Tunable Trimers: Using Temperature and Pressure to Control Luminescent Emission in Gold(I) Pyrazolate‐Based Trimers. Issue 51 (21st October 2014)

• Record Type: Journal Article
• Authors: 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.
• Is Part Of: Chemistry. Volume 20:Issue 51(2014)
• Page Start: 16933
• Page End: 16942
• Publication Date: 2014-10-21
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201404058
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>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<sub>2</sub>‐pyrazolato‐<italic>N</italic>, <italic>N</italic>′)‐tri‐gold(I) (<bold>1</bold>), tris(μ<sub>2</sub>‐3, 4, 5‐ trimethylpyrazolato‐<italic>N</italic>, <italic>N</italic>′)‐tri‐gold(I) (<bold>2</bold>), tris(μ<sub>2</sub>‐3‐methyl‐5‐phenylpyrazolato‐<italic>N</italic>, <italic>N</italic>′)‐tri‐gold(I) (<bold>3</bold>) and tris(μ<sub>2</sub>‐3, 5‐diphenylpyrazolato‐<italic>N</italic>, <italic>N</italic>′)‐tri‐gold(I) (<bold>4</bold>) 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 <bold>1</bold> and <bold>2</bold> display a red shift with decreasing temperature or increasing pressure. Compound <bold>3</bold> does not emit under ambient conditions but displays increasingly red‐shifted luminescence upon cooling or compression. Compound <bold>4</bold> remains emissionless, consistent with the absence of intermolecular Au⋅⋅⋅Au interactions. The largest pressure induced shift in emission is observed in <bold>2</bold> with a red shift of approximately 630 cm<sup>−1</sup> 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.</p> </abstract>