Chemisorption-Induced Formation of Biphenylene Dimer on Ag(111)
Zhiwen Zeng, Dezhou Guo, Tao Wang, Qifan Chen, Adam Matěj, Jianmin Huang, Dong Han, Qian Xu, Aidi Zhao, Pavel Jelı́nek, Dimas G. de Oteyza, Jean‐Sabin McEwen, Junfa Zhu
Abstract
We report an example that demonstrates the clear interdependence between surface-supported reactions and molecular-adsorption configurations. Two biphenyl-based molecules with two and four bromine substituents, i.e., 2,2′-dibromobiphenyl (DBBP) and 2,2′,6,6′-tetrabromo-1,1′-biphenyl (TBBP), show completely different reaction pathways on a Ag(111) surface, leading to the selective formation of dibenzo[e,l]pyrene and biphenylene dimer, respectively. By combining low-temperature scanning tunneling microscopy, synchrotron radiation photoemission spectroscopy, and density functional theory calculations, we unravel the underlying reaction mechanism. After debromination, a biradical biphenyl can be stabilized by surface Ag adatoms, while a four-radical biphenyl undergoes spontaneous intramolecular annulation due to its extreme instability on Ag(111). Such different chemisorption-induced precursor states between DBBP and TBBP consequently lead to different reaction pathways after further annealing. In addition, using bond-resolving scanning tunneling microscopy and scanning tunneling spectroscopy, we determine with atomic precision the bond-length alternation of the biphenylene dimer product, which contains 4-, 6-, and 8-membered rings. The 4-membered ring units turn out to be radialene structures.