A Block Supramolecular Polymer and Its Kinetically Enhanced Stability

Biomolecular systems serve as an inspiration for the creation of multicomponent synthetic supramolecular systems that can be utilized to develop functional materials with complexity. However, supramolecular systems rapidly reach an equilibrium state through dynamic and reversible noncovalent bonds, resulting in a disorganized mixture of components rather than a system in which individual components function cooperatively and/or independently. Thus, efficient synthetic strategies and characterization methods for intricate multicomponent supramolecular assemblies need to be developed. Herein, we report the synthesis of porphyrin-based supramolecular polymers (SPs) in which two distinct block segments consisting of different metal porphyrins are connected: i.e., block supramolecular polymers (BSPs). BSPs with a controlled length and narrow polydispersity were achieved through seeded-growth by a solvent mixing protocol. Interestingly, the block structure permitted the SP as an inner block to coexist with a reagent that was otherwise incompatible with the SP alone. We infer that the inner SP block is compartmentalized in the block structure and endowed with the kinetic stability. Molecular simulations revealed that monomer exchange occurs from the termini of the SP, which corroborated the enhanced stability of the BSP. These results are expected to pave the way for the design of more complex multicomponent supramolecular systems.