In-Chul Hwang

A continuous flow methodology for the facile and high‐yielding synthesis of the porphyrin‐based self‐assembled organic cage, P 12 L 24 is reported, along with the serendipitous discovery of a kinetic product, P 9 L 18 cage, which has been characterized by MALDI‐TOF MS, NMR, and AFM analysis. A theoretical study suggests a tricapped trigonal prismatic geometry for P 9 L 18 . Unlike P 12 L 24 , P 9 L 18 is unstable and readily decomposes into monomers and small oligomers. While the batch synthesis produces only the thermodynamic product P 12 L 24 , the continuous flow process generates not only the thermodynamic product but also kinetic products, such as P 9 L 18 , illustrating the advantages of the continuous flow process for the synthesis of self‐assembled cages and the exploration of new non‐equilibrium assemblies.