Restriction of Intramolecular Motion(RIM):Investigating AIE Mechanism from Experimental and Theoreti

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Mechanistic studies promote scientific development from phenomena to theories.Aggregation-induced emis-sion(AIE),as an unusual photophysical phenomenon,builds the bridge between molecular science and aggregate mesoscience.With the twenty-year development of AIE,restriction of intramolecular motion(RIM)has been verified as the working mechanism of AIE effect.In this review,these mechanistic works about RIM are summarized from experimental and theoretical per-spectives.Thereinto,the experimental studies are introduced from three parts:external rigidification,structural modification and struc-tural characterization.In the theoretical part,calculations on the low-frequency motion of AIEgens have been performed to prove the RIM mechanism.By virtue of the theoretical calculations,some new mechanisms are proposed to supplement the RIM,such as re-striction of access to conical intersection,suppression of Kasha tran-sition,restriction of access to dark state,etc.It is foreseeable that the RIM mechanism will unify the photophysical theories for both molecules and aggregates,and inspire more progress in aggregate science.
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