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

Abstract

AbstractSelf‐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.