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

Christopher H. Woodall, S Fuertes Lorda, 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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Abstract

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.

LanguageEnglish
Pages16933-16942
Number of pages10
JournalChemistry - A European Journal
Volume20
Issue number51
DOIs
StatusPublished - 15 Dec 2014

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Gold
Luminescence
Temperature
X ray crystallography
Emission spectroscopy
Raman spectroscopy
Diffraction
Display devices
Single crystals
Cooling
X rays

Keywords

  • Aurophilicity
  • Crystallography
  • Gold
  • High pressure
  • Luminescence

Cite this

Tunable trimers : using temperature and pressure to control luminescent emission in gold(i) pyrazolate-based trimers. / Woodall, Christopher H.; Fuertes Lorda, S; Beavers, Christine M.; Hatcher, Lauren E.; Parlett, Andrew; Shepherd, Helena J.; Christensen, Jeppe; Teat, Simon J.; Intissar, Mourad; Rodrigue-Witchel, Alexandre; Suffren, Yan; Reber, Christian; Hendon, Christopher H.; Tiana, Davide; Walsh, Aron; Raithby, Paul R.

In: Chemistry - A European Journal, Vol. 20, No. 51, 15.12.2014, p. 16933-16942.

Research output: Contribution to journalArticle

Woodall, CH, Fuertes Lorda, S, Beavers, CM, Hatcher, LE, Parlett, A, Shepherd, HJ, Christensen, J, Teat, SJ, Intissar, M, Rodrigue-Witchel, A, Suffren, Y, Reber, C, Hendon, CH, Tiana, D, Walsh, A & Raithby, PR 2014, 'Tunable trimers: using temperature and pressure to control luminescent emission in gold(i) pyrazolate-based trimers' Chemistry - A European Journal, vol. 20, no. 51, pp. 16933-16942. https://doi.org/10.1002/chem.201404058
Woodall, Christopher H. ; Fuertes Lorda, S ; Beavers, Christine M. ; Hatcher, Lauren E. ; Parlett, Andrew ; Shepherd, Helena J. ; Christensen, Jeppe ; Teat, Simon J. ; Intissar, Mourad ; Rodrigue-Witchel, Alexandre ; Suffren, Yan ; Reber, Christian ; Hendon, Christopher H. ; Tiana, Davide ; Walsh, Aron ; Raithby, Paul R. / Tunable trimers : using temperature and pressure to control luminescent emission in gold(i) pyrazolate-based trimers. In: Chemistry - A European Journal. 2014 ; Vol. 20, No. 51. pp. 16933-16942.
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abstract = "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.",
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