Engineering Supramolecular [<i>c</i>2]Daisy Chains for Structural Hierarchy-Dependent Emission and Photoreactivity

Organic photofunctional materials exhibit properties that are highly dependent on their structural hierarchy. The variability in intermolecular interactions and molecular packing in both monomeric and aggregated states complicates the controllability and predictability of their photophysical and photochemical properties. To address this challenge, we developed three luminescent supramolecular [<i>c</i>2]daisy chains as simplified models. The rigid and mutually embedded linkers between the host and guests facilitate the formation of [<i>c</i>2]daisy chains with balanced stability and dynamics. Additionally, the close and tunable π-π interactions between the luminescent units provide a structural basis for fluorescence modulation and topochemical photoreactions. We performed two sets of comparisons to assess luminescence and photoreactivity: one comparison involves molecules with and without crown ethers, and the other contrasting their behavior under UV excitation in solution (diluted and concentrated) versus in the aggregated and crystalline states. Specifically, in the crystalline state, [<i>c</i>2]daisy chains effectively stabilize molecular packing, leading to highly efficient dimer-dependent emission. This unique structure remains in both solution (<i>c</i> > 1 mM) and aggregated states, which can direct the reaction pathway toward rapid and efficient intermolecular photocycloaddition upon UV irradiation. However, in highly diluted solution (10 μM), [<i>c</i>2]daisy chains dissociate into monomers, which further undergo intramolecular photocyclization. This study provides new insights into employing supramolecular strategies for controllable molecular aggregation and the fine-tuning of photoreaction pathways and kinetics.