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Spatial Confinement Tunes Cleavage and Re‐Formation of C=N Bonds in Fluorescent Molecules
Author(s) -
Liu Keyan,
Qiao Xuezhi,
Huang Chuanhui,
Li Xiao,
Xue Zhenjie,
Wang Tie
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202103471
Subject(s) - fluorophore , nile red , fluorescence , molecule , chemistry , chemical physics , cationic polymerization , photochemistry , cleavage (geology) , micelle , nanotechnology , materials science , optics , organic chemistry , aqueous solution , physics , fracture (geology) , composite material
Molecules in confined spaces exhibit unusual behaviors that are not typically observed in bulk systems. Such behavior can provide alternative strategies for exploring new reaction pathways. Cleavage of the C=N bond of Nile red (NR) in solution is an irreversible reaction. Here, we used spatial confinement within a cationic micelle‐confined system to convert this reaction to a reversible process. The fluorescence of NR shifted between red and green for nine cycles. The new chemical pathway based on spatial confinement can be attributed to two factors: increasing the local concentration of reactants and reducing the reaction energy barrier. This effect is supported by both experimental evidence and theoretical calculations. The cross‐linked silica shell comprising the confinement chamber stabilizes the enclosed molecules. This reduces fluorophore leakage and maintains fluorescence intensity in most environments, including in solution, on paper, and in hydrogel films, and expands practical applications in encrypted information and multi‐informational displays.