Publication detail

Measurement of Magnetic Exchange in Asymmetric Lanthanide Dimetallics: Toward a Transferable Theoretical Framework

Giansiracusa, MJ. Moreno-Pineda, E. Hussain, R. Marx, R. Prada, MM. Neugebauer, P. Al-Badran, S. Collison, D. Tuna, F. van Slageren, J. Carretta, S. Guidi, T. Mclnnes, EJL., Winpenny, REP. Chilton, NF

Original Title

Measurement of Magnetic Exchange in Asymmetric Lanthanide Dimetallics: Toward a Transferable Theoretical Framework

Type

journal article in Web of Science

Language

English

Original 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 modeled 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 and INS and far-IR measurements are all employed to further support the identification and modeling 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.

Authors

Giansiracusa, MJ.; Moreno-Pineda, E.; Hussain, R.; Marx, R.; Prada, MM.; Neugebauer, P.; Al-Badran, S.; Collison, D. ; Tuna, F.; van Slageren, J. ; Carretta, S. ; Guidi, T. ; Mclnnes, EJL., Winpenny, REP. ; Chilton, NF

Released

21. 2. 2018

ISBN

0002-7863

Periodical

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

Year of study

140

Number

7

State

United States of America

Pages from

2504

Pages to

2513

Pages count

10

BibTex

@article{BUT148084,
  author="Giansiracusa, MJ. and Moreno-Pineda, E. and Hussain, R. and Marx, R. and Prada, MM. and Neugebauer, P. and Al-Badran, S. and Collison, D. and Tuna, F. and van Slageren, J. and Carretta, S. and Guidi, T. and Mclnnes, EJL., Winpenny, REP. and Chilton, NF",
  title="Measurement of Magnetic Exchange in Asymmetric Lanthanide Dimetallics: Toward a Transferable Theoretical Framework",
  journal="JOURNAL OF THE AMERICAN CHEMICAL SOCIETY",
  year="2018",
  volume="140",
  number="7",
  pages="2504--2513",
  doi="10.1021/jacs.7b10714",
  issn="0002-7863"
}