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 for constructing heteromultinuclear metal oxo clusters in polyoxometalates (POMs) were explored using a custom-built automated platform. As a result, new nonanuclear tetrametallic oxo clusters {FeMn4} Lu(2)A(2) in TBA(5)[(A-alpha-SiW9O34)(2)FeMn4O2{Lu-(acac)(2)}(2)A(2)] (IIA; A = Ag, Na, K; TBA = tetra-n-butylammonium; acac = acetylacetonate) were discovered by the installation of diamagnetic metal cations A(+) into a paramagnetic {FeMn4}Lu-2 unit in TBA(7)[(A-alpha-SiW9O34)(2)FeMn4O2{Lu(acac)(2)}(2)] (I). POMs IIA exhibited single-molecule magnet properties with the higher energy barriers for magnetization reversal (IIAg, 40.0 K; IINa, 40.3 K; IIK, 26.7 K) compared with that of the parent I (19.7 K). Importantly, these clusters with unique properties were constructed as designed by a step of the predictable sequential multistep reactions with the time-efficient platform.