Journal article
Lanthanide Differentiation using Acetylacetonate: Insights into the Solution Speciation and Crystallization Behavior of Homo‐ and Heterometal Complexes
European journal of inorganic chemistry, Vol.28(16), e202500171
06/05/2025
DOI: 10.1002/ejic.202500171
Abstract
The lanthanides form a chemically cohesive series, and identifying differences that can be leveraged to separate near neighbors remains an ongoing need. Here, the synthesis, structural chemistry, and spectroscopic properties of a neodymium‐acetylacetonate monomer, [Nd(acac)3(H2O)2] (Nd‐1), and an acac‐bridged Nd‐dimer, [Nd2(acac)6(H2O)2] (Nd‐2), are described. Interestingly, the Nd dimer readily precipitated from solution; however, efforts to the crystallize the Dy analog using the same synthetic approach were unsuccessful. Yet heterometal dimers, [Nd2‐xDyx(acac)6(H2O)2] (NdDy‐2), could be prepared from mixed metal solutions. To understand these differences in crystallization behavior of Nd‐ and Dy‐acac complexes, the solution speciation of Ln‐acac systems was examined using nano‐electrospray ionization mass spectrometry (nESI‐MS). Both homometal and heterometal solutions were prepared (Ln = Nd, Dy, Nd/Dy). nESI‐MS showed the presence of homometallic dimeric species for Nd and Dy and peaks consistent with both homo‐ and heterometallic complexes in mixed metal solutions. Density functional theory was used to further understand intrinsic differences in nucleation energetics in dimeric homo‐ and heterometallic species. Overall, this work provides fundamental insight into the correlation between solution‐ and solid‐state structural units and differences in the crystallization behavior of Ln complexes; the latter is particularly relevant to separating metal ions with otherwise very similar chemical behavior.
Details
- Title: Subtitle
- Lanthanide Differentiation using Acetylacetonate: Insights into the Solution Speciation and Crystallization Behavior of Homo‐ and Heterometal Complexes
- Creators
- Morgan A. McDonald - Georgetown UniversityFrenio A. Redeker - Georgetown UniversityPaschal Akubuiro - University of South DakotaPere Miró - University of IowaJeffery A. Bertke - Georgetown UniversityKaveh Jorabchi - Georgetown UniversityKarah E. Knope - Georgetown University
- Resource Type
- Journal article
- Publication Details
- European journal of inorganic chemistry, Vol.28(16), e202500171
- DOI
- 10.1002/ejic.202500171
- ISSN
- 1434-1948
- eISSN
- 1099-0682
- Publisher
- WILEY-V C H VERLAG GMBH
- Grant note
- U.S. Department of Energy: DE-SC0023477 US Department of Energy
This work was supported by the US Department of Energy under Award DE-SC0023477. Additionally, we acknowledge seed funding from a Georgetown University Earth Commons EcoImpact Award (2022) that helped support the nESI-MS studies. We thank Lulio Sanz for his assistance in optical absorption spectroscopy data collection. We also thank Gunjan Gupta for her design of the TOC.
- Language
- English
- Electronic publication date
- 05/16/2025
- Date published
- 06/05/2025
- Academic Unit
- Chemistry
- Record Identifier
- 9984824329602771
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