The radical fluoroalkylation of isocyanides with fluorinated sulfones is enabled by visible-light photoredox catalysis. A wide range of readily available mono-, di-, and trifluoromethyl heteroaryl sulfones can thus be used as efficient radical fluoroalkylation reagents under mild conditions. This method not only describes a new synthetic application of fluorinated sulfones, but also provides a new route to fluoroalkyl radicals.

Photoresponsive metal–organic frameworks (PMOFs) are of interest for tailorable CO2 adsorption. However, modulation of CO2 adsorption on PMOFs is based on steric hindrance or structural change owing to weak interactions between CO2 and active sites. It is challenging to fabricate PMOFs with strong but tailorable sites for CO2 adsorption. Now, the construction of PMOFs with target‐specific (strong) active sites is achieved by introducing tetraethylenepentamine into azobenzene‐functionalized MOFs for tailorable CO2 adsorption. Amines are specific active sites for CO2, contributing to capture CO2 selectively. Cis/trans isomerization of azobenzene motifs trigged by UV/Vis light adjusts the electrostatic potential of amines significantly, leading to exposure/shelter of amines and modulation of CO2 adsorption on strong active sites. This system enables us to design adsorption processes for CO2 capture from mixtures, which is impossible to realize by traditional PMOFs.

Fluorinated sulfinate salts RfSO2Na (Rf = CF2H, CF2Ph, and CH2F) have been prepared via NaBH4-mediated reduction of the corresponding benzo[d]thiazol-2-yl sulfones, and their synthetic application as di- and monofluoroalkyl radical precursors is demonstrated in the silver-catalyzed cascade fluoroalkylation/aryl migration/SO2 extrusion of conjugated N-arylsulfonylated amides.