Observation of a re-entrant phase transition in the molecular complex tris(μ2-3,5-diisopropyl-1,2,4-triazolato-κ2N1:N2)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(μ2-3,5-diisopropyl-1,2,4-triazolato-κ2N1:N2)trigo...
Main Authors: | , , , , , , , , , , , , |
---|---|
Format: | Article |
Language: | English |
Published: |
International Union of Crystallography
2016-09-01
|
Series: | IUCrJ |
Subjects: | |
Online Access: | http://scripts.iucr.org/cgi-bin/paper?S2052252516013129 |
id |
doaj-e438a285aa4e4d7f9ca590d04a54f295 |
---|---|
record_format |
Article |
spelling |
doaj-e438a285aa4e4d7f9ca590d04a54f2952020-11-24T23:15:33ZengInternational Union of CrystallographyIUCrJ2052-25252016-09-013536737610.1107/S2052252516013129ed5009Observation of a re-entrant phase transition in the molecular complex tris(μ2-3,5-diisopropyl-1,2,4-triazolato-κ2N1:N2)trigold(I) under high pressureChristopher H. Woodall0Jeppe Christensen1Jonathan M. Skelton2Lauren E. Hatcher3Andrew Parlett4Paul R. Raithby5Aron Walsh6Stephen C. Parker7Christine M. Beavers8Simon J. Teat9Mourad Intissar10Christian Reber11David R. Allan12Department of Chemistry, University of Bath, Bath BA2 7AY, UKResearch Complex at Harwell, Rutherford Appleton Laboratory, Harwell Oxford, Didcot, Oxfordshire, OX11 0FA, UKDepartment of Chemistry, University of Bath, Bath BA2 7AY, UKDepartment of Chemistry, University of Bath, Bath BA2 7AY, UKDepartment of Chemistry, University of Bath, Bath BA2 7AY, UKDepartment of Chemistry, University of Bath, Bath BA2 7AY, UKDepartment of Chemistry, University of Bath, Bath BA2 7AY, UKDepartment of Chemistry, University of Bath, Bath BA2 7AY, UKStation 11.3.1, Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USAStation 11.3.1, Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USADépartement de Chimie, Université de Montréal, Montréal, Québec, H3C 3J7, CanadaDépartement de Chimie, Université de Montréal, Montréal, Québec, H3C 3J7, CanadaStation I19, Diamond Light Source, Didcot, Oxfordshire, OX11 0QX, UKWe 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(μ2-3,5-diisopropyl-1,2,4-triazolato-κ2N1:N2)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 P21/n phase above 1 GPa, followed by a P21/a phase above 2 GPa and a large-volume C2/c supercell at 2.70 GPa, with the previously observed P21/n phase then reappearing at higher pressure. The observation of crystallographically identical low- and high-pressure P21/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.http://scripts.iucr.org/cgi-bin/paper?S2052252516013129re-entrant phase transitionshigh-pressure crystallographygold(I)luminescence spectroscopyDFT calculations |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
Christopher H. Woodall Jeppe Christensen Jonathan M. Skelton Lauren E. Hatcher Andrew Parlett Paul R. Raithby Aron Walsh Stephen C. Parker Christine M. Beavers Simon J. Teat Mourad Intissar Christian Reber David R. Allan |
spellingShingle |
Christopher H. Woodall Jeppe Christensen Jonathan M. Skelton Lauren E. Hatcher Andrew Parlett Paul R. Raithby Aron Walsh Stephen C. Parker Christine M. Beavers Simon J. Teat Mourad Intissar Christian Reber David R. Allan Observation of a re-entrant phase transition in the molecular complex tris(μ2-3,5-diisopropyl-1,2,4-triazolato-κ2N1:N2)trigold(I) under high pressure IUCrJ re-entrant phase transitions high-pressure crystallography gold(I) luminescence spectroscopy DFT calculations |
author_facet |
Christopher H. Woodall Jeppe Christensen Jonathan M. Skelton Lauren E. Hatcher Andrew Parlett Paul R. Raithby Aron Walsh Stephen C. Parker Christine M. Beavers Simon J. Teat Mourad Intissar Christian Reber David R. Allan |
author_sort |
Christopher H. Woodall |
title |
Observation of a re-entrant phase transition in the molecular complex tris(μ2-3,5-diisopropyl-1,2,4-triazolato-κ2N1:N2)trigold(I) under high pressure |
title_short |
Observation of a re-entrant phase transition in the molecular complex tris(μ2-3,5-diisopropyl-1,2,4-triazolato-κ2N1:N2)trigold(I) under high pressure |
title_full |
Observation of a re-entrant phase transition in the molecular complex tris(μ2-3,5-diisopropyl-1,2,4-triazolato-κ2N1:N2)trigold(I) under high pressure |
title_fullStr |
Observation of a re-entrant phase transition in the molecular complex tris(μ2-3,5-diisopropyl-1,2,4-triazolato-κ2N1:N2)trigold(I) under high pressure |
title_full_unstemmed |
Observation of a re-entrant phase transition in the molecular complex tris(μ2-3,5-diisopropyl-1,2,4-triazolato-κ2N1:N2)trigold(I) under high pressure |
title_sort |
observation of a re-entrant phase transition in the molecular complex tris(μ2-3,5-diisopropyl-1,2,4-triazolato-κ2n1:n2)trigold(i) under high pressure |
publisher |
International Union of Crystallography |
series |
IUCrJ |
issn |
2052-2525 |
publishDate |
2016-09-01 |
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(μ2-3,5-diisopropyl-1,2,4-triazolato-κ2N1:N2)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 P21/n phase above 1 GPa, followed by a P21/a phase above 2 GPa and a large-volume C2/c supercell at 2.70 GPa, with the previously observed P21/n phase then reappearing at higher pressure. The observation of crystallographically identical low- and high-pressure P21/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. |
topic |
re-entrant phase transitions high-pressure crystallography gold(I) luminescence spectroscopy DFT calculations |
url |
http://scripts.iucr.org/cgi-bin/paper?S2052252516013129 |
work_keys_str_mv |
AT christopherhwoodall observationofareentrantphasetransitioninthemolecularcomplextrism235diisopropyl124triazolatok2n1n2trigoldiunderhighpressure AT jeppechristensen observationofareentrantphasetransitioninthemolecularcomplextrism235diisopropyl124triazolatok2n1n2trigoldiunderhighpressure AT jonathanmskelton observationofareentrantphasetransitioninthemolecularcomplextrism235diisopropyl124triazolatok2n1n2trigoldiunderhighpressure AT laurenehatcher observationofareentrantphasetransitioninthemolecularcomplextrism235diisopropyl124triazolatok2n1n2trigoldiunderhighpressure AT andrewparlett observationofareentrantphasetransitioninthemolecularcomplextrism235diisopropyl124triazolatok2n1n2trigoldiunderhighpressure AT paulrraithby observationofareentrantphasetransitioninthemolecularcomplextrism235diisopropyl124triazolatok2n1n2trigoldiunderhighpressure AT aronwalsh observationofareentrantphasetransitioninthemolecularcomplextrism235diisopropyl124triazolatok2n1n2trigoldiunderhighpressure AT stephencparker observationofareentrantphasetransitioninthemolecularcomplextrism235diisopropyl124triazolatok2n1n2trigoldiunderhighpressure AT christinembeavers observationofareentrantphasetransitioninthemolecularcomplextrism235diisopropyl124triazolatok2n1n2trigoldiunderhighpressure AT simonjteat observationofareentrantphasetransitioninthemolecularcomplextrism235diisopropyl124triazolatok2n1n2trigoldiunderhighpressure AT mouradintissar observationofareentrantphasetransitioninthemolecularcomplextrism235diisopropyl124triazolatok2n1n2trigoldiunderhighpressure AT christianreber observationofareentrantphasetransitioninthemolecularcomplextrism235diisopropyl124triazolatok2n1n2trigoldiunderhighpressure AT davidrallan observationofareentrantphasetransitioninthemolecularcomplextrism235diisopropyl124triazolatok2n1n2trigoldiunderhighpressure |
_version_ |
1725590628231806976 |