Determining the Effects of Zero-Field Splitting and Magnetic Exchange in Dimeric Europium(II) Complexes

Carpenter, Stephanie H.; Mengell, Joshua; Chen, Ju; Jones, Margaret R.; Kirk, Martin L.; Tondreau, Aaron M.

doi:10.1021/acs.inorgchem.4c00694

Title: Determining the Effects of Zero-Field Splitting and Magnetic Exchange in Dimeric Europium(II) Complexes

Journal Article · 25 April 2024 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.4c00694 · OSTI ID:2475577

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Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Univ. of New Mexico, Albuquerque, NM (United States)

Related BAP [BAP = bis(acyl)phosphide] and Acac (Acac = β-diketonate) molecules perform as robust supports for both lanthanide and actinide metals. Here, a molecular bimetallic Eu²⁺ complex was successfully targeted and isolated by employing sodium bis(mesitoyl)phosphide [Na(^mesBAP)] in a salt metathesis with EuI₂, producing [Eu(^mesBAP)₂(et₂o)]₂ (et₂o = metal-coordinated diethyl ether). The corresponding Acac-Eu²⁺ complex was targeted using ^mesAcac– (1,3-dimesityl-1,3-propanedione), generating [Eu(^mesAcac)₂(et₂o)]₂. Both complexes were characterized by single-crystal X-ray diffraction, UV–vis, IR, and NMR spectroscopies, and variable-temperature magnetic susceptibility. [Eu(^mesBAP)₂(et₂o)]₂ was persistent under anaerobic, anhydrous conditions, whereas the analogous [Eu(^mesAcac)₂(et₂o)]₂ showed evidence of decomposition under identical conditions. Finally, variable-temperature magnetic susceptibility and magnetization studies of [Eu(^mesBAP)₂(et₂o)]₂ and [Eu(^mesAcac)₂(et₂o)]₂ were performed, resulting in similar magnetic exchange coupling values of J_ex = –0.018 and –0.023 cm^–1 and axial zero-field-splitting D values of –0.38 and –0.51 cm^–1, respectively.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 2475577

Report Number(s):: LA-UR--23-20279

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 19 Vol. 63; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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europium magnetism
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ligands
magnetic properties
quantum mechanics

CCDC 2245753: Experimental Crystal Structure Determination H., Carpenter, Stephanie; Joshua, Mengell,; Ju, Chen, https://doi.org/10.5517/ccdc.csd.cc2fcwnc The current record is supplemented by this dataset	dataset	January 2024
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Title: Determining the Effects of Zero-Field Splitting and Magnetic Exchange in Dimeric Europium(II) Complexes

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