Phase Transitions in Tetramethylammonium Hexachlorometalate Compounds (TMA)2MCl6 (M = U, Np, Pt, Sn, Hf, Zr)
Abstract
A study of the phase transitions occurring in tetramethylammonium hexachlorometalate compounds with M = U IV , Np IV , Zr IV , Sn IV , Hf IV , and Pt IV were performed using single‐crystal X‐ray diffraction across the temperature range 120–400 K. When the crystals are cooled, movement of the octahedral [MCl 6 ] 2– anions induces a phase transition from Fm 3 m to Fd 3 c with a doubling of the unit cell. For the actinide compounds, no correlation between the f‐electron configuration and the transition temperature was observed; instead, a correlation between the transition temperatures and both the [MCl 6 ] 2– anion and the TMA cation size is highlighted. Two phase transitions were observed and characterized. The first phase transition occurs with the ordering of the TMA cation and the second from a rotation of the [MCl 6 ] 2– octahedra. A third phase transition was observed at lower temperatures and was ascribed to a tetragonal distortion of the [MCl 6 ] 2– anions. Synthesis and study of the deuterated compounds did not show a significant isotope effect. Raman spectra of the protonated and deuterated compounds indicate only weak hydrogen bonding interactions between themore »
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1422404
- Alternate Identifier(s):
- OSTI ID: 1408148
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- European Journal of Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 2017; Journal Issue: 41; Journal ID: ISSN 1434-1948
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Phase transitions; Actinides; Structure elucidation; Raman spectroscopy
Citation Formats
Autillo, Matthieu, and Wilson, Richard E. Phase Transitions in Tetramethylammonium Hexachlorometalate Compounds (TMA)2MCl6 (M = U, Np, Pt, Sn, Hf, Zr). United States: N. p., 2017.
Web. doi:10.1002/ejic.201700764.
Autillo, Matthieu, & Wilson, Richard E. Phase Transitions in Tetramethylammonium Hexachlorometalate Compounds (TMA)2MCl6 (M = U, Np, Pt, Sn, Hf, Zr). United States. https://doi.org/10.1002/ejic.201700764
Autillo, Matthieu, and Wilson, Richard E. Fri .
"Phase Transitions in Tetramethylammonium Hexachlorometalate Compounds (TMA)2MCl6 (M = U, Np, Pt, Sn, Hf, Zr)". United States. https://doi.org/10.1002/ejic.201700764. https://www.osti.gov/servlets/purl/1422404.
@article{osti_1422404,
title = {Phase Transitions in Tetramethylammonium Hexachlorometalate Compounds (TMA)2MCl6 (M = U, Np, Pt, Sn, Hf, Zr)},
author = {Autillo, Matthieu and Wilson, Richard E.},
abstractNote = {A study of the phase transitions occurring in tetramethylammonium hexachlorometalate compounds with M = U IV , Np IV , Zr IV , Sn IV , Hf IV , and Pt IV were performed using single‐crystal X‐ray diffraction across the temperature range 120–400 K. When the crystals are cooled, movement of the octahedral [MCl 6 ] 2– anions induces a phase transition from Fm 3 m to Fd 3 c with a doubling of the unit cell. For the actinide compounds, no correlation between the f‐electron configuration and the transition temperature was observed; instead, a correlation between the transition temperatures and both the [MCl 6 ] 2– anion and the TMA cation size is highlighted. Two phase transitions were observed and characterized. The first phase transition occurs with the ordering of the TMA cation and the second from a rotation of the [MCl 6 ] 2– octahedra. A third phase transition was observed at lower temperatures and was ascribed to a tetragonal distortion of the [MCl 6 ] 2– anions. Synthesis and study of the deuterated compounds did not show a significant isotope effect. Raman spectra of the protonated and deuterated compounds indicate only weak hydrogen bonding interactions between the TMA cations and the [MCl 6 ] 2– octahedra.},
doi = {10.1002/ejic.201700764},
journal = {European Journal of Inorganic Chemistry},
number = 41,
volume = 2017,
place = {United States},
year = {Fri Sep 22 00:00:00 EDT 2017},
month = {Fri Sep 22 00:00:00 EDT 2017}
}
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