A Chiral Recognition System Orchestrated by Self‐Assembly: Molecular Chirality, Self‐Assembly Morphology, and Fluorescence Response. Issue 41 (28th August 2017)

• Record Type: Journal Article
• Authors: Noguchi, Takao; Roy, Bappaditya; Yoshihara, Daisuke; Sakamoto, Junji; Yamamoto, Tatsuhiro; Shinkai, Seiji
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 41(2017)
• Page Start: 12518
• Page End: 12522
• Publication Date: 2017-08-28
• Subjects: chirality -- fluorescent probes -- molecular recognition -- self-assembly -- supramolecular chemistry; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201706142
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The newly developed oligophenylenevinylene (OPV)‐based fluorescent (FL) chiral chemosensor (OPV‐Me) for the representative enantiomeric guest, 1, 2‐cyclohexanedicarboxylic acid (1, 2‐CHDA: RR ‐ and SS ‐form) showed the high chiral discrimination ability, resulting in the different aggregation modes of OPV‐Me self‐assembly: RR ‐CHDA directed the fibrous supramolecular aggregate, whereas SS ‐CHDA directed the finite aggregate. The consequent FL intensity toward RR ‐CHDA was up to 30 times larger than that toward SS ‐CHDA. Accordingly, highly enantioselective recognition was achieved. Application to the chirality sensing was also possible: OPV‐Me exhibited a linear relationship between the FL intensity and the enantiomeric excess through the morphological development of stereocomplex aggregates. These results clearly show that the chiral recognition ability is manifested by the amplification cascade of the chirality difference through self‐assembly. Abstract : Chiral recognition of a guest enantiomer has been achieved by self‐assembly of a fluorescent chiral chemosensor. The highly enantioselective recognition is due to the amplification of the small steric difference through self‐assembly into the macroscopic aggregation properties (see picture). This molecular assembly system is advantageous for chiral discrimination by the fluorescent sensing.