Helically Chiral Hybrid Cyclodextrin Metal-Organic Framework with Circularly Polarized Luminescence Kazem-Rostami, Masoud Orte Gutiérrez, Ángel Ortuño Guzmán, Ana María David, Arthur H. G. Roy, Indranil Miguel, Delia Garci, Amine Cruz, Carlos M. Stern, Charlotte L. Cuerva, Juan M. Stoddart, J. Fraser This document is the Accepted Manuscript version of a Published Work that appeared in final form in the Journal of the American Chemical Society, copyright © 2022 American Chemical Society, after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/articlesonrequest/AOR-NT9ZADBV72RDBFDSZNJY?_gl=1*1yv2wic*_ga*MTI3NjkyMTU3LjE3MjYxMzY0NTQ.*_ga_XP5JV6H8Q6*MTczNzYyMjQwNC40LjAuMTczNzYyMjQwNC42MC4wLjA 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)2 tunnels and held uniformly around an enantiomorphous 32 screw 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. 2025-01-23T09:18:29Z 2025-01-23T09:18:29Z 2022 journal article J. Am. Chem. Soc. 2022, 144, 21, 9380–9389 https://hdl.handle.net/10481/100098 10.1021/jacs.2c01554 eng http://creativecommons.org/licenses/by-nc-sa/4.0/ open access Atribución-NoComercial-CompartirIgual 4.0 Internacional