Chemically fueled dynamic switching between assembly-encoded emissions

Abstract

Self-assembly provides access to non-covalently synthesized supramolecular materials with distinct properties from a single building block. However, dynamic switching between functional states still remains challenging, but holds enormous potential in material chemistry to design smart materials. Herein, we demonstrate a chemical fuel-mediated strategy to dynamically switch between two distinctly emissive aggregates, originating from the self-assembly of a naphthalimide-appended peptide building block. A molecularly dissolved building block shows very weak blue emission, whereas, in the assembled state (Agg-1), it shows cyan emission through π stacking-mediated excimer emission. The addition of a chemical fuel, ethyl-3-(3-(dimethylamino)propyl)carbodiimide (EDC), converts the terminal aspartic acid present in the building block to an intra-molecularly cyclized anhydride in situ forming a second aggregated state, Agg-2, by changing the molecular packing, thereby transforming the emission to strong blue. Interestingly, the anhydride gets hydrolyzed gradually to reform Agg-1 and the initial cyan emission is restored. The kinetic stability of the strong blue emissive aggregate, Agg-2, can be regulated by the added concentration of the chemical fuel. Moreover, we expand the scope of this system within an agarose gel matrix, which allows us to gain spatiotemporal control over the properties, thereby producing a self-erasable writing system where the chemical fuel acts as the ink.