Competing Interactions in Hierarchical Porphyrin Self-Assembly Introduce Robustness in Pathway Complexity.

ABSTRACT: Pathway complexity in supramolecular polymerization has recently sparked interest as a method to generate complex material behavior. The response of these systems relies on the existence of a metastable, kinetically trapped state. In this work, we show that strong switch-like behavior in supramolecular polymers can also be achieved through the introduction of competing aggregation pathways. This behavior is illustrated with the supramolecular polymerization of a porphyrin-based monomer at various concentrations, solvent compositions, and temperatures. It is found that the monomers aggregate via an isodesmic mechanism in weakly coupled J-type aggregates at intermediate solvent quality and temperature, followed by nucleated H-aggregates at lower solvent qualities and temperatures. At further

SUBMITTER: Mabesoone MFJ 

PROVIDER: S-EPMC6026832 | biostudies-literature | 2018 Jun

REPOSITORIES: biostudies-literature