Tunable Trimers: Using Temperature and Pressure to Control Luminescent Emission in Gold(I) Pyrazolate-Based Trimers

摘要

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.