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Controllable Density of Atomic Bromine in a Two-Dimensional Hydrogen Bond Network

Using atomic bromine (Br) and pentacene molecules, we successfully constructed and characterized a large-scale Br atom-mediated two-dimensional (2D) organic network on a Ag(111) surface by combining molecular beam epitaxy with scanning tunneling microscopy. The Br atoms form −C–H···Br hydrogen bonds with pentacene molecules in the network, and the number of Br atoms among pentacene molecules can be tuned from one to five by increasing the pressure or exposure time of hydrogen bromide (HBr) gas. In addition, all of the Br atoms of five 2D organic networks fill themselves in the position of maximum number of hydrogen bonds.