Tunable trimers: using temperature and pressure to control luminescent emission in gold(I) pyrazolate-based trimers

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dc.contributor.authorWoodall, Christopher H.
dc.contributor.authorFuertes, Sara
dc.contributor.authorBeavers, Christine M.
dc.contributor.authorHatcher, Lauren E.
dc.contributor.authorParlett, Andrew
dc.contributor.authorShepherd, Helena J.
dc.contributor.authorChristensen, Jeppe
dc.contributor.authorTeat, Simon J.
dc.contributor.authorIntissar, Mourad
dc.contributor.authorRodrigue-Witchel, Alexandre
dc.contributor.authorSuffren, Yan
dc.contributor.authorReber, Christian
dc.contributor.authorHendon, Christopher H.
dc.contributor.authorTiana, Davide
dc.contributor.authorWalsh, Aron
dc.contributor.authorRaithby, Paul R.
dc.contributor.funderEngineering and Physical Sciences Research Councilen
dc.contributor.funderUniversity of Bathen
dc.contributor.funderEuropean Research Councilen
dc.contributor.funderSeventh Framework Programmeen
dc.contributor.funderU.S. Department of Energyen
dc.contributor.funderNational Science Foundationen
dc.contributor.funderNatural Sciences and Engineering Research Council of Canadaen
dc.date.accessioned2018-07-05T10:51:36Z
dc.date.available2018-07-05T10:51:36Z
dc.date.issued2014-10-21
dc.date.updated2018-07-03T11:22:21Z
dc.description.abstractA systematic investigation into the relationship between the solid‐state luminescence and the intermolecular Au⋅⋅⋅Au interactions in a series of pyrazolate‐based gold(I) trimers; tris(μ2‐pyrazolato‐N,N′)‐tri‐gold(I) (1), tris(μ2‐3,4,5‐ trimethylpyrazolato‐N,N′)‐tri‐gold(I) (2), tris(μ2‐3‐methyl‐5‐phenylpyrazolato‐N,N′)‐tri‐gold(I) (3) and tris(μ2‐3,5‐diphenylpyrazolato‐N,N′)‐tri‐gold(I) (4) has been carried out using variable temperature and high pressure X‐ray crystallography, solid‐state emission spectroscopy, Raman spectroscopy and computational techniques. Single‐crystal X‐ray studies show that there is a significant reduction in the intertrimer Au⋅⋅⋅Au distances both with decreasing temperature and increasing pressure. In the four complexes, the reduction in temperature from 293 to 100 K is accompanied by a reduction in the shortest intermolecular Au⋅⋅⋅Au contacts of between 0.04 and 0.08 Å. The solid‐state luminescent emission spectra of 1 and 2 display a red shift with decreasing temperature or increasing pressure. Compound 3 does not emit under ambient conditions but displays increasingly red‐shifted luminescence upon cooling or compression. Compound 4 remains emissionless, consistent with the absence of intermolecular Au⋅⋅⋅Au interactions. The largest pressure induced shift in emission is observed in 2 with a red shift of approximately 630 cm−1 per GPa between ambient and 3.80 GPa. The shifts in all the complexes can be correlated with changes in Au⋅⋅⋅Au distance observed by diffraction.en
dc.description.sponsorshipEngineering and Physical Sciences Research Council (Projects (EP/K012576/1 and EP/K004956/1), Studentship funding (EP/F021151/1), (Grant No. EP/F067496)); U.S. Department of Energy (Advanced Light Source is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under Contract No. DE-AC02-05CH11231); National Science Foundation ( COMPRES, the Consortium for Materials Properties Research in Earth Sciences under NSF Cooperative Agreement EAR 11-57758)en
dc.description.statusPeer revieweden
dc.description.versionPublished Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationWoodall, C. H., Fuertes, S. , Beavers, C. M., Hatcher, L. E., Parlett, A. , Shepherd, H. J., Christensen, J. , Teat, S. J., Intissar, M. , Rodrigue‐Witchel, A. , Suffren, Y. , Reber, C. , Hendon, C. H., Tiana, D. , Walsh, A. and Raithby, P. R. (2014) 'Tunable Trimers: Using Temperature and Pressure to Control Luminescent Emission in Gold(I) Pyrazolate-Based Trimers', Chemistry – A European Journal, 20(51), pp. 16933-16942. doi: 10.1002/chem.201404058en
dc.identifier.doi10.1002/chem.201404058
dc.identifier.endpage16942en
dc.identifier.issn0947-6539
dc.identifier.journaltitleChemistry - A European Journalen
dc.identifier.startpage16933en
dc.identifier.urihttps://hdl.handle.net/10468/6415
dc.identifier.volume20en
dc.language.isoenen
dc.publisherWileyen
dc.relation.projectinfo:eu-repo/grantAgreement/EC/FP7::SP2::ERC/277757/EU/Hybrid Semiconductors: Design Principles and Material Applications/HYBRIDSen
dc.relation.projectinfo:eu-repo/grantAgreement/RCUK/EPSRC/EP/K012576/1/GB/Understanding and engineering function in switchable molecular crystals/
dc.relation.projectinfo:eu-repo/grantAgreement/RCUK/EPSRC/EP/K004956/1/GB/Applying Long-lived Metastable States with Switchable Functionality via Kinetic Control of Molecular Assembly - a Programme in Functional Materials/
dc.relation.projectinfo:eu-repo/grantAgreement/RCUK/EPSRC/EP/F021151/1/GB/Non-ambient Studies on Opto-electronic Materials/
dc.relation.projectinfo:eu-repo/grantAgreement/RCUK/EPSRC/EP/F067496/1/GB/Modelling of Advanced Functional Materials using Terascale Computing/
dc.relation.urihttps://onlinelibrary.wiley.com/doi/abs/10.1002/chem.201404058
dc.rights© 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.en
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/en
dc.subjectNegative linear compressibilityen
dc.subjectMolecular-crystal structuresen
dc.subjectHirshfeld surface-analysisen
dc.subjectTrinuclear gold(I)en
dc.subjectIntermolecular interactionsen
dc.subjectAurophilic interactionsen
dc.subjectComplexesen
dc.subjectDiffractionen
dc.subjectClusteren
dc.subjectGPAen
dc.subjectAurophilicityen
dc.subjectCrystallographyen
dc.subjectGolden
dc.subjectHigh pressureen
dc.subjectLuminescenceen
dc.titleTunable trimers: using temperature and pressure to control luminescent emission in gold(I) pyrazolate-based trimersen
dc.typeArticle (peer-reviewed)en
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