Long-Range Ferromagnetic Exchange Interactions Mediated by Mn–CeIV–Mn Superexchange Involving Empty 4f Orbitals

  • Sayak Das Gupta
    Sayak Das Gupta
    Department of Chemistry, University of Florida, Gainesville, Florida 32611, United States
  • Robert L. Stewart
    Robert L. Stewart
    National High Magnetic Field Laboratory and Department of Physics, Florida State University, Tallahassee, Florida 32310, United States
  • Dian-Teng Chen
    Dian-Teng Chen
    Department of Physics, University of Florida, Gainesville, Florida 32611, United States
  • Khalil A. Abboud
    Khalil A. Abboud
    Department of Chemistry, University of Florida, Gainesville, Florida 32611, United States
  • Hai-Ping Cheng
    Hai-Ping Cheng
    Department of Physics, University of Florida, Gainesville, Florida 32611, United States
  • Stephen Hill
    Stephen Hill
    National High Magnetic Field Laboratory and Department of Physics, Florida State University, Tallahassee, Florida 32310, United States
    More by Stephen Hill
  • , and 
  • George Christou*
    George Christou
    Department of Chemistry, University of Florida, Gainesville, Florida 32611, United States
    *E-mail: [email protected]
Cite this: Inorg. Chem. 2020, 59, 13, 8716–8726
Publication Date (Web):June 23, 2020
https://doi.org/10.1021/acs.inorgchem.0c00332
Copyright © 2020 American Chemical Society
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Abstract

Reactions involving reductive aggregation of MnO4 in methanol in the presence of CeIV and an excess of carboxylic acid have led to the synthesis of structurally related Ce/Mn clusters, [Ce3Mn5O8(OMe)(O2CBut)13(MeOH)] (1) and [Ce2Mn3O5(O2CPh)9(MeOH)3] (2), containing at least one {Mn2Ce2O4} cubane unit. The cores of both clusters contain Mnx units separated by three (1) or two (2) CeIV ions. Fits of variable-temperature, solid-state dc and ac magnetic susceptibility data reveal dominant ferromagnetic interactions within 1 and 2, resulting in the maximum S = 17/2 and S = 5 ground state spins, respectively, and thus suggesting significant ferromagnetic (F) interactions between the Mnx units that are ≥6 Å apart and separated by four intervening bonds through diamagnetic CeIV. Fits of magnetic susceptibility data also revealed unusual long-range F interactions, and this finding was further supported by high-field EPR measurements and simulations. Density functional theory calculations and a Wannier function analysis confirm long-range interactions and indicate a Mn–Ce–Mn superexchange pathway via Mn-d/Ce-f orbital overlap/hybridization

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  • Tables of selected bond distances and angles, bond valence sums, magnetic data (reduced magnetization plots and error surfaces), HFEPR data and PDOS plots for 1 and 2 (PDF)

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Cited By


This article is cited by 4 publications.

  1. Dian-Teng Chen, Jia Chen, Xiang-Guo Li, George Christou, Stephen Hill, Xiao-Guang Zhang, Hai-Ping Cheng. Long-Range Magnetic Exchange Pathways in Complex Clusters from First Principles. The Journal of Physical Chemistry C 2021, 125 (20) , 11124-11131. https://doi.org/10.1021/acs.jpcc.1c00706
  2. Li Tang, Xi Kang, Xiangyu Wang, Xianhui Zhang, Xun Yuan, Shuxin Wang. Dynamic Metal Exchange between a Metalloid Silver Cluster and Silver(I) Thiolate. Inorganic Chemistry 2021, 60 (5) , 3037-3045. https://doi.org/10.1021/acs.inorgchem.0c03269
  3. Linh Pham, Thai Son Cao, Khalil A. Abboud, George Christou. New family of Ln9Mn4 (Ln = Gd, Tb, Dy) and Y9Mn4 clusters from the use of methyl-2-pyridyl-ketone oxime in heterometallic Mn chemistry. Polyhedron 2021, 209 , 115462. https://doi.org/10.1016/j.poly.2021.115462
  4. Ashlyn R. Hale, Philippa King, Khalil A. Abboud, George Christou. Unusual Mn5 cluster with a ‘twisted bow-tie’ topology and MnIIMnIII2MnIV2 oxidation states: Synthesis, structure, and magnetic properties. Polyhedron 2021, 200 , 115141. https://doi.org/10.1016/j.poly.2021.115141