Molecular Reprogramming of Hydrogen-Bond Networks: Scanning Tunneling Microscopy Insights into Guest-Induced Transition from Random Tiling to Ordered Architectures.

-terphenyl-2',3,3″,5,5″-pentacarboxylic acid (TPPC) at the heptanoic acid/highly oriented pyrolytic graphite interface was investigated using scanning tunneling microscopy and density functional theory calculations. Assemblies of TPPC formed a random tiling network with molecular cavities composed of five distinct molecular cavities. Upon introduction of coronene (COR) and pyridine derivatives (Bispy and BD), the modulation of the self-assembly process was further investigated. The structure of the TPPC/COR coassembly shows obvious concentration dependence. At low concentrations, COR molecules entered the star-shaped cavities of the TPPC network preferentially. As the concentration increased, COR occupied all cavities within the TPPC network. The introduction of pyridine derivatives (Bispy and BD) with varying backbones can completely remodel the original TPPC architecture and induce a complete structural transformation to form long-range ordered TPPC/Bispy or TPPC/BD coassembly structures. This study realizes the molecular reprogramming of hydrogen-bond networks and the controllable transition from random tiling to ordered architectures, providing a robust strategy for the precise fabrication of two-dimensional supramolecular nanostructures.