Although post-functionalization is extensively used to introduce diverse functional groups into supramolecular polymers (SPs) in solution, post-functionalization of SPs on surfaces still remains unexplored. Here we achieved the onsurface post-functionalization of two SPs derived from 5,10,15-tri-(4-pyridyl)-20-bromophenyl porphyrin (Br-TPyP) via cross-coupling reactions on Au(111).T he ladder-shaped, Cu-coordinated SPs preformed from Br-TPyP were functionalized through Heck reaction with 4-vinyl-1,1'-biphenyl. In the absence of Cu, Br-TPyP formed chiral SPs as two enantiomers via self-assembly,w hich were functionalized via divergent cross-coupling reaction with 4-isocyano-1,1'-biphenyl (ICBP). Surprisingly,t his reaction was discovered as an enantioselective on-surface reaction induced by the chirality of SPs. Mechanistic analysis and DFT calculations indicated that after debromination of Br-TPyP and the first addition of ICBP,only one attackd irection of ICBP to the chiral SP intermediate is permissive in the second addition step due to the steric hindrance,w hichg uaranteed the high enantioselectivity of the reaction.

3]Radialenes are the smallest carbocyclic structures with unusual topologies and cross-conjugated π-electronic structures. Here, we report a novel [1+1+1] cycloaddition reaction for the synthesis of aza-[3]radialenes on the Ag(111) surface, where the steric hindrance of the chlorine substituents guides the selective and orientational assembling of the isocyanide precursors. By combining scanning tunneling microscopy, non-contact atomic force microscopy, and timeof-flight secondary ion mass spectrometry, we determined the atomic structure of the produced aza-[3]radialenes. Furthermore, two reaction pathways including synergistic and stepwise are proposed based on density functional theory calculations, which reveal the role of the chlorine substituents in the activation of the isocyano groups via electrostatic interaction.