Phase Transitions in Tetramethylammonium Hexachlorometalate Compounds (TMA)2MCl6 (M = U, Np, Pt, Sn, Hf, Zr)

Autillo, Matthieu; Wilson, Richard E.

doi:10.1002/ejic.201700764

Title: Phase Transitions in Tetramethylammonium Hexachlorometalate Compounds (TMA)₂MCl₆ (M = U, Np, Pt, Sn, Hf, Zr)

Journal Article · Fri Sep 22 00:00:00 EDT 2017 · European Journal of Inorganic Chemistry

DOI:https://doi.org/10.1002/ejic.201700764· OSTI ID:1422404

Autillo, Matthieu ^[1];

^[1]

Argonne National Lab. (ANL), Argonne, IL (United States)

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.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

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

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1422404

Alternate ID(s):: OSTI ID: 1408148

Journal Information:: European Journal of Inorganic Chemistry, Vol. 2017, Issue 41; ISSN 1434-1948

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 13 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Phase transitions
Actinides
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CCDC 1879017: Experimental Crystal Structure Determination Matthieu, Autillo,; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2128gw The current record is supplemented by this dataset	dataset	January 2019
CCDC 1879018: Experimental Crystal Structure Determination Matthieu, Autillo,; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2128hx The current record is supplemented by this dataset	dataset	January 2019
CCDC 1879019: Experimental Crystal Structure Determination Matthieu, Autillo,; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2128jy The current record is supplemented by this dataset	dataset	January 2019
CCDC 1879020: Experimental Crystal Structure Determination Matthieu, Autillo,; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2128kz The current record is supplemented by this dataset	dataset	January 2019
CCDC 1879021: Experimental Crystal Structure Determination Matthieu, Autillo,; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2128l0 The current record is supplemented by this dataset	dataset	January 2019
CCDC 1879022: Experimental Crystal Structure Determination Matthieu, Autillo,; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2128m1 The current record is supplemented by this dataset	dataset	January 2019
CCDC 1879023: Experimental Crystal Structure Determination Matthieu, Autillo,; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2128n2 The current record is supplemented by this dataset	dataset	January 2019
CCDC 1879024: Experimental Crystal Structure Determination Matthieu, Autillo,; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2128p3 The current record is supplemented by this dataset	dataset	January 2019
CCDC 1879025: Experimental Crystal Structure Determination Matthieu, Autillo,; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2128q4 The current record is supplemented by this dataset	dataset	January 2019
CCDC 1879026: Experimental Crystal Structure Determination Matthieu, Autillo,; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2128r5 The current record is supplemented by this dataset	dataset	January 2019
CCDC 1879027: Experimental Crystal Structure Determination Matthieu, Autillo,; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2128s6 The current record is supplemented by this dataset	dataset	January 2019
CCDC 1879028: Experimental Crystal Structure Determination Matthieu, Autillo,; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2128t7 The current record is supplemented by this dataset	dataset	January 2019
CCDC 1879029: Experimental Crystal Structure Determination Matthieu, Autillo,; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2128v8 The current record is supplemented by this dataset	dataset	January 2019
CCDC 1879033: Experimental Crystal Structure Determination Matthieu, Autillo,; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2128zd The current record is supplemented by this dataset	dataset	January 2019
CCDC 1879034: Experimental Crystal Structure Determination Matthieu, Autillo,; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc21290g The current record is supplemented by this dataset	dataset	January 2019
CCDC 1879035: Experimental Crystal Structure Determination Matthieu, Autillo,; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc21291h The current record is supplemented by this dataset	dataset	January 2019
CCDC 1879036: Experimental Crystal Structure Determination Matthieu, Autillo,; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc21292j The current record is supplemented by this dataset	dataset	January 2019
CCDC 1879037: Experimental Crystal Structure Determination Matthieu, Autillo,; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc21293k The current record is supplemented by this dataset	dataset	January 2019

Title: Phase Transitions in Tetramethylammonium Hexachlorometalate Compounds (TMA)2MCl6 (M = U, Np, Pt, Sn, Hf, Zr)

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Title: Phase Transitions in Tetramethylammonium Hexachlorometalate Compounds (TMA)₂MCl₆ (M = U, Np, Pt, Sn, Hf, Zr)