Please use this identifier to cite or link to this item: https://doi.org/10.1002/chem.202001365
Title: Highly Oxidized States of Phthalocyaninato Terbium(III) Multiple-Decker Complexes Showing Structural Deformations, Biradical Properties and Decreases in Magnetic Anisotropy
Authors: Horii, Y
Damjanović, M
Ajayakumar, MR
Katoh, K
Kitagawa, Y
Chibotaru, L
Ungur, L 
Mas-Torrent, M
Wernsdorfer, W
Breedlove, BK
Enders, M
Veciana, J
Yamashita, M
Keywords: NMR
biradical
crystal engineering
magnetic anisotropy
redox
Issue Date: 14-Jul-2020
Publisher: Wiley
Citation: Horii, Y, Damjanović, M, Ajayakumar, MR, Katoh, K, Kitagawa, Y, Chibotaru, L, Ungur, L, Mas-Torrent, M, Wernsdorfer, W, Breedlove, BK, Enders, M, Veciana, J, Yamashita, M (2020-07-14). Highly Oxidized States of Phthalocyaninato Terbium(III) Multiple-Decker Complexes Showing Structural Deformations, Biradical Properties and Decreases in Magnetic Anisotropy. Chemistry - A European Journal 26 (39) : 8621-8630. ScholarBank@NUS Repository. https://doi.org/10.1002/chem.202001365
Abstract: Presented here is a comprehensive study of highly oxidized multiple-decker complexes composed of TbIII and CdII ions and two to five phthalocyaninato ligands, which are stabilized by electron-donating n-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 +4e charged species. From paramagnetic 1H 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 +2e charged 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.
Source Title: Chemistry - A European Journal
URI: https://scholarbank.nus.edu.sg/handle/10635/228895
ISSN: 09476539
15213765
DOI: 10.1002/chem.202001365
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