Periodicity of Single-Molecule Magnet Behaviour of Heterotetranuclear Lanthanide Complexes across the Lanthanide Series: A Compendium

David Chukwuma Izuogu, Takefumi Yoshida, Goulven Cosquer, Jonnie N. Asegbeloyin, Haitao Zhang, Alex J.W. Thom, Masahiro Yamashita

Research output: Contribution to journalArticlepeer-review

1 Citation (Scopus)

Abstract

Acetato-bridged palladium–lanthanide tetranuclear heterometallic complexes of the form [Pd2Ln2(H2O)2(CH3COO)10]⋅2 CH3COOH [Ln2=Ce2 (1), Pr2 (2), Nd2 (3), Sm2 (4), Tb2 (5), Dy2 (6), Dy0.2Y1.8 (6′′), Ho2 (7), Er2 (8), Er0.24Y1.7 (8′′), Tm2 (9), Yb2 (10), Y2(11)] were synthesised and characterised by experimental and theoretical techniques. All complexes containing Kramers lanthanide ions [Ln3+=Ce (1), Nd (3), Sm (4), Dy (6), DyY (6′′), Er (8), ErY (8′′), Yb (10)] showed field-induced slow magnetic relaxation, characteristic of single-molecule magnetism and purely of molecular origin. In contrast, all non-Kramers lanthanide ions [Ln3+=Pr (2), Tb (5), Ho (7), Tm (9), Y3+ (11) is diamagnetic and non-lanthanide] did not show any slow magnetic relaxation. The variation in the electronic structure and accompanying consequences across the complexes representing all Kramers and non-Kramers lanthanide ions were investigated. The origin of the magnetic properties and the extent to which the axial donor–acceptor interaction involving the lanthanide ions and an electron-deficient dz2 orbital of palladium affects the observed magnetic and electronic properties across the lanthanide series are presented. Unique consistent electronic and magnetic properties of isostructural complexes spanning the lanthanide series with properties dependent on whether the ions are Kramers or non-Kramers are reported.

Original languageEnglish
Pages (from-to)6036-6049
Number of pages14
JournalChemistry - A European Journal
Volume26
Issue number27
DOIs
Publication statusPublished - 2020 May 12

Keywords

  • electronic structure
  • heterometallic complexes
  • lanthanides
  • magnetic properties
  • palladium
  • single-molecule magnets

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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