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

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. Chemistry - A European Journal 20 (51) , pp. 16933-16942. 10.1002/chem.201404058

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Abstract

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.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Publisher: Wiley
ISSN: 0947-6539
Date of First Compliant Deposit: 18 March 2020
Date of Acceptance: 21 October 2014
Last Modified: 14 Sep 2020 16:15
URI: https://orca.cardiff.ac.uk/id/eprint/130481

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