Journal article
Lanthanoid-, Yttrium-, and Thorium-Centered Polyoxopalladates
Inorganic chemistry, Vol.64(25), pp.12658-12667
06/30/2025
DOI: 10.1021/acs.inorgchem.5c01282
PMID: 40505151
Abstract
Polyoxopalladates (POPs) are an extension of classic polyoxometalates. The two most frequently observed POP topologies are the nanostar (Pd15) and the cube (Pd12), where the heterometal cation in the central cavity may influence topology selection. Here, we crystallize ten lanthanoid-centered, phenylphosphonate-capped POPs (YIII, LaIII, CeIII, PrIII, NdIII, SmIII, EuIII, GdIII, YbIII, and LuIII) and one actinide-centered (ThIV) POP. Single-crystal X-ray analysis reveals that most LnIII favors the Pd15 nanostar, while Yb and Lu favor the Pd12 cube. Between Tb and Tm, no single-crystal growth occurred, challenging our initial hypothesis that topology selection was entirely based on the central metal cation size. Computation supported this hypothesis; the transition from Pd15 to Pd12 as the favored topology occurs in the third quarter of the lanthanide series. On the other hand, PXRD of all the crystallized/precipitated bulk materials suggested Pd15 is always the favored topology, and inspection of the lattices reveals that Pd15–Na interactions likely promote incipient crystallization, while no such interactions are seen in the Pd12 lattices. Electrospray ionization mass spectrometry confirmed the presence of both Pd12 and Pd15 for the smaller lanthanides (Yb), only Pd15 for the larger lanthanides (Ce), and no clusters were observed between Tb and Tm, where crystal growth was also challenging.
Details
- Title: Subtitle
- Lanthanoid-, Yttrium-, and Thorium-Centered Polyoxopalladates
- Creators
- Doctor Stephen - Oregon State UniversityAlexander Roseborough - Oregon State UniversityDhruba R Paudel - Department of Chemistry, University of Iowa, Iowa, Iowa 52240, United StatesPere Miro - University of IowaMay Nyman - Oregon State University
- Resource Type
- Journal article
- Publication Details
- Inorganic chemistry, Vol.64(25), pp.12658-12667
- DOI
- 10.1021/acs.inorgchem.5c01282
- PMID
- 40505151
- NLM abbreviation
- Inorg Chem
- ISSN
- 1520-510X
- eISSN
- 1520-510X
- Publisher
- American Chemical Society; WASHINGTON
- Grant note
- Basic Energy Sciences: DE-SC0023477 U.S. Department of Energy: SR-2017297 Murdock Charitable Trust
This work was performed at Oregon State University and the University of Iowa, supported by the U.S. Department of Energy under Grant # DE-SC0023477. The authors thank Dr. Lev N. Zakharov for assistance with SCXRD data. We also acknowledge the Murdock Charitable Trust (Grant SR-2017297) for the acquisition of the single-crystal X-ray diffractometer.
- Language
- English
- Electronic publication date
- 06/12/2025
- Date published
- 06/30/2025
- Academic Unit
- Chemistry
- Record Identifier
- 9984829020202771
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