Electrochemiluminescent COFs and HOFs as Porous Material Engineering Systems for Bioanalysis and Environmental Monitoring

Electrochemiluminescence (ECL) has emerged as a powerful biosensing technique owing to its high sensitivity and low background signal; however, limitations in stability, efficiency, and material diversity remain. This review summarizes recent advances in porous crystalline materials, with a focus on covalent organic frameworks (COFs) and hydrogen-bonded organic frameworks (HOFs), as emerging platforms for ECL sensing. COFs offer structural robustness, high surface area, and extended π-conjugated networks, enabling efficient charge transfer and ultrasensitive detection of biomolecules, toxins, and pesticides. In contrast, HOFs, constructed through reversible hydrogen bonding, provide superior processability, structural adaptability, and biocompatibility, making them attractive for detecting pathogens and heavy metal ions. Recent progress in luminophore engineering, nanostructure design, and co-reactant modulation has significantly improved ECL signal amplification, selectivity, and operational stability, leading to lower detection limits. Despite remaining challenges in large-scale synthesis, cost control, and the development of environmentally benign co-reactants, COF- and HOF-based systems show strong potential for integration with nanomaterials, biomolecular interfaces, and data-driven design strategies. These advances position porous organic frameworks as promising materials for next-generation, sustainable, and point-of-care ECL sensing technologies.