Measurement of magnetic exchange in asymmetric lanthanide dimetallics: towards a transferable theoretical framework

Research output: Contribution to journalArticle

  • External authors:
  • Marcus Giansiracusa
  • Eufemio Moreno Pineda
  • Riaz Hussain
  • Raphael Marx
  • Maria Martinez Prada
  • Petr Neugebauer
  • Susan Al-Badran
  • David Collison
  • Joris Van Slageren
  • Stefano Carretta
  • Tatiana Guidi

Abstract

Magnetic exchange interactions within the asymmetric dimetallic compounds [hqH2][Ln2(hq)4(NO3)3]∙MeOH, (Ln = Er(III) and Yb(III), hqH = 8-hydroxyquinoline) have been directly probed with EPR spectroscopy and accurately modelled by spin Hamiltonian techniques. Exploitation of site selectivity via doping experiments in Y(III) and Lu(III) matrices yields simple EPR spectra corresponding to isolated Kramers doublets, allowing determination of the local magnetic properties of the individual sites within the dimetallic compounds. CASSCF-SO calculations, INS and far-IR measurements are all employed to further support the identification and modelling of the local electronic structure for each site. EPR spectra of the pure dimetallic compounds are highly featured and correspond to transitions within the lowest-lying exchange-coupled manifold, permitting determination of the highly anisotropic magnetic exchange between the lanthanide ions. We find a unique orientation for the exchange interaction, corresponding to a common elongated oxygen bridge for both isostructural analogs. This suggests a microscopic physical connection to the magnetic superexchange. These results are of fundamental importance for building and validating model microscopic Hamiltonians to understand the origins of magnetic interactions between lanthanides and how they may be controlled with chemistry

Bibliographical metadata

Original languageEnglish
JournalAmerican Chemical Society. Journal
Early online date26 Jan 2018
DOIs
Publication statusPublished - 2018

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