Abstract
Porphyrins and phthalocyanines are cornerstone molecular architectures for photodynamic therapy (PDT), organic photovoltaics, and artificial photosynthesis, prized for their exceptional photophysical properties. However, their extended planar π-conjugated systems inevitably induce aggregation-caused quenching (ACQ) through strong π-π stacking interactions, severely diminishing critical performance metrics like photothermal conversion efficiency and reactive oxygen species (ROS) generation. Porous organic polymers (POPs) have emerged as a transformative platform to overcome this limitation, offering unique capabilities for spatially isolating these photoactive units while maintaining structural integrity and enabling precise porosity control. This comprehensive review systematically analyzes structure-property relationships in porphyrin/phthalocyanine-based POPs. It presents detailed case studies showcasing effective π-stacking suppression strategies and offers forward-looking perspectives for designing next-generation materials optimized for photophysical performance. Key design strategies include host-guest architectures (e.g., β-cyclodextrin-threaded Por-CD-COF), modulating interlayer spacing to enhance photodynamic efficiency, stereochemical engineering (e.g., isomeric iso-CMPs), leveraging steric hindrance to prevent π-stacking while amplifying enzyme-mimetic activities, and dynamic covalent linkages (e.g., imine/boronate bonds), enabling stimuli-responsive chromophore repositioning, multi-component hybrids (e.g., MOF@COF heterostructures), integrating catalytic cores with photoactive shells for synergistic performance enhancement. By summarizing key advances and providing forward-looking perspectives, this review aims to inspire the rational design of next-generation POP-based materials with optimized photophysical properties, paving the way for their broader application in antimicrobial therapy, energy conversion, and beyond.