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

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, Masahiro Yamashita

Research output: Contribution to journalArticlepeer-review

3 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)8621-8630
Number of pages10
JournalChemistry - A European Journal
Volume26
Issue number39
DOIs
Publication statusPublished - 2020 Jul 14
Externally publishedYes

Keywords

  • NMR
  • biradical
  • crystal engineering
  • magnetic anisotropy
  • redox

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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