Solvent‐Regulated CPL Enhancement via Chiral Transfer in Efficient Luminescent Ionic Hydrogen‐Bonded Frameworks for Information Encryption

Circularly polarized luminescence (CPL) materials have garnered significant attention due to their broad application prospects in information-encryption and optical storage. However, chiral small-molecule systems face challenges such as intramolecular chiral-transfer confinement and low energy transfer efficiency, making it difficult to achieve breakthroughs in chiral optical properties using a single component. We propose a multistage chiral-transfer-strategy based on ionic hydrogen-bonded organic frameworks (iHOFs), utilizing (1R/1S,2R/2S)-1, 2-diphenylethylenediamine-(R/S-DPEN) as the chiral source and 4,4'-bis(2-sulfonatostyryl)biphenyl-(H₂CBS) as the chromophore to synthesize R/S-iHOF-40. Our study reveals that the introduction of an effective charge donor modulates the excited-state energy gap, which is the primary reason for R/S-iHOF-40's high quantum yield (QY) of 67.8% (compared to 5.41% for HOF-R/S-DPEN). Furthermore, the strong mirror cotton effect observed at 323 nm for R/S-iHOF-40 confirms effective intermolecular chiral-transfer, while the crystal structure clearly reveals a double-helix supramolecular assembly mechanism mediated by hydrogen-bond bridging. Interestingly, the interference of water molecule motion within the structure on the chiral coupling between ions demonstrates the crucial role of hydrogen-bond dynamics in regulating the chiral emission of the R/S-iHOF-40 excited state. This work deepens our understanding of the mechanisms of chiral-transfer and amplification, and provides new strategies for the application of solid-state chiral materials in information-encryption.