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

Takuo Minato; Daniel Salley; Noritaka Mizuno; Kazuya Yamaguchi; Leroy Cronin; Kosuke Suzuki

doi:10.1021/jacs.1c06047

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

J Am Chem Soc. 2021 Aug 18;143(32):12809-12816. doi: 10.1021/jacs.1c06047. Epub 2021 Aug 6.

Authors

Takuo Minato^{1

2

3}, Daniel Salley², Noritaka Mizuno¹, Kazuya Yamaguchi¹, Leroy Cronin², Kosuke Suzuki^{1

4}

Affiliations

¹ Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.
² School of Chemistry, The University of Glasgow, Glasgow G12 8QQ, United Kingdom.
³ Department of Applied Chemistry, Graduate School of Advanced Science and Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8527, Japan.
⁴ Precursory Research for Embryonic Science and Technology (PRESTO), Japan Science and Technology Agency (JST), 4-1-8, Honcho, Kawaguchi, Saitama 332-0012, Japan.

PMID: 34358427
DOI: 10.1021/jacs.1c06047

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; 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^A exhibited single-molecule magnet properties with the higher energy barriers for magnetization reversal (II^Ag, 40.0 K; II^Na, 40.3 K; II^K, 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.