Ruiz Del Árbol Nerea, Sánchez-Sánchez Carlos, Otero-Irurueta Gonzalo, Martínez José I, de Andrés Pedro L, Gómez-Herrero Ana C, Merino Pablo, Piantek Marten, Serrate David, Lacovig Paolo, Lizzit Silvano, Alemán José, Ellis Gary J, López María F, Martín-Gago José A
ESISNA Group, Materials Science Factory, Institute of Materials Science of Madrid (ICMM-CSIC), Sor Juana Inés de la Cruz 3, 28049, Madrid, Spain.
Centre for Mechanical Technology and Automation (TEMA), University of Aveiro, 3810-193, Aveiro, Portugal.
Angew Chem Int Ed Engl. 2020 Dec 14;59(51):23220-23227. doi: 10.1002/anie.202009863. Epub 2020 Oct 12.
On-surface synthesis is emerging as a highly rational bottom-up methodology for the synthesis of molecular structures that are unattainable or complex to obtain by wet chemistry. Here, oligomers of meta-polyaniline, a known ferromagnetic polymer, were synthesized from para-aminophenol building-blocks via an unexpected and highly specific on-surface formal 1,4 Michael-type addition at the meta position, driven by the reduction of the aminophenol molecule. We rationalize this dehydrogenation and coupling reaction mechanism with a combination of in situ scanning tunneling and non-contact atomic force microscopies, high-resolution synchrotron-based X-ray photoemission spectroscopy and first-principles calculations. This study demonstrates the capability of surfaces to selectively modify local molecular conditions to redirect well-established synthetic routes, such as Michael coupling, towards the rational synthesis of new covalent nanostructures.
表面合成正在成为一种高度合理的自下而上的方法，用于合成通过湿化学难以获得或复杂的分子结构。在这里，一种已知的铁磁聚合物间聚苯胺的低聚物，由对氨基苯酚构建块通过在间位意外且高度特异性的表面形式1,4迈克尔型加成反应合成，该反应由氨基酚分子的还原驱动。我们通过原位扫描隧道显微镜和非接触原子力显微镜、基于同步加速器的高分辨率X射线光电子能谱和第一性原理计算相结合，对这种脱氢和偶联反应机理进行了合理化解释。这项研究证明了表面能够选择性地改变局部分子条件，以将成熟的合成路线（如迈克尔偶联）导向合理合成新的共价纳米结构。
