Porphyrin based covalent organic frameworks via self-polycondensation for heterogeneous photocatalysis

A novel porphyrin based covalent organic frameworks (Por-BABN-COF) has been successfully constructed via self-polycondensation of a newly developed A2B2 porphyrin building block possessing two amino groups and two neopentyl acetal at the meso-position. Por-BABN-COF was employed as a heterogeneous photocatalyst for the selective oxidation of sulfides and CO2 cycloaddition due to its superior light absorption capacity, strong crystallinity and high stability. The high conversion, good selectivity and excellent reusability indicate Por-BABNCOF is a promising photocatalyst for both reactions. Mechanistic investigations confirm that electron transfer pathways contribute to the formation of sulfoxides. This study presents a new strategy for designing and developing high-efficient porphyrin-based COFs as heterogeneous photocatalysts for selective organic transformations.