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

doi:10.1002/chem.202000161

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

Chemistry. 2020 May 12;26(27):6036-6049. doi: 10.1002/chem.202000161. Epub 2020 Apr 28.

Authors

David Chukwuma Izuogu^{1

2

3}, Takefumi Yoshida^{2

4}, Goulven Cosquer⁵, Jonnie N Asegbeloyin³, Haitao Zhang², Alex J W Thom¹, Masahiro Yamashita^{2

4

6}

Affiliations

¹ Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK.
² Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aza-Aoba, Aramaki, Sendai, 980-8578, Japan.
³ Department of Pure and Industrial Chemistry, University of Nigeria, Nsukka, 410001, Enugu State, Nigeria.
⁴ WPI-Advanced Institute for Materials Research (AIMR), Tohoku University, 2-1-1 Katahira, Sendai, 980-8577, Japan.
⁵ Department of Chemistry, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashihiroshima, 739-8526, Japan.
⁶ School of Materials Science and Engineering, Nankai University, Tianjin, 300350, P.R. China.

PMID: 32045039
DOI: 10.1002/chem.202000161

Abstract

Acetato-bridged palladium-lanthanide tetranuclear heterometallic complexes of the form [Pd₂ Ln₂ (H₂ O)₂ (CH₃ COO)₁₀ ]⋅2 CH₃ COOH [Ln₂ =Ce₂ (1), Pr₂ (2), Nd₂ (3), Sm₂ (4), Tb₂ (5), Dy₂ (6), Dy_0.2 Y_1.8 (6''), Ho₂ (7), Er₂ (8), Er_0.24 Y_1.7 (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 $d_{z^{2}}$ 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.

Keywords: electronic structure; heterometallic complexes; lanthanides; magnetic properties; palladium; single-molecule magnets.

Abstract

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