Fine-Tuning of Luminescence through Changes in Au-S Bond Lengths as a Function of Temperature or Solvent
Fine-Tuning of Luminescence through Changes in Au-S Bond Lengths as a Function of Temperature or Solvent
复制标题
通过改变 Au-S 键长作为温度或溶剂的函数来微调发光
DOI：
10.1021/acs.inorgchem.9b00845
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发表时间：
2019
影响因子：
4.6
通讯作者：
Lang Jian Ping
中科院分区：
文献类型：
--
作者：
Liu Chun Yu;Wang Hui Fang;Ren Zhi Gang;Braunstein Pierre;Lang Jian Ping
金（I）-硫化合物的发光性质因其在传感领域的潜在应用而备受关注。发光的分子水平调控仍然是一个挑战。因此，研究发光与结构之间的关系是十分重要的。本文报道了一个双核配合物[Au_2（dppaptc）_2] Cl_2（1，dppaptc =N，N-双（二苯基膦基甲基）-氨基-4-苯基硫脲），其Au-S键长随温度或溶剂的变化而变化。X射线衍射分析表明，1·2CHCl 3在300 ~ 80 K温度范围内从2.900（3）降至2.745（15）nm，并与其475 nm处的发光强度呈线性相关，这一结果得到了TD-DFT计算的证实。化合物1与水和乙醇溶剂化后，Au-S键变短，发光增强。发光强度和Au-S长度之间的密切关系作为现有发光金（I）-硫系统的补充，并为理解金（I）-硫化合物的热致变色性和溶剂化变色性提供了一些见解。
The luminescent properties of gold(I)–sulfur compounds have received much attention for their potential applications in the sensing field. The molecular level regulation of luminescence remains a challenge. It is critical to unravel the relationship between the luminescence and the structure. Herein we report a binuclear complex [Au2(dppaptc)2]Cl2(1, dppaptc =N,N-bis(diphenylphosphanylmethyl)-amino-4-phenyl-thiocarbamide), which exhibits variations at Au–S bond lengths as a function of temperature or solvent. X-ray analysis reveals a linear decrease from 2.900(3) to 2.745(15) Å upon cooling1·2CHCl3from 300 to 80 K combined with a linear correlation with its luminescence intensity at 475 nm, which was confirmed by TD-DFT calculations. Compound1, if solvated with H2O and alcohol, possesses the shorter Au–S bonds and enhanced luminescence. The close relationship between luminescence intensity and Au–S length serves as a complement to existing luminescent gold(I)–sulfur systems and provides some insight into understanding the thermochromism and solvatochromism of the gold(I)–sulfur compounds.