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Observation of a re-entrant phase transition in the molecular complex tris(μ(2)-3,5-diisopropyl-1,2,4-triazolato-κ(2) N (1):N (2))trigold(I) under high pressure
We report a molecular crystal that exhibits four successive phase transitions under hydrostatic pressure, driven by aurophilic interactions, with the ground-state structure re-emerging at high pressure. The effect of pressure on two polytypes of tris(μ(2)-3,5-diisopropyl-1,2,4-triazolato-κ(2) N (1...
Autores principales: | , , , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
International Union of Crystallography
2016
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5391858/ https://www.ncbi.nlm.nih.gov/pubmed/28461897 http://dx.doi.org/10.1107/S2052252516013129 |
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author | Woodall, Christopher H. Christensen, Jeppe Skelton, Jonathan M. Hatcher, Lauren E. Parlett, Andrew Raithby, Paul R. Walsh, Aron Parker, Stephen C. Beavers, Christine M. Teat, Simon J. Intissar, Mourad Reber, Christian Allan, David R. |
author_facet | Woodall, Christopher H. Christensen, Jeppe Skelton, Jonathan M. Hatcher, Lauren E. Parlett, Andrew Raithby, Paul R. Walsh, Aron Parker, Stephen C. Beavers, Christine M. Teat, Simon J. Intissar, Mourad Reber, Christian Allan, David R. |
author_sort | Woodall, Christopher H. |
collection | PubMed |
description | We report a molecular crystal that exhibits four successive phase transitions under hydrostatic pressure, driven by aurophilic interactions, with the ground-state structure re-emerging at high pressure. The effect of pressure on two polytypes of tris(μ(2)-3,5-diisopropyl-1,2,4-triazolato-κ(2) N (1):N (2))trigold(I) (denoted Form-I and Form-II) has been analysed using luminescence spectroscopy, single-crystal X-ray diffraction and first-principles computation. A unique phase behaviour was observed in Form-I, with a complex sequence of phase transitions between 1 and 3.5 GPa. The ambient C2/c mother cell transforms to a P2(1)/n phase above 1 GPa, followed by a P2(1)/a phase above 2 GPa and a large-volume C2/c supercell at 2.70 GPa, with the previously observed P2(1)/n phase then reappearing at higher pressure. The observation of crystallographically identical low- and high-pressure P2(1)/n phases makes this a rare example of a re-entrant phase transformation. The phase behaviour has been characterized using detailed crystallographic theory and modelling, and rationalized in terms of molecular structural distortions. The dramatic changes in conformation are correlated with shifts of the luminescence maxima, from a band maximum at 14040 cm(−1) at 2.40 GPa, decreasing steeply to 13550 cm(−1) at 3 GPa. A similar study of Form-II displays more conventional crystallographic behaviour, indicating that the complex behaviour observed in Form-I is likely to be a direct consequence of the differences in crystal packing between the two polytypes. |
format | Online Article Text |
id | pubmed-5391858 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2016 |
publisher | International Union of Crystallography |
record_format | MEDLINE/PubMed |
spelling | pubmed-53918582017-05-01 Observation of a re-entrant phase transition in the molecular complex tris(μ(2)-3,5-diisopropyl-1,2,4-triazolato-κ(2) N (1):N (2))trigold(I) under high pressure Woodall, Christopher H. Christensen, Jeppe Skelton, Jonathan M. Hatcher, Lauren E. Parlett, Andrew Raithby, Paul R. Walsh, Aron Parker, Stephen C. Beavers, Christine M. Teat, Simon J. Intissar, Mourad Reber, Christian Allan, David R. IUCrJ Research Papers We report a molecular crystal that exhibits four successive phase transitions under hydrostatic pressure, driven by aurophilic interactions, with the ground-state structure re-emerging at high pressure. The effect of pressure on two polytypes of tris(μ(2)-3,5-diisopropyl-1,2,4-triazolato-κ(2) N (1):N (2))trigold(I) (denoted Form-I and Form-II) has been analysed using luminescence spectroscopy, single-crystal X-ray diffraction and first-principles computation. A unique phase behaviour was observed in Form-I, with a complex sequence of phase transitions between 1 and 3.5 GPa. The ambient C2/c mother cell transforms to a P2(1)/n phase above 1 GPa, followed by a P2(1)/a phase above 2 GPa and a large-volume C2/c supercell at 2.70 GPa, with the previously observed P2(1)/n phase then reappearing at higher pressure. The observation of crystallographically identical low- and high-pressure P2(1)/n phases makes this a rare example of a re-entrant phase transformation. The phase behaviour has been characterized using detailed crystallographic theory and modelling, and rationalized in terms of molecular structural distortions. The dramatic changes in conformation are correlated with shifts of the luminescence maxima, from a band maximum at 14040 cm(−1) at 2.40 GPa, decreasing steeply to 13550 cm(−1) at 3 GPa. A similar study of Form-II displays more conventional crystallographic behaviour, indicating that the complex behaviour observed in Form-I is likely to be a direct consequence of the differences in crystal packing between the two polytypes. International Union of Crystallography 2016-08-18 /pmc/articles/PMC5391858/ /pubmed/28461897 http://dx.doi.org/10.1107/S2052252516013129 Text en © Christopher H. Woodall et al. 2016 http://creativecommons.org/licenses/by/2.0/uk/ This is an open-access article distributed under the terms of the Creative Commons Attribution Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited. |
spellingShingle | Research Papers Woodall, Christopher H. Christensen, Jeppe Skelton, Jonathan M. Hatcher, Lauren E. Parlett, Andrew Raithby, Paul R. Walsh, Aron Parker, Stephen C. Beavers, Christine M. Teat, Simon J. Intissar, Mourad Reber, Christian Allan, David R. Observation of a re-entrant phase transition in the molecular complex tris(μ(2)-3,5-diisopropyl-1,2,4-triazolato-κ(2) N (1):N (2))trigold(I) under high pressure |
title | Observation of a re-entrant phase transition in the molecular complex tris(μ(2)-3,5-diisopropyl-1,2,4-triazolato-κ(2)
N
(1):N
(2))trigold(I) under high pressure |
title_full | Observation of a re-entrant phase transition in the molecular complex tris(μ(2)-3,5-diisopropyl-1,2,4-triazolato-κ(2)
N
(1):N
(2))trigold(I) under high pressure |
title_fullStr | Observation of a re-entrant phase transition in the molecular complex tris(μ(2)-3,5-diisopropyl-1,2,4-triazolato-κ(2)
N
(1):N
(2))trigold(I) under high pressure |
title_full_unstemmed | Observation of a re-entrant phase transition in the molecular complex tris(μ(2)-3,5-diisopropyl-1,2,4-triazolato-κ(2)
N
(1):N
(2))trigold(I) under high pressure |
title_short | Observation of a re-entrant phase transition in the molecular complex tris(μ(2)-3,5-diisopropyl-1,2,4-triazolato-κ(2)
N
(1):N
(2))trigold(I) under high pressure |
title_sort | observation of a re-entrant phase transition in the molecular complex tris(μ(2)-3,5-diisopropyl-1,2,4-triazolato-κ(2)
n
(1):n
(2))trigold(i) under high pressure |
topic | Research Papers |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5391858/ https://www.ncbi.nlm.nih.gov/pubmed/28461897 http://dx.doi.org/10.1107/S2052252516013129 |
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