Substrate Effects in the Self-Assembling of N,N-Diphenylquinodimethyl Thioamide on Transition Metals
Substrate Effects in the Self-Assembling of N,N-Diphenylquinodimethyl Thioamide on Transition Metals
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DOI：
10.1021/acs.jpcc.3c01663
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发表时间：
2023-07-17
影响因子：
3.7
通讯作者：
Jiang，Nan
中科院分区：
文献类型：
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作者：
Wang，Kai;Liu，Dairong;Jiang，Nan
藜芦醇烯-硫代酰胺是一类新型的有机捕光发色团，可用于金属离子的三重态光敏化和光度传感。这些发色团的多功能性和诱人的光物理特性使它们适合于工程上过渡金属-有机杂化光材料。在这方面，我们研究了n，N-二苯基奎诺二甲基硫代酰胺(Ph2QDM)纳米结构在过渡金属表面的自组装和行为，以期在光催化和光传感器方面有潜在的应用。在这项工作中，Ph2QDM分子被沉积在Au(111)、Au(100)和Ag(100)表面。扫描隧道显微镜(STM)图像表明，Ph2QDM分子在Au(111)表面形成无定形结构，而在Au(100)和Ag(100)表面形成自组装结构。此外，孤立的单硫原子存在于银(100)面上，而不是金衬底上。高分辨率扫描隧道显微镜图像结合密度泛函理论模拟结果表明，Ph_2QDM分子在Ag(100)面上发生了脱硫反应，导致C-═S键断裂，并在脱硫剂Ph_2QDM与Ag原子之间形成了新的共价键。这些结果不仅揭示了底物对Ph2QDM自组装的影响，而且为金属-有机催化剂和纳米器件开辟了新的途径。
Quinoidal acene-thioamides are a new class of organic light-harvesting chromophores used for several applications, including triplet photosensitization and photometric sensing of metal ions. These chromophores’ versatility and attractive photophysics make them suitable for engineering transition-metal–organic hybrid photomaterials. In this regard, we investigated the self-assembly and behavior ofN,N-diphenylquinodimethyl thioamide (Ph2QDM) nanostructures on transition-metal surfaces for potential applications in photocatalysis and photosensors. In this work, Ph2QDM molecules were deposited onto Au(111), Au(100), and Ag(100) surfaces. The scanning tunneling microscopy (STM) images indicate that the Ph2QDM molecules form an amorphous structure on Au(111) but self-assembled structures on Au(100) and Ag(100). Furthermore, the isolated single sulfur atoms are found on Ag(100) but not on Au substrates. High-resolution STM images combined with density functional theory (DFT) simulation results indicate that the Ph2QDM molecules experience desulfurization on Ag(100) that induces the cleaving of the C═S bond and new covalent bonds between the desulfurized Ph2QDM and Ag atoms. The present results not only uncover the effect of substrates on the self-assembly of Ph2QDM but also open new avenues for metal–organic catalysts and nanodevices.