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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 |
Appears in Collections: | Staff Publications Elements |
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Yamashita_CEJ_2020.pdf | Published version | 3.15 MB | Adobe PDF | OPEN | Published | View/Download |
Yamashita_CEJ_2020_ESI.pdf | Supporting information | 15.79 MB | Adobe PDF | OPEN | Published | View/Download |
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