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 ; Raithby, Paul R.

Resumen: 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.

Idioma: Inglés

DOI: 10.1002/chem.201404058

Año: 2014

Publicado en: Chemistry - A European Journal 20, 51 (2014), 16933-16942
ISSN: 0947-6539

Factor impacto JCR: 5.731 (2014)

Categ. JCR: CHEMISTRY, MULTIDISCIPLINARY rank: 22 / 154 = 0.143 (2014) - Q1 - T1

Tipo y forma: Artículo (Versión definitiva)