Promoting the Furan Ring?Opening Reaction to Access New Donor–Acceptor Stenhouse Adducts with Hexafluoroisopropanol

Donor–acceptor Stenhouse adducts (DASAs) are visible-light-responsive photoswitches with a variety of emerging applications in photoresponsive materials. Their two-step modular synthesis, centered on the nucleophilic ring opening an activated furan, makes DASAs readily accessible. However, use less reactive donors or acceptors renders process slow and low yielding, which has limited their development. We demonstrate here that 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) promotes ring-opening reaction stabilizes open isomer, allowing greatly reduced times increased yields for known derivatives. In addition, it provides access to previously unattainable DASA-based DASA–polymer conjugates. The role HFIP photochromic properties set new is probed using combination 1H NMR UV/Vis spectroscopy. sterically hindered, electron-poor amines enabled dark equilibrium be decoupled from closed-isomer half-lives first time.