Multistate Aggregation‐Induced Chiroptical Properties of Enantiopure Disulfide‐Mediated BisPyrene Macrocycles

نویسندگان

چکیده

A chiral bispyrene macrocycle designed for exclusive intermolecular excimer fluorescence upon aggregation was synthesized by a double hydrothiolation of bis-enol ether followed intramolecular oxidation free thiols. Unusually high stereoselectivity achieved the thiol-ene additions under templated conditions and Et3B/O2 radical initiation. After enantiomer separation (chiral stationary phase HPLC), aqueous provoked aggregation. Detailed structural evolution afforded ECD/CPL monitoring. Three regimes can be observed characterized strong modifications in chiroptical patterns under, at, or above 70 % H2O : THF threshold. In luminescence, glum dissymmetry factors values were obtained, up to 0.022, as well sign inversion CPL signals during aggregation, behavior rationalized time-dependent density functional theory (TDDFT) calculations. Langmuir layers enantiopure disulfide macrocycles formed at air–water interface transferred onto solid substrates afford Langmuir–Blodgett films, which then studied AFM UV/ECD/fluorescence/CPL.

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ژورنال

عنوان ژورنال: Angewandte Chemie

سال: 2023

ISSN: ['1521-3773', '1433-7851', '0570-0833']

DOI: https://doi.org/10.1002/ange.202304075