Snapshots of Dynamic Adaptation: Two-Dimensional Molecular Architectonics with Linear Bis-Hydroxamic Acid Modules

Linear modules equipped with two terminal hydroxamic acid groups act as the building block of diverse two-dimensional supramolecular motifs and patterns with room-temperature stability on the close-packed single-crystal surfaces of silver and gold, revealing a complex self-assembly scenario. By combining multiple investigation techniques (scanning tunneling microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, and density functional theory calculations), we analyze the characteristics of the ordered assemblies which range from close-packed structures to polyporous networks featuring an exceptionally extended primitive unit cell with a side length exceeding 7 nm. The polyporous network shows potential for hosting and promoting the formation of chiral supramolecules, whereas a transition from 1D chiral randomness to an ordered racemate is discovered in a different porous phase. We correlate the observed structural changes to the adaptivity of the building block and surface-induced changes in the chemical state of the hydroxamic acid functional group.