explored custom-built automated platform. As result, nonanuclear tetrametallic {FeMn4}Lu2A2 TBA5[(A-α-SiW9O34)2FeMn4O2{Lu(acac)2}2A2] (IIA; A = Ag, Na, K; TBA tetra-n-butylammonium; acac acetylacetonate) discovered by the installation of diamagnetic cations A+ into paramagnetic {FeMn4}Lu2 unit TBA7[(A-α-SiW9O34)2FeMn4O2{Lu(acac)2}2] (I). POMs IIA exhibited single-molecule magnet properties with higher energy barriers magnetization reversal (IIAg, 40.0 IINa, 40.3 IIK, 26.7 K) compared that parent I (19.7 K). Importantly, these unique constructed as designed step predictable sequential multistep reactions time-efficient