Alkyl Chain Length Dependent Luminescence and Single‐Component White‐Light Emission from Gemini Aliphatic Quaternary Ammonium Salts

Abstract Aliphatic quaternary ammonium salts (QASs) with intrinsic photoluminescence (PL) have drawn increasing attention due to the importance of exploring the mechanism of ionic emissive clusters, whereas it remains challenging to clarify structure–property relationships. Here, the effective modulation of photophysical properties of gemini aliphatic QASs (n‐BTADB) is managed by altering the alkyl chain length. Boosted quantum yields (up to 24.6%), prolonged phosphorescence lifetimes (up to 515.2 ms), and varied PL colors are achieved by manipulating the aggregation states of the compounds. Interlaced herringbone packing patterns and strong ionic interactions facilitate the intersystem crossing process and stabilize the triplets. The confluence of varied hydrophobic interactions and chain flexibility results in the fluctuation of phosphorescence lifetimes as the alkyl chain lengthens. Furthermore, the single‐component white‐light emission is obtained in 12‐HBTADB crystals by introducing electron‐rich hydroxyls. These results shed new light on the structure–property relationships of ionic emissive clusters and the rational design of nonconventional ionic luminophores.