Highly Oxidized States of Phthalocyaninato Terbium(III) Multiple-Decker Complexes Showing Structural Deformations, Biradical Properties and Decreases in Magnetic Anisotropy
Open Access
- 14 July 2020
- journal article
- research article
- Published by Wiley in Chemistry – A European Journal
- Vol. 26 (39), 8621-8630
- https://doi.org/10.1002/chem.202001365
Abstract
Presented here is a comprehensive study of highly oxidized multiple-decker complexes composed of Tb(III)and Cd(II)ions and two to five phthalocyaninato ligands, which are stabilized by electron-donatingn-butoxy groups. From X-ray structural analyses, all the complexes become axially compressed upon ligand oxidation, resulting in bowl-shaped distortions of the ligands. In addition, unusual coexistence of square antiprism and square prism geometries around metal ions was observed in +4echarged species. From paramagnetic(1)H NMR studies on the resulting series of triple, quadruple and quintuple-decker complexes, ligand oxidation leads to a decrease in the magnetic anisotropy, as predicted from theoretical calculations. Unusual paramagnetic shifts were observed in the spectra of the +2echarged quadruple and quintuple-decker complexes, indicating that those two species are actually unexpected triplet biradicals. Magnetic measurements revealed that the series of complexes show single-molecule magnet properties, which are controlled by the multi-step redox induced structural changes.Keywords
Funding Information
- Japan Society for the Promotion of Science (JP14J02656, JP20225003, JP15K05467, JP24750119, 18K14242, 19K05401, JP17K19102)
- Core Research for Evolutional Science and Technology (JPMJCR12L3)
- Beilstein-Institut zur Förderung der Chemischen Wissenschaften
- Deutsche Forschungsgemeinschaft (INST 40/467-1 FUGG)
- European Commission (ERC StG 2012-306826)
- Ministerio de Economía y Competitividad (FANCY CTQ2016-80030-R, MAT2016-80826-R, SEV-2015-0496)
- Generalitat de Catalunya (2017SGR918)
- Centro de Investigación Biomédica en Red en Bioingeniería, Biomateriales y Nanomedicina
- Higher Education Discipline Innovation Project (B18030)
- National University of Singapore (R-143-000-A80-114, R-143-000-A65-133)
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