Restriction of Access to the Dark State: A New Mechanistic Model for Heteroatom‐Containing AIE Systems

Abstract Restriction of intramolecular motion (RIM), as the working mechanism of aggregation‐induced emission (AIE), cannot fully explain some heteroatom‐containing systems. Now, two excited states are taken into account and a mechanism, restriction of access to dark state (RADS), is specified to elaborate RIM and complete the picture of AIE mechanism. A nitrogen‐containing molecule named APA is chosen as a model compound; its weak fluorescence in solution is ascribed to the easy access from the bright (π,π*) state to the close‐lying dark (n,π*) state. By either metal complexation or aggregation, the dark state is less accessible due to restriction of the molecular motion leading to the dark state and elevation of the dark state energy, thus the bright state emission is restored. RADS is powerful in elucidating the AIE effect of molecules with excited states favoring non‐radiative decay, including overlap‐forbidden states such as (n,π*) and CT states, spin‐forbidden triplet states, and so on.