Tunable trimers: using temperature and pressure to control luminescent emission in gold(I) pyrazolate-based trimers.
Tunable trimers: using temperature and pressure to control luminescent emission in gold(I) pyrazolate-based trimers.
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DOI：
10.1002/chem.201404058
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发表时间：
2014-12-15
影响因子：
4.3
通讯作者：
Raithby, Paul R.
中科院分区：
文献类型：
--
作者：
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.
一系列吡唑基金（I）三聚体的固态发光与分子间Au与Au相互作用关系的系统研究Tris（μ2-吡唑基-N，N′）-三-金（I）（1），三（μ2- 3，4，5-三甲基吡唑-N，N′）-三-金（I）（2），三（μ2-3-甲基-5-苯基吡唑并-N，N′）-三-金（I）（3）和三用变温高压X射线晶体学、固体发射光谱、拉曼光谱和计算技术。单晶X-射线研究表明，有一个显着的减少在intertrimer Au晶体的距离Au与降低温度和增加压力。在这四种配合物中，温度从293 K降低到100 K时，伴随着分子间最短的Au键合Au接触的减少，减少了0.04到0.08 Ω。 化合物1和2的固态发光发射光谱随着温度的降低或压力的增加而出现红移。化合物3在环境条件下不发光，但在冷却或压缩时显示出越来越红移的发光。化合物4保持无发射，这与不存在分子间Au互穿Au相互作用一致。在2中观察到最大的压力引起的发射位移，在环境和3.80 GPa之间的红移约为630 cm−1/GPa。 在所有的配合物中的位移可以与衍射观察到的Au电子-Au距离的变化相关。
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.
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影响因子：
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