Helically Chiral Hybrid Cyclodextrin Metal-Organic Framework Exhibiting Circularly Polarized Luminescence

Masoud Kazem-Rostami, Angel Orte, Ana M. Ortuño, Arthur H.G. David, Indranil Roy, Delia Miguel, Amine Garci, Carlos M. Cruz, Charlotte L. Stern, Juan M. Cuerva*, J. Fraser Stoddart*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

31 Scopus citations

Abstract

Three achiral polycyclic aromatic fluorophores-namely, 1-pyrenecarboxylic acid, 9-anthracenecarboxylic acid, and perylene-3,9-dicarboxylic acid-were chosen based on their desired properties before being incorporated into the construction of a K+-carrying gamma-cyclodextrin (γ-CD)-based metal-organic framework (CD-MOF-1) and γ-CD-containing hybrid frameworks (CD-HFs). Among these fluorophores, only the pyrene-carrying one shows significant noncovalent bonding interactions with γ-CD in solution. This fluorophore is encapsulated in a CD-HF with a trigonal superstructure instead of the common cubic CD-MOF-1 found in the case of the other two fluorophores. Single-crystal X-ray diffraction analysis of the trigonal CD-HF reveals a π-stacked chiral positioning of the pyrene-carrying fluorophore inside the (γ-CD)2tunnels and held uniformly around an enantiomorphous 32screw axis along the c direction in the solid-state structure. This helix-like structure demonstrates an additional level of chirality over and above the point-chiral stereogenic centers of γ-CD and the axial chirality associated with the self-assembled π-stacked fluorophores. These arrangements result in specifically generated photophysical and chiroptical properties, such as the controlled emergence of circularly polarized luminescence (CPL) emission. In this manner, a complete understanding of the mechanism of chirality transfer from a chiral host (CD-HF) to an encapsulated achiral fluorophore has been achieved, an attribute which is often missing in the development of materials with CPL.

Original languageEnglish (US)
Pages (from-to)9380-9389
Number of pages10
JournalJournal of the American Chemical Society
Volume144
Issue number21
DOIs
StatePublished - Jun 1 2022

ASJC Scopus subject areas

  • Chemistry(all)
  • Biochemistry
  • Catalysis
  • Colloid and Surface Chemistry

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