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Photoinduced Surface Catalytic Coupling Reactions of Aminothiophenol Derivatives Investigated by SERS and DFT
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2016-07-13 00:00:00 , DOI: 10.1021/acs.jpcc.6b04638 Rui Jiang 1 , Meng Zhang 2 , Shu-Li Qian 1 , Feng Yan 1 , Lin-Qi Pei 1 , Shan Jin 1 , Liu-Bin Zhao 3 , De-Yin Wu 2 , Zhong-Qun Tian 2
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2016-07-13 00:00:00 , DOI: 10.1021/acs.jpcc.6b04638 Rui Jiang 1 , Meng Zhang 2 , Shu-Li Qian 1 , Feng Yan 1 , Lin-Qi Pei 1 , Shan Jin 1 , Liu-Bin Zhao 3 , De-Yin Wu 2 , Zhong-Qun Tian 2
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p-Aminothiophenol (PATP) is an important probe molecule in surface-enhanced Raman spectroscopy. The unique and strong SERS signals of PATP distinguished from its normal Raman spectrum were considered as a signal of an existing charge transfer mechanism. Recent theoretical and experimental studies demonstrate that PATP undergoes surface catalytic coupling reaction to produce an aromatic azo species p,p′-dimercaptoazobenzene (DMAB), which should be responsible for the abnormal signals in the observed SERS spectra of PATP. In this work, three aminothiophenol derivatives with different substitute position and conjugation degree between the amino group (−NH2) and mercapto group (−SH) were chosen to study the effects of substituent including adsorption orientation effect and conjugation effect on the reactivity of photoinduced surface catalytic coupling reactions. A combined SERS and DFT study indicated that no surface reactions occurred for compound C1 and compound C2, while compound C3 was converted to the corresponding azo species during their SERS measurements. The differences in reactivity of the selected probe molecules were investigated on the basis of proposed photoexcitation and photoreaction mechanisms.
中文翻译：
SERS和DFT研究的氨基硫酚衍生物的光诱导表面催化偶联反应
对氨基硫酚（PATP）是表面增强拉曼光谱中的重要探针分子。与正常拉曼光谱区分开的PATP独特而强大的SERS信号被认为是现有电荷转移机制的信号。最近的理论和实验研究表明，PATP进行表面催化偶联反应，生成芳香族偶氮物质p，p'-二巯基偶氮苯（DMAB），这应该是所观察到的PATP SERS光谱中异常信号的原因。在这项工作中，三种具有不同取代位置和氨基之间共轭度的氨基硫酚衍生物（-NH 2）和巯基（-SH）被选择来研究包括吸附取向作用和共轭作用在内的取代基对光诱导的表面催化偶联反应的反应性的影响。SERS和DFT的组合研究表明，化合物C1和化合物C2没有表面反应发生，而化合物C3在其SERS测量过程中转化为相应的偶氮类。在提议的光激发和光反应机理的基础上，研究了所选探针分子的反应性差异。
更新日期：2016-07-13
中文翻译：
SERS和DFT研究的氨基硫酚衍生物的光诱导表面催化偶联反应
对氨基硫酚（PATP）是表面增强拉曼光谱中的重要探针分子。与正常拉曼光谱区分开的PATP独特而强大的SERS信号被认为是现有电荷转移机制的信号。最近的理论和实验研究表明，PATP进行表面催化偶联反应，生成芳香族偶氮物质p，p'-二巯基偶氮苯（DMAB），这应该是所观察到的PATP SERS光谱中异常信号的原因。在这项工作中，三种具有不同取代位置和氨基之间共轭度的氨基硫酚衍生物（-NH 2）和巯基（-SH）被选择来研究包括吸附取向作用和共轭作用在内的取代基对光诱导的表面催化偶联反应的反应性的影响。SERS和DFT的组合研究表明，化合物C1和化合物C2没有表面反应发生，而化合物C3在其SERS测量过程中转化为相应的偶氮类。在提议的光激发和光反应机理的基础上，研究了所选探针分子的反应性差异。
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