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Peer-reviewedCC BY 4.0Inorganic Chemistry

Oxidation State Effects on Decoherence in Isovalent 4f7 Complexes

  • Grant R. Wilkinson1
  • Manoj V. H. Subramanya2
  • Maximilian G. Bernbeck1
  • Kavipriya Thangavel2
  • Stephen Hill2,3,4
  • Henry S. La Pierre1,5,6
6 affiliations
  1. 1School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, United States
  2. 2National High Magnetic Field Laboratory, Florida State University, Tallahassee, Florida 32310, United States
  3. 3Department of Physics, Florida State University, Tallahassee, Florida 32306, United States
  4. 4Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States
  5. 5Nuclear and Radiological Engineering and Medical Physics Program, School of Mechanical Engineering, Georgia Institute of Technology, Atlanta Georgia 30332-0400, United States
  6. 6Physical Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99352, United States
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Abstract

The results of pulsed EPR measurements at W-band (94 GHz) on a series of isovalent 4f7 ions (Eu2+, Gd3+, Tb4+) are presented, constituting the first example to date of pulsed EPR on molecular Tb4+. An inverse correlation is found between the 5 K phase memory relaxation times (T m) and the degree of zero-field splitting (ZFS) in these complexes. This observation reveals the role of ZFS as an effective reporter not only of structural distortions away from ideal cubic symmetry, but also of the overall electronic structure changes wrought by chemical oxidation, which undermine the seemingly advantageous increases in excited state energies and metal–ligand covalency across the series. Building upon previous studies of the physical properties of high oxidation state lanthanide complexes, these results further highlight the necessity for detailed electronic structure–property relationship studies to fully map the electronic consequences of chemical oxidation in the lanthanides.

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Cite

BibTeXRIS
BibTeX
@article{wilkinson2026oxidation,
  title = {{Oxidation State Effects on Decoherence in Isovalent 4f7 Complexes}},
  author = {Grant R. Wilkinson and Manoj V. H. Subramanya and Maximilian G. Bernbeck and Kavipriya Thangavel and Stephen Hill and Henry S. La Pierre},
  journal = {Inorganic Chemistry},
  year = {2026},
  month = oct,
  doi = {10.1021/acs.inorgchem.6c04187},
  url = {https://doi.org/10.1021/acs.inorgchem.6c04187},
  note = {CC BY 4.0},
}
RIS
TY  - JOUR
TI  - Oxidation State Effects on Decoherence in Isovalent 4f7 Complexes
AU  - Grant R. Wilkinson
AU  - Manoj V. H. Subramanya
AU  - Maximilian G. Bernbeck
AU  - Kavipriya Thangavel
AU  - Stephen Hill
AU  - Henry S. La Pierre
PY  - 2026
DA  - 2026/10/08
JO  - Inorganic Chemistry
DO  - 10.1021/acs.inorgchem.6c04187
UR  - https://doi.org/10.1021/acs.inorgchem.6c04187
AB  - The results of pulsed EPR measurements at W-band (94 GHz) on a series of isovalent 4f7 ions (Eu2+, Gd3+, Tb4+) are presented, constituting the first example to date of pulsed EPR on molecular Tb4+. An inverse correlation is found between the 5 K phase memory relaxation times (T m) and the degree of zero-field splitting (ZFS) in these complexes. This observation reveals the role of ZFS as an effective reporter not only of structural distortions away from ideal cubic symmetry, but also of the overall electronic structure changes wrought by chemical oxidation, which undermine the seemingly advantageous increases in excited state energies and metal–ligand covalency across the series. Building upon previous studies of the physical properties of high oxidation state lanthanide complexes, these results further highlight the necessity for detailed electronic structure–property relationship studies to fully map the electronic consequences of chemical oxidation in the lanthanides.
SN  - 0020-1669
SN  - 1520-510X
ER  -