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

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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
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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.
Negative linear compressibility , Molecular-crystal structures , Hirshfeld surface-analysis , Trinuclear gold(I) , Intermolecular interactions , Aurophilic interactions , Complexes , Diffraction , Cluster , GPA , Aurophilicity , Crystallography , Gold , High pressure , Luminescence
Woodall, C. H., Fuertes, S. , Beavers, C. M., Hatcher, L. E., Parlett, A. , Shepherd, H. J., Christensen, J. , Teat, S. J., Intissar, M. , Rodrigue‐Witchel, A. , Suffren, Y. , Reber, C. , Hendon, C. H., Tiana, D. , Walsh, A. and Raithby, P. 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. doi: 10.1002/chem.201404058