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

[Image: see text] 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.