Journal article
Delineating the Effects of Counterions on the Structural and Vibrational Properties of U(IV) Lindqvist Polyoxometalate Complexes
Inorganic chemistry, Vol.64(23), pp.11380-11397
05/30/2025
DOI: 10.1021/acs.inorgchem.5c00033
PMCID: PMC12175120
PMID: 40445109
Appears in UI Libraries Support Open Access
Abstract
Herein we conducted a full investigation into the fundamental structural and vibrational properties of uranium(IV) Peacock–Weakley-type lacunary Lindqvist (W10) polyoxometalate (POM) complexes. We recently demonstrated the importance of the secondary lattice elements in tuning the distortion of the D4d symmetry in W10 POM complexes, and here, we synthesized eight UW10 complexes with different alkali metal counterions and evaluated how the composition and packing of counterion species affected complex structural and vibrational properties. Single-crystal X-ray diffraction analysis on complexes 1–8 revealed changes in structural distortion parameters as a function of differences in counterion configurations, while far-infrared and Raman spectra for 1–8 also demonstrated that vibrational mode frequencies were sensitive to changes in counterion composition and packing. To more effectively compare different counterion configurations, we developed counterion effective ionic radius (eIR) as a new structural parameter, and comparisons between structural distortion parameters and eIR values strongly suggested that modulation by the secondary lattice elements can affect structural and vibrational manifolds within POM complexes. Partial least squares (PLS) analysis was used to quantitatively evaluate correlations observed within this investigation, and PLS statistical models showed a strong correlation between counterion eIR and both structural distortion parameters and vibrational mode frequencies.
Details
- Title: Subtitle
- Delineating the Effects of Counterions on the Structural and Vibrational Properties of U(IV) Lindqvist Polyoxometalate Complexes
- Creators
- Primadi J Subintoro - University of IowaKorey P Carter - University of Iowa
- Resource Type
- Journal article
- Publication Details
- Inorganic chemistry, Vol.64(23), pp.11380-11397
- DOI
- 10.1021/acs.inorgchem.5c00033
- PMID
- 40445109
- PMCID
- PMC12175120
- NLM abbreviation
- Inorg Chem
- ISSN
- 1520-510X
- eISSN
- 1520-510X
- Publisher
- American Chemical Society
- Copyright
- Copyright © 2025 The Authors
- Grant note
- Basic Energy Sciences: DE-SC0024035 U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Early Career Research Program: CHE-1828117, NRC 31310018M0042 University of Iowa Materials, Analysis, Testing - NSF Award
This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Early Career Research Program under Award DE-SC0024035. We acknowledge the University of Iowa Materials, Analysis, Testing, and Fabrication Facility for use of single-crystal and powder X-ray diffractometers as well as the Raman microscope used in this study. Single-crystal XRD data was collected on an instrument funded by NSF Award CHE-1828117. Mid- and far-IR spectra were collected on an instrument funded by a Nuclear Regulatory Commission Faculty Development Grant (NRC 31310018M0042).
- Language
- English
- Date published
- 05/30/2025
- Academic Unit
- Chemistry
- Record Identifier
- 9984825636402771
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