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

Horii, Yoji; Damjanović, Marko; Ajayakumar, M. R.; Katoh, Keiichi; Kitagawa, Yasutaka; Chibotaru, Liviu; Ungur, Liviu; Mas‐Torrent, Marta; Wernsdorfer, Wolfgang; Breedlove, Brian K.; Enders, Markus; Veciana, Jaume; Yamashita, Masahiro

Abstract:
Presented here is a comprehensive study of highly oxidized multiple‐decker complexes composed of Tb$_{III}$ and Cd$_{III}$ 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 $^{1}$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 +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.

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Verlagsausgabe §
DOI: 10.5445/IR/1000124816
Veröffentlicht am 19.10.2020
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Nanotechnologie (INT)
Publikationstyp Zeitschriftenaufsatz
Publikationsmonat/-jahr 07.2020
Sprache Englisch
Identifikator ISSN: 0947-6539, 1521-3765
KITopen-ID: 1000124816
Erschienen in Chemistry - a European journal
Band 26
Heft 39
Seiten 8621–8630
Vorab online veröffentlicht am 18.06.2020
Nachgewiesen in Scopus
Web of Science
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