Temperature-Controlled Pathway Complexity in Self-Assembly of Perylene Diimide-Polydiacetylene Supramolecule

Self-assembly process represents one of the most powerful and efficient methods for designing functional nanomaterials. For generating optimal functional materials, understanding the pathway complexity during self-assembly is essential, which involves the aggregation of molecules into thermodynamically or kinetically favored pathways. Herein, a functional perylene diimide (PDI) derivative by introducing diacetylene (DA) chains (PDI-DA) is designed. Temperature control pathway complexity with the evolution of distinct morphology for the kinetic and thermodynamic product of PDI-DA is investigated in detail. A facile strategy of UV-induced polymerization is adopted to trap and capture metastable kinetic intermediates to understand the self-assembly mechanism. PDI-DA showed two kinetic intermediates having the morphology of nanosheets and nanoparticles before transforming into the thermodynamic product having fibrous morphology. Spectroscopic studies revealed the existence of distinct H- and J-aggregates for kinetic and thermodynamic products respectively. The polymerized fibrous PDI-DA displayed reversible switching between J-aggregate and H-aggregate.