Supramolecular Hydrogen-Bonding Networks Amplify Luminol/O₂ Chemiluminescence by over 4000-Fold: Mechanistic Insights and Biosensing Application

Classic luminol-H₂O₂ chemiluminescence (CL) systems are plagued by inherent self-decomposition, which compromises detection reliability. Although luminol-dissolved oxygen systems circumvent this issue, their ultralow reactivity necessitates innovative catalytic microreactor design. Herein, we pioneer a hydrogen-bonded organic framework (HOF) constructed from metal-organic square units and 1,2-propanediamine ligands as terminal hydrogen-bonding sites, achieving an unprecedented 4284-fold CL enhancement in luminol-O₂ systems. HOF with porous zeolite-like supramolecular assemblies (ZSA) serves as the coreaction accelerator with strong O₂ adsorption at tetrahedral Co-N/O sites that activates O₂ to generate reactive oxygen species (ROS). And the kinetic confinement effect provided by the ZSA host with suitable channel and hydrogen-bonding contributions efficiently captured the luminol emitter in the nanocages, shortening electron-transfer pathways and reducing nonradiative energy loss. And the synergistic confinement catalysis enhanced CL performance is linearly related to the O₂ adsorption capacity of the ZSA series (ZSA-1, ZSA-3, and ZSA-4). Theoretical calculations further confirmed that the adsorption of O₂ and luminol in ZSA-1 optimizes the electron-transfer pathways to promote CL emission performances compared with those of zeolitic imidazolate framework-67 (ZIF-67). This work not only expands the application of HOF in the field of CL but also provides new insights for engineering materials to boost the CL photon emission efficiency of weak luminol-O₂ systems.