Woodall, CH;Fuertes, S;Beavers, CM;Hatcher, LE;Parlett, A;Shepherd, HJ;Christensen, J;Teat, SJ;Intissar, M;Rodrigue-Witchel, A;Suffren, Y;Reber, C;Hendon, CH;Tiana, D;Walsh, A;Raithby, PR

2014

December

Chemistry - A European Journal

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

Validated

Altmetric: 2 ()

NEGATIVE LINEAR COMPRESSIBILITY MOLECULAR-CRYSTAL STRUCTURES HIRSHFELD SURFACE-ANALYSIS TRINUCLEAR GOLD(I) INTERMOLECULAR INTERACTIONS AUROPHILIC INTERACTIONS COMPLEXES DIFFRACTION CLUSTER GPA

20

16933

16942

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(mu(2)-pyrazolato-N, N')-tri-gold(I) (1), tris(mu(2)-3,4,5-trimethylpyrazolato- N, N')-tri-gold(I) (2), tris(mu(2)-3-methyl-5phenylpyrazolato- N, N')-tri-gold(I) (3) and tris(mu(2)-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 tempera-ture from 293 to 100 K is accompanied by a reduction in the shortest intermolecular Au ... Au contacts of between 0.04 and 0.08 angstrom. 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.

WEINHEIM

0947-6539

10.1002/chem.201404058