Surface Tectonics of Nanoporous Networks of Melamine‐Capped Molecular Building Blocks formed through Interface Schiff‐Base Reactions

Abstract Control over the assembly of molecules on a surface is of great importance for the fabrication of molecule‐based miniature devices. Melamine (MA) and molecules with terminal MA units are promising candidates for supramolecular interfacial packing patterning, owing to their multiple hydrogen‐bonding sites. Herein, we report the formation of self‐assembled structures of MA‐capped molecules through a simple on‐surface synthetic route. MA terminal groups were successfully fabricated onto rigid molecular cores with 2‐fold and 3‐fold symmetry through interfacial Schiff‐base reactions between MA and aldehyde groups. Sub‐molecular scanning tunneling microscopy (STM) imaging of the resultant adlayer revealed the formation of nanoporous networks. Detailed structural analysis indicated that strong hydrogen‐bonding interactions between the MA groups persistently drove the formation of nanoporous networks. Herein, we demonstrate that functional groups with strong hydrogen‐bond‐formation ability are promising building blocks for the guided assembly of nanoporous networks and other hierarchical 2D assemblies.