Coordination-Controlled C–C Coupling Products via ortho-Site C–H Activation

• Published in: ACS nano Vol. 13; no. 2; pp. 1385 - 1393
• Main Authors: 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
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 26.02.2019
• Subjects: dehydrogenative homocoupling; AFM; C−H bond activation; coordination interaction; STM
• ISSN: 1936-0851; 1936-086X; 1936-086X
• DOI: 10.1021/acsnano.8b06885

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.