Photoresponsive molecules can undergo conformational changes, such as cis/trans isomerization or ring-opening/closing, and these structural changes often lead to diverse responses. For example, optical changes (UV-vis, luminescence) of these molecules have been studied for sensors, bioimaging, and other light-controlled materials. To develop this type of molecule, the important point is how to design them in a rational way. For this, understanding the properties of the isomers and the thermodynamic energy profile is essential, so we can predict stability, switching pathways, and the expected behavior in the excited state. Recently, our group published the paper “Semi-Automated Pipeline for Transition State Search of Molecular Photoswitches” (http://doi.org/10.1002/cptc.202500126), where we calculated a set of potential photoswitches using a programmed workflow to automatically identify transition states and select the most promising compounds. Currently, we are interested in diarylethene (DAE) photoswitches. DAE molecules are known for their reversible ring-opening/closing reaction under UV or visible light and typically show good fatigue resistance. However, in this project, we focus on a non-conventional version, specifically aza-DAE systems. Experimentally, we observed that the aza-DAE switch shows a more red-shifted absorption band and switching on the nanosecond time scale. Therefore, in this project, we aim to perform computational studies to understand the switching mechanism and photophysical properties of this new type of aza-DAE photoswitches.