Unraveling Pathway Complexity in the Supramolecular Polymerization of Z-Shaped Perylenediimides: From Kinetic <i>H</i>-Aggregates to Thermodynamic Null Supramolecular Polymers.

ABSTRACT: This work reports the synthesis of Z-shaped PDI (Z-PDI) 1 and explores its self-assembly behavior. The lateral trialkoxybenzamide moieties in compound 1 promote the formation of metastable monomeric units (M*) through intramolecular hydrogen bonds, which undergo kinetically controlled supramolecular polymerization. This process exhibits pathway complexity, yielding H-type aggregates (AggI_H) under kinetic control and, remarkably, null aggregates (AggII_n) under thermodynamic control. The conversion follows a competitive pathway, in which both aggregated states compete for the free monomeric species. A combination of experimental data and theoretical calculations reveals that the formation of AggI_H

SUBMITTER: Schwalb AJ 

PROVIDER: S-EPMC12272694 | biostudies-literature | 2025 Jul

REPOSITORIES: biostudies-literature