Mesoscale Acid–Base Complexes Display Size‐Associated Photophysical Property and Photochemical Activity

Abstract The properties of single molecules and molecular aggregates can differ dramatically, leading to a long‐standing interest in mesoscale aggregation processes. Herein, a series of acid‐base molecular complexes is developed by using a tetraphenylethylene‐backboned fluorophore, and investigated the photophysical properties and photochemical activities at different aggregation length scales. This fluorophore, with two basic diethylamine groups and two acidic tetrazole groups, exhibits sparse solubility due to multivalent interactions that cause infinite aggregation. The addition of a third acid leads to the formation of fluorophore/acid complexes with good dispersibility and colloidal stability. This assembly process can be controlled by the use of different acids and their stoichiometry, resulting in aggregates ranging in size from a few to hundreds of nanometers. A crystalline structure is obtained to illustrate the complex properties of the acid‐base network. Unlike the single molecule, these complexes show a trend of size‐related properties for photoluminescence efficiency and photochemical activity. As the amount of acid added increases, the size of the complexes decreases, the aggregation effect of the complexes on fluorescence emission increases, and the rates of the oxidative photocyclization and photodecomposition slow down. This work may help to understand size‐controlled molecular materials at the mesoscale for functional design.