Stepwise self-organization of hydrogen-bonded fibers in a minimalist glucose-pyrene system <i>via</i> CH–π-stabilized “iotamers”

A kinetically controlled self-organization system was realized using the synthetically simple molecule 4,6-<i>O</i>-pyrenylidene glucose (Py-Glc). Unlike conventional supramolecular saccharide systems that converge into a thermodynamically stable state <i>via</i> strong hydrogen bonding, Py-Glc temporarily suppresses primary nucleation by forming kinetically favored CH-π-stabilized aggregates as a dormant product. These aggregates then directly transform into microfibers through hydrogen bonding. Notably, this transformation is not initiated from large aggregates but "iotamers" such as dimers, trimers, or tetramers. This stepwise transition is significantly accelerated by the addition of fibrous seeds. To the best of our knowledge, this is the first demonstration of the seeded self-assembly in a monosaccharide-based system. This study introduces a novel minimalist molecular-design strategy for the precise control over the self-assembly and provides a generalizable platform for carbohydrate-aromatic conjugate systems.