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

A 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(μ 2-pyrazolato-N,N')-tri-gold(I) (1), tris(μ 2-3,4,5-trimethylpyrazolato-N,N')-tri-gold(I) (2), tris(μ 2-3-methyl-5-phenylpyrazolato-N,N')-tri-gold(I) (3) and tris(μ 2-3,5-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.
Authors:
 [1] ;  [1] ;  [2] ;  [1] ;  [1] ;  [1] ;  [1] ;  [2] ;  [3] ;  [3] ;  [3] ;  [3] ;  [1] ;  [1] ;  [1] ;  [1]
  1. Univ. of Bath, Bath (United Kingdom). Dept. of Chemistry.
  2. Lawrence Berkeley National Lab., CA (United States). Advanced Light Source.
  3. Universite de Montreal, Montreal, QC (Canada). Departement de Chimie.
Publication Date:
Grant/Contract Number:
AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 20; Journal Issue: 51; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; aurophilicity; crystallography; gold; high pressure; luminescence
OSTI Identifier:
1213528

Woodall, Christopher H., Fuertes, Sara, 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, and Raithby, Paul R.. Tunable trimers: Using temperature and pressure to control luminescent emission in gold(I) pyrazolate-based trimers. United States: N. p., Web. doi:10.1002/chem.201404058.
Woodall, Christopher H., Fuertes, Sara, 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. United States. doi:10.1002/chem.201404058.
Woodall, Christopher H., Fuertes, Sara, 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, and Raithby, Paul R.. 2014. "Tunable trimers: Using temperature and pressure to control luminescent emission in gold(I) pyrazolate-based trimers". United States. doi:10.1002/chem.201404058. https://www.osti.gov/servlets/purl/1213528.
@article{osti_1213528,
title = {Tunable trimers: Using temperature and pressure to control luminescent emission in gold(I) pyrazolate-based trimers},
author = {Woodall, Christopher H. and Fuertes, Sara and Beavers, Christine M. and Hatcher, Lauren E. and Parlett, Andrew and Shepherd, Helena J. and Christensen, Jeppe and Teat, Simon J. and Intissar, Mourad and Rodrigue-Witchel, Alexandre and Suffren, Yan and Reber, Christian and Hendon, Christopher H. and Tiana, Davide and Walsh, Aron and Raithby, Paul R.},
abstractNote = {A 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.},
doi = {10.1002/chem.201404058},
journal = {Chemistry - A European Journal},
number = 51,
volume = 20,
place = {United States},
year = {2014},
month = {10}
}

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A short history of SHELX
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