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

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

    Organizational unit
    Laboratory of Professor Jérôme Lacour
    Type
    Dataset
    DOI
    10.26037/yareta:xu2ej353hnekvh2tcan2kjgbva
    License
    Creative Commons Attribution 4.0 International
    Keywords
    Stereoselective Double Thiol-Ene , Aggregation-Induced Excimer Fluorescence , Time-Dependent ECD , Multistate CPL , Langmuir-Blodgett Films
Publication date01/12/2022
Retention date06/05/2033
accessLevelPublicAccess levelPublic
SensitivityUndefined
duaNoneContract on the use of data
Contributors
  • Zhang, Ke-Feng orcid
  • Saleh, Nidal orcid
  • Swierczewski, Michal
  • Rosspeintner, Arnulf
  • Zinna, Francesco orcid
  • Besnard, Céline orcid
  • Guénée, Laure
  • Bürgi, Thomas orcid
  • Lacour, Jérôme orcid
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