Structural Variation in Surface-Supported Synthesis by Adjusting the Stoichiometric Ratio of the Reactants

Surface-supported coupling reactions between 1,3,5-tris(4-formylphenyl)benzene and aromatic amines have been investigated on Au(111) using scanning tunneling microscopy under ultra-high-vacuum conditions. Upon annealing to moderate temperatures, various products, involving the discrete oligomers and the surface covalent organic frameworks, are obtained through thermal-triggered on-surface chemical reactions. We conclude from the systematic experiments that the stoichiometric composition of the reactants is vital to the surface reaction products, which is rarely reported so far. With this knowledge, we have successfully prepared two-dimensional covalently bonded networks by optimizing the stoichiometric proportions of the reaction precursors.