Divergent Carbonization of Pillar[5]Arenes Produces Porous and Lamellar Carbon Architectures.

Carbonization of organic precursors is widely used to produce carbon materials. However, the morphology and properties of the resulting carbons remain difficult to predict and control owing to complex pyrolytic reactions. Here, by using pillar[5]arenes as a structurally defined macrocyclic platform, we show that their peripheral functionality regulates carbonization in three distinct pathways, early-stage fixation, progressive coalescence, and melt-assisted reconstruction, providing microporous frameworks and fused lamellar carbons. Modulating the precursor aggregation further tunes the morphology at the micrometer scale. These pathway-defined architectures result in distinct functions, with microporous carbons favoring gas adsorption and lamellar carbons enabling electrical transport in exfoliated sheets. This work links the macrocyclic structure to the carbonization pathway and resulting properties, providing design guidance for converting molecular precursors into functional carbon materials.