Turning on Singlet Oxygen Generation by Outer‐Sphere Microenvironment Modulation in Porphyrinic Covalent Organic Frameworks for Photocatalytic Oxidation

Abstract Singlet oxygen ( 1 O 2 ) is ubiquitously involved in various photocatalytic oxidation reactions; however, efficient and selective production of 1 O 2 is still challenging. Herein, we reported the synthesis of nickel porphyrin‐based covalent organic frameworks (COFs) incorporating functional groups with different electron‐donating/‐withdrawing features on their pore walls. These functional groups established a dedicated outer‐sphere microenvironment surrounding the Ni catalytic center that tunes the activity of the COFs for 1 O 2 ‐mediated thioether oxidation. With the increase of the electron‐donating ability of functional groups, the modulated outer‐sphere microenvironment turns on the catalytic activity from a yield of nearly zero by the cyano group functionalized COF to an excellent yield of 98 % by the methoxy group functionalized one. Electronic property investigation and density‐functional theory (DFT) calculations suggested that the distinct excitonic behaviors attributed to the diverse band energy levels and orbital compositions are responsible for the different activities. This study represents the first regulation of generating reactive oxygen species (ROS) based on the strategy of outer‐sphere microenvironment modulation in COFs.