Here we demonstrate a strategy of using metal-directed template to control the on-surface polymerization process. We chose bifunctional porphyrin derivatives with pyridyl and bromine end groups as the model system. Linear template afforded by pyridyl�Cu�pyridyl coordination effectively control the Ullmann coupling of the monomers on a Au(111) surface. Taking advantage of efficient topochemical enhancement owing to the conformation flexibility of the Cu�pyridyl bonds, macromolecular porphyrin structures that exhibit a narrow size distribution were synthesized. We used scanning tunneling microscopy and kinetic Monte Carlo simulation to gain insights into the metal-directed polymerization at the single molecule level. The results reveal that the polymerization process profited from the rich chemistry of Cu which catalyzed the C�C bond formation, controlled the size of the macromolecular products, and organized the macromolecules in a highly ordered manner on the surface.

Steering on-surface polymerization with metal-directed template

247th National Meeting (2014)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.