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Highly oxidized States of Phthalocyaninato Terbium(III) Multiple-Decker Complexes Showing Structural Deformations, Biradical Properties and Decreases in Magnetic Anisotropy

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 l...

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Hauptverfasser: Horii, Yoji (VerfasserIn) , Damjanović, Marko (VerfasserIn) , Ajayakumar, M. R. (VerfasserIn) , Katoh, Keiichi (VerfasserIn) , Kitagawa, Yasutaka (VerfasserIn) , Chibotaru, Liviu (VerfasserIn) , Ungur, Liviu (VerfasserIn) , Mas-Torrent, Marta (VerfasserIn) , Wernsdorfer, Wolfgang (VerfasserIn) , Breedlove, Brian K. (VerfasserIn) , Enders, Markus (VerfasserIn) , Veciana, Jaume (VerfasserIn) , Yamashita, Masahiro (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: 2020
In: Chemistry - a European journal
Year: 2020, Jahrgang: 26, Heft: 39, Pages: 8621-8630
ISSN:1521-3765
DOI:10.1002/chem.202001365
Online-Zugang:Verlag, kostenfrei, Volltext: https://doi.org/10.1002/chem.202001365
Verlag, kostenfrei, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.202001365
Volltext
Verfasserangaben:Yoji Horii, Marko Damjanović, M.R. Ajayakumar, Keiichi Katoh, Yasutaka Kitagawa, Liviu Chibotaru, Liviu Ungur, Marta Mas-Torrent, Wolfgang Wernsdorfer, Brian K. Breedlove, Markus Enders, Jaume Veciana, and Masahiro Yamashita
Beschreibung
Zusammenfassung: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.
Beschreibung:First published: 19 May 2020
Gesehen am 05.11.2021
Beschreibung:Online Resource
ISSN:1521-3765
DOI:10.1002/chem.202001365

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