In the first instance, we focused our efforts towards exploring the effect of H-TEDA(BF 4 ) 2 on the kinetics of a photochemical fluorination reaction. The kinetic studies were performed by a photoirradiation probe that allows on-line LED irradiation within the NMR spectrometer (see Supporting Information (SI) for details). Time-resolved 1 H{ F} NMR was used to track consumption of all starting materials and formation of all products. To mimic the exact conditions of the batch reaction, the same concentration (0.31 M) was used for kinetic measurements. The reaction yield/time of the NMR reactions are not directly comparable to the stirred reactions in batch due to the following limitations such as i) the light intensity transmitted from the LED to the reaction is low (due to losses from using an optical fiber to transmit light inside the NMR spectrometer), ii) the lack of stirring (an unavoidable disadvantage of in situ NMR kinetics) and iii) SF ® not being fully dissolved under these conditions. Reactions in NMR tubes do not reach as high yields/conversion rates as the batch reactions. Nevertheless, this approach was considered sufficient to interpret relative trends in reactions.