Solution Preparation of Two-Dimensional Covalently Linked Networks by Polymerization of 1,3,5-Tri(4-iodophenyl)benzene on Au(111)

The polymerization of 1,3,5-tri(4-iodophenyl)benzene (TIPB) on Au(111) through covalent aryl-aryl coupling is accomplished using a solution-based approach and investigated by scanning tunneling microscopy. Drop-casting of the TIPB monomer onto Au(111) at room temperature results in poorly ordered noncovalent arrangements of molecules and partial dehalogenation. However, drop-casting on a preheated Au(111) substrate yields various topologically distinct covalent aggregates and networks. Interestingly, some of these covalent nanostructures do not adsorb directly on the Au(111) surface, but are loosely bound to a disordered layer of a mixture of chemisorbed iodine and molecules, a conclusion that is drawn from STM data and supported by X-ray photoelectron spectroscopy. We argue that the gold surface becomes covered by a strongly chemisorbed iodine monolayer which eventually inhibits further polymerization.