Proton‐Gated Ring‐Closure of a Negative Photochromic Azulene‐Based Diarylethene

Abstract Proton‐responsive photochromic molecules are attractive for their ability to react on non‐invasive rapid optical stimuli and the importance of protonation/deprotonation processes in various fields. Conventionally, their acidic/basic sites are on hetero‐atoms, which are orthogonal to the photo‐active π‐center. Here, we incorporate azulene, an acid‐sensitive pure hydrocarbon, into the skeleton of a diarylethene‐type photoswitch. The latter exhibits a novel proton‐gated negative photochromic ring‐closure and its optical response upon protonation in both open and closed forms is much more pronounced than those of diarylethene photoswitches with hetero‐atom based acidic/basic moieties. The unique behavior of the new photoswitch can be attributed to direct protonation on its π‐system, supported by 1 H NMR and theoretical calculations. Our results demonstrate the great potential of integrating non‐alternant hydrocarbons into photochromic systems for the development of multi‐responsive molecular switches.