Meng Xiangzhi, Klaasen Henning, Viergutz Lena, Schulze Lammers Bertram, Witteler Melanie C, Mönig Harry, Amirjalayer Saeed, Liu Lacheng, Neugebauer Johannes, Gao Hong-Ying, Studer Armido, Fuchs Harald
Physikalisches Institut, Westfälische Wilhelms-Universität Münster, Wilhelm-Klemm-Strasse 10, 48149, Münster, Germany.
Center for Nanotechnology, Heisenbergstrasse 11, 48149, Münster, Germany.
Angew Chem Int Ed Engl. 2021 Jan 18;60(3):1458-1464. doi: 10.1002/anie.202011858. Epub 2020 Dec 11.
The formation of azo compounds via redox cross-coupling of nitroarenes and arylamines, challenging in solution phase chemistry, is achieved by on-surface chemistry. Reaction products are analyzed with a cryogenic scanning tunneling microscope (STM) and X-ray photoelectron spectroscopy (XPS). By using well-designed precursors containing both an amino and a nitro functionality, azo polymers are prepared on surface via highly efficient nitro-amino cross-coupling. Experiments conducted on other substrates and surface orientations reveal that the metal surface has a significant effect on the reaction efficiency. The reaction was further found to proceed from partially oxidized/reduced precursors in dimerization reactions, shedding light on the mechanism that was studied by DFT calculations.
通过硝基芳烃和芳胺的氧化还原交叉偶联形成偶氮化合物，这在溶液相化学中具有挑战性，而通过表面化学得以实现。反应产物用低温扫描隧道显微镜（STM）和X射线光电子能谱（XPS）进行分析。通过使用同时含有氨基和硝基官能团的精心设计的前体，通过高效的硝基 - 氨基交叉偶联在表面制备偶氮聚合物。在其他底物和表面取向上进行的实验表明，金属表面对反应效率有显著影响。进一步发现该反应在二聚反应中从部分氧化/还原的前体开始进行，这为通过密度泛函理论（DFT）计算研究的机理提供了线索。
