Molecular self-assembly from building blocks synthesized on a surface in ultrahigh vacuum: kinetic control and topo-chemical reactions.

Self-assembly of organic molecules on solid surfaces under ultrahigh vacuum conditions has been the focus of intense study, in particular utilizing the technique of scanning tunneling microscopy. The size and complexity of the organic compounds used in such studies are in general limited by thermal decomposition in the necessary vacuum sublimation step. An interesting alternative approach is to deposit smaller molecular precursors, which react with each other on the surface and form the building blocks for the subsequent self-assembly. This has however hitherto not been explored to any significant extent. Here, we perform a condensation reaction between aldehyde and amine precursors codeposited on a Au(111) surface. The reaction product consists of a three-spoke oligo-phenylene-ethynylene backbone with alkyl chains attached through imine coupling. We characterize the self-assembled structures and molecular conformations of the complex reaction product and find that the combined reaction and self-assembly process exhibits pronounced kinetic effects leading to formation of qualitatively different molecular structures depending on the reaction/assembly conditions. At high amine flux/low substrate temperature, compact triimine structures of high conformational order are formed, which inherit organizational motifs from structures formed from one of the reactants. This suggests a topochemical reaction. At low amine flux/high substrate temperature, open porous networks with a high degree of conformational disorder are formed. Both structures are entirely different from that obtained when the triimine product synthesized ex-situ is deposited onto the surface. This demonstrates that the approach of combined self-assembly and on-surface synthesis may allow formation of unique structures that are not obtainable through self-assembly from conventionally deposited building blocks.