Computational Design and Synthesis of a Deeply Red-Shifted and Bistable Azobenzene

We computationally dissected the electronic and geometrical influences of ortho -chlorinated azobenzenes on their photophysical properties. X-ray analysis provided the insight that trans -tetra- ortho -chloro azobenzene is conformationally flexible and thus subject to molecular motions. This allows the photoswitch to adopt a range of red-shifted geometries, which account for the extended n → π* band tails. On the basis of our results, we designed the di -ortho -fluoro di- ortho -chloro ( dfdc ) azobenzene and provided computational evidence for the superiority of this substitution pattern to tetra- ortho -chloro azobenzene. Thereafter, we synthesized dfdc azobenzene by ortho -chlorination via 2-fold C-H activation and experimentally confirmed its structural and photophysical properties through UV-vis, NMR, and X-ray analyses. The advantages include near-bistable isomers and an increased separation of the n → π* bands between the trans - and cis -conformations, which allows for the generation of unusually high levels of the cis -isomer by irradiation with green/yellow light as well as red light within the biooptical window.