Zhang Xue, Xue Na, Li Chao, Li Na, Wang Hao, Kocić Nemanja, Beniwal Sumit, Palotás Krisztián, Li Ruoning, Xue Qiang, Maier Sabine, Hou Shimin, Wang Yongfeng
Key Laboratory for the Physics and Chemistry of Nanodevices, Department of Electronics , Peking University , Beijing 100871 , China.
Peking University Information Technology Institute (Tianjin Binhai), Tianjin 300450 , China.
ACS Nano. 2019 Feb 26;13(2):1385-1393. doi: 10.1021/acsnano.8b06885. Epub 2019 Feb 11.
The coordination-restricted ortho-site C-H bond activation and dehydrogenative homocoupling of 4,4'-(1,3-phenylene)dipyridine (1,3-BPyB) and 4,4'-(1,4-phenylene)dipyridine (1,4-BPyB) on different metal surfaces were studied by a combination of scanning tunneling microscopy, noncontact atomic force microscopy, and density functional theory calculations. The coupling products on Cu(111) exhibited certain configurations subject to the spatial restriction of robust two-fold Cu-N coordination bonds. Compared to the V-shaped 1,3-BPyB, the straight backbone of 1,4-BPyB helped to further reduce the variety of reactive products. By utilizing the three-fold coordination of Fe atoms with 1,4-BPyB molecules on Au(111), a large-scale network containing single products was constructed. Our results offer a promising protocol for controllable on-surface synthesis with the aid of robust coordination interactions.
通过扫描隧道显微镜、非接触原子力显微镜和密度泛函理论计算相结合的方法，研究了4,4'-(1,3-亚苯基)二吡啶(1,3-BPyB)和4,4'-(1,4-亚苯基)二吡啶(1,4-BPyB)在不同金属表面上的配位受限邻位C-H键活化和脱氢均偶联反应。Cu(111)上的偶联产物呈现出一定的构型，这受到稳定的双折Cu-N配位键的空间限制。与V形的1,3-BPyB相比，1,4-BPyB的直链主链有助于进一步减少反应产物的种类。通过利用金(111)表面铁原子与1,4-BPyB分子的三重配位，构建了一个包含单一产物的大规模网络。我们的结果为借助强大的配位相互作用进行可控的表面合成提供了一个有前景的方案。
