We have used DFT to calculate the vertical excitation energies and t 1/2 of a set of 26 hemi-thiophene photoswitches. Our findings suggest it is possible to simultaneously optimize these properties, generally considered inversely related simultaneously. We have also established a relationship between the Hammett parameters σ para and the calculated thermal barriers for 20 hemi-azothiophene systems. We found that EWGs lower the energy of the TS geometry through the delocalization of the 𝜋-NN electrons. We are collaborating with experimentalists to validate these design principles and produce azoarenes of interest to photopharmacology. D. M. A. and S.A.L. acknowledge the National Science Foundation CAREER award (NSF-CHE-2144556) and Camille Dreyfus Teacher-Scholar Award for funding. All authors appreciate the assistance from the Northeastern Research Computing Team and the computing resources provided by the Massachusetts Life Science Center grant (G00006360).