Charge‐Delocalized Chiral Metal‐Organic Frameworks: Full‐Color Solvent‐Switchable Circularly Polarized Luminescence Toward Multi‐System Information Encryption

ABSTRACT The systematic design of chiral metal‐organic frameworks (MOFs) that combine structural rigidity with dynamic, full‐color gamut circularly polarized luminescence (CPL) remains a significant challenge. This study proposes a charge delocalization‐guided ligand functionalization strategy that enhances ligand p‐π conjugation and intramolecular charge transfer (ICT) by systematically regulating the quantity and location of amino groups on aromatic pyridine ligands, thereby enabling solid‐state continuous emission tuning across the full‐color gamut (385–661 nm). This series of MOFs exhibits rapid and reversible fluorescence switching in dichloromethane (DCM). Spectroscopic analysis and DFT calculations indicate that this is due to the weak N─H···Cl host‐guest interactions, which cause electronic localization of the ligands and a shift in the charge transfer mechanism from LMCT to LLCT. Notably, D/L‐DPA‐MOF and D/L‐DPAD‐MOF exhibit an asymmetry factor |g lum | as high as 10 −2 and outstanding CPL brightness in DCM. Capitalizing on the scalability of this series of layered columnar structures, we synthesized 2D chiral metal‐organic heterostructures and explored their applications in advanced optoelectronics. This work establishes a universal new paradigm for the development and information encryption application of dynamic full‐color gamut luminescent chiral MOFs through the precise control of excited‐state electron distribution.