By inspecting the FMOs (Figure ), one can easily anticipate whether these molecules are capable of photoswitching or not. Indeed, T-CP-T is a well-known photoswitch, while photoswitching of compounds TNaph-CP-TNaph and TAnt-CP-TAnt has not been reported, in line with delocalization of the LUMO towards the extended π-conjugated side groups, preventing the ring closing photoreaction. On the other hand, our calculations predict that TfPh-CP-TfPh and its backbone-fluorinated counterpart, TfPh-F6CP-TfPh, should be able to undergo photocyclization. Indeed, photoswitching in the latter has been experimentally demonstrated. Note that while there are additional factors that may affect the photoswitching activity of these compounds, our results only inform on the capability to photoswitch or not. Moreover, the consistency of our results with experimental observations is not proof that our approach can explain all the details of the photocyclization process, but rather an indication that it can capture the relevant chemical characteristics that largely dictate whether a photoreaction can occur or not.