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

Christopher H. Woodall, Sara Fuertes, Christine M. Beavers, Lauren E. Hatcher, Andrew Parlett, Helena J. Shepherd, Jeppe Christensen, Simon J. Teat, Mourad Intissar, Alexandre Rodrigue-Witchel, Yan Suffren, Christian Reber, Christopher H. Hendon, Davide Tiana, Aron Walsh, Paul R. Raithby

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23 Scopus citations


A systematic investigation into the relationship between the solid-state luminescence and the intermolecular AuAu 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 AuAu 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 AuAu contacts of between 0.04 and 0.08 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 AuAu 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 AuAu distance observed by diffraction.

Original languageEnglish
Pages (from-to)16933-16942
Number of pages10
JournalChemistry - A European Journal
Issue number51
StatePublished - 15 Dec 2014

Bibliographical note

Publisher Copyright:
© 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.


  • Aurophilicity
  • Crystallography
  • Gold
  • High pressure
  • Luminescence


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