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Updated: Dec 21, 2025
The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Highly Oxidized States of Phthalocyaninato Terbium(III) Multiple-Decker Complexes Showing Structural Deformations,
Yoji Horii1, Marko Damjanović2,3, M R Ajayakumar4
1Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba Aoba-ku, Sendai, Miyagi, 980-8578, Japan.
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 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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