X₃ synthon geometries in two-dimensional halogen-bonded 1,3,5-tris(3,5-dibromophenyl)benzene self-assembled...

The self-assembly of star-shaped 1,3,5-tris(3,5-dibromophenyl)benzene molecules on Au(111)-() in a vacuum is investigated using scanning tunneling microscopy and core-level spectroscopy. Scanning tunneling microscopy shows that the molecules self-assemble into a hexagonal porous halogen-bonded nanoarchitecture. This structure is stabilized by X_3-A synthons composed of three type-II halogen-interactions (halogen-bonds). The molecules are oriented along the same direction in this arrangement. Domain boundaries are observed in the hcp region of the herringbone gold surface reconstruction. Molecules of the neighboring domains are rotated by 180°. The domain boundaries are stabilized by the formation of X_3-B synthons composed of two type-II and one type-I halogen-interactions between molecules of the neighboring domains. Core-level spectroscopy confirms the existence of two types of halogen-interactions in the organic layer. These observations show that the gold surface reconstructions can be exploited to modify the long-range supramolecular halogen-bonded self-assemblies.