Porphyrin-Based Covalent Organic Frameworks: Design, Synthesis, Photoelectric Conversion Mechanism, and Applications

Photosynthesis occurs in high plants, and certain organisms show brilliant technology in converting solar light to chemical energy and producing carbohydrates from carbon dioxide (CO₂). Mimicking the mechanism of natural photosynthesis is receiving wide-ranging attention for the development of novel materials capable of photo-to-electric, photo-to-chemical, and photocatalytic transformations. Porphyrin, possessing a similar highly conjugated core ring structure to chlorophyll and flexible physical and chemical properties, has become one of the most investigated photosensitizers. Chemical modification and self-assembly of molecules as well as constructing porphyrin-based metal (covalent) organic frameworks are often used to improve its solar light utilization and electron transfer rate. Especially porphyrin-based covalent organic frameworks (COFs) in which porphyrin molecules are connected by covalent bonds combine the structural advantages of organic frameworks with light-capturing properties of porphyrins and exhibit great potential in light-responsive materials. Porphyrin-based COFs are expected to have high solar light utilization, fast charge separation/transfer performance, excellent structural stability, and novel steric selectivity by special molecular design. In this paper, we reviewed the research progress of porphyrin-based COFs in the design, synthesis, properties, and applications. We focused on the intrinsic relationship between the structure and properties, especially the photoelectric conversion properties and charge transfer mechanism of porphyrin-based COFs, and tried to provide more valuable information for the design of advanced photosensitizers. The applications of porphyrin-based COFs in photocatalysis and phototherapy were emphasized based on their special structure design and light-to-electric (or light-to-heat) conversion control.