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

Clerc, Michèle; Stricker, Friedrich; Ulrich, Sebastian; Sroda, Miranda; Bruns, Nico; Boesel, Luciano F.; Read de Alaniz, Javier

doi:10.1002/ange.202100115

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

Journal Article · 17 March 2021 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202100115 · OSTI ID:1771375

Clerc, Michèle ^[1]; Stricker, Friedrich ^[2];

^[3]; Sroda, Miranda ^[2];

^[4];

^[3];

^[2]

Empa Swiss Federal Laboratories for Materials Science and Technology Laboratory for Biomimetic Membranes and Textiles Lerchenfeldstrasse 5 9014 St. Gallen Switzerland, Department of Chemistry University of Fribourg 1700 Fribourg Switzerland, Department of Pure and Applied Chemistry University of Strathclyde Glasgow G1 1XL UK
Department of Chemistry and Biochemistry University of California Santa Barbara CA 93106 USA
Empa Swiss Federal Laboratories for Materials Science and Technology Laboratory for Biomimetic Membranes and Textiles Lerchenfeldstrasse 5 9014 St. Gallen Switzerland
Department of Pure and Applied Chemistry University of Strathclyde Glasgow G1 1XL UK

Abstract 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 of an activated furan, makes DASAs readily accessible. However, the use of less reactive donors or acceptors renders the 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 the ring‐opening reaction and stabilizes the open isomer, allowing greatly reduced reaction times and increased yields for known derivatives. In addition, it provides access to previously unattainable DASA‐based photoswitches and DASA–polymer conjugates. The role of HFIP and the photochromic properties of a set of new DASAs is probed using a combination of ¹ H NMR and UV/Vis spectroscopy. The use of sterically hindered, electron‐poor amines enabled the dark equilibrium to be decoupled from closed‐isomer half‐lives for the first time.

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Sponsoring Organization:: USDOE

OSTI ID:: 1771375

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 18 Vol. 133; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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