Light- and Chemical-Doping-Induced Magnetic Behavior of Eu Molecular Systems

Tijana Rajh, Eric Masson, Kyaw Zin Latt, Ashton Smith, Alexander M. Brugh, Naveen Dandu, Daniel Trainer, Larry A. Curtiss, Anh T. Ngo, Saw Wai Hla

Research output: Contribution to journalArticlepeer-review

1 Scopus citations


Variable temperature electron paramagnetic resonance (VT-EPR) was used to investigate the role of the environment and oxidation states of several coordinated Eu compounds. We find that while Eu(III) chelating complexes are diamagnetic, simple chemical reduction results in the formation of paramagnetic species. In agreement with the distorted D3h symmetry of Eu molecular complexes investigated in this study, the EPR spectrum of reduced complexes showed axially symmetric signals (g = 2.001 and g = 1.994) that were successfully simulated with two Eu isotopes with nuclear spin 5/2 (151Eu and 153Eu with 48% and 52% natural abundance, respectively) and nuclear g-factors 151Eu/153Eu = 2.27. Illumination of water-soluble complex Eu(dipic)3 at 4 K led to the ligand-to-metal charge transfer (LMCT) that resulted in the formation of Eu(II) in a rhombic environment (gx = 2.006, gy = 1.995, gz = 1.988). The existence of LMCT affects the luminescence of Eu(dipic)3, and pre-reduction of the complex to Eu(II)(dipic)3 reversibly reduces red luminescence with the appearance of a weak CT blue luminescence. Furthermore, encapsulation of a large portion of the dipic ligand with Cucurbit[7]uril, a pumpkin-shaped macrocycle, inhibited ligand-to-metal charge transfer, preventing the formation of Eu(II) upon illumination.

Original languageEnglish (US)
Pages (from-to)12721-12729
Number of pages9
JournalInorganic chemistry
Issue number32
StatePublished - Aug 14 2023
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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