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Published on: August 22, 2014
Robotic Stepwise Synthesis of Hetero-Multinuclear Metal Oxo Clusters as Single-Molecule Magnets
Takuo Minato1,2,3, Daniel Salley2, Noritaka Mizuno1
1Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.
Abstract:
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}Lu2A2 in TBA5[(A-α-SiW9O34)2FeMn4O2{Lu(acac)2}2A2] (II; A = Ag, Na, K; TBA = tetra-n-butylammonium; acac = acetylacetonate) were discovered by the installation of diamagnetic metal cations A+ into a paramagnetic {FeMn4}Lu2 unit in TBA7[(A-α-SiW9O34)2FeMn4O2{Lu(acac)2}2] (I). POMs II exhibited single-molecule magnet properties with the higher energy barriers for magnetization reversal (II, 40.0 K; II, 40.3 K; II, 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.
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