Research progress on the structural regulation of porphyrinand phthalocyanine-based materials and their photoelectrocatalytic applications

Porphyrins and phthalocyanines, endowed with highly conjugated p-systems and tunable coordination environments, have shown remarkable promise in photoelectrocatalysis and energy conversion. Yet, their intrinsic planar stacking, restricted charge transport, and insufficient structural stability remain major obstacles to performance optimization. This review focuses on the molecular design and structural regulation of porphyrin/phthalocyanine systems, summarizing representative modification strategies, including site substitution, side-chain engineering, axial coordination, and macromolecular framework construction. The underlying mechanisms by which these strategies modulate electronic structures, facilitate charge migration, and enhance catalytic activity are systematically elucidated. Recent advances in porphyrin- and phthalocyanine-based COFs, MOFs, and hybrid architectures for electrocatalysis, photocatalysis, and photodynamic therapy are also discussed. Finally, synergistic multilevel structuring and cross-scale regulation are identified as key directions for further performance enhancement, providing new insights into the rational design of high-efficiency photoelectrocatalytic materials.