TY - JOUR

T1 - Reversible Switching Based on Truly Intramolecular Long-Range Proton Transfer─Turning the Theoretical Concept into Experimental Reality

AU - Rehhagen, Chris

AU - Argüello Cordero, Miguel A.

AU - Kamounah, Fadhil S.

AU - Deneva, Vera

AU - Angelov, Ivan

AU - Krupp, Marvin

AU - Svenningsen, So̷ren W.

AU - Pittelkow, Michael

AU - Lochbrunner, Stefan

AU - Antonov, Liudmil

N1 - Funding Information: Bulgarian National Science Fund (projects KP-06-DV-9/2019 and D01–168/2022); Alexander von Humboldt Foundation; German Science Foundation (projects 441234705, 404479188, and 437567992); Danish Council for Independent Research (DFF 4181–00206 and 9040–00265). Funding Information: Dedicated to Jakob (Joggi) Wirz (1942–2022), an inspiring mentor and generous colleague. The Bulgarian National Science Fund within the National Science Program VIHREN by project T-Motors (contracted as KP-06-DV-9/2019) is acknowledged for the financial support for this investigation. The authors acknowledge also the generous support from The Alexander von Humboldt Foundation (follow-up fellowship of L.A.) and the access provided to the e-infrastructure of the NCHDC ─part of the Bulgarian National Roadmap on RIs─with the financial support of Grant No. D01-168/28.07.2022. Furthermore, the authors are thankful to the German Science Foundation for financial support via the collaborative research center SFB 1477 “Light-Matter Interactions at Interfaces” (project number 441234705), the priority program SPP 2102 “Light Controlled Reactivity of Metal Complexes” (project number 404479188), and the international research training group IRTG 2676 “Imaging quantum systems: photons, molecules, materials” (project number 437567992). M.P. appreciates the support from the Danish Council for Independent Research (DFF 4181-00206 and 9040-00265) and from the University of Copenhagen. Publisher Copyright: © 2024 American Chemical Society.

PY - 2024

Y1 - 2024

N2 - Herein, we demonstrate a working prototype of a conjugated proton crane, a reversible tautomeric switching molecule in which truly intramolecular long-range proton transfer occurs in solution at room temperature. The system consists of a benzothiazole rotor attached to a 7-hydroxy quinoline stator. According to the experimental and theoretical results, the OH proton is delivered under irradiation to the quinolyl nitrogen atom through a series of consecutive proton transfer and twisting steps. The use of a rigid rotor prevents undesired side processes that decrease the switching performance in previously described proton cranes and provides an unprecedented switching efficiency and fatigue resistance. The newly designed system confirms the theoretical concept for the application of proton transfer-initiated intramolecular twisting as the switching mechanism, developed more than 10 years ago, and provides unique insights for the further development of tautomeric molecular switches and motors, molecular logic gates, and new molecular-level energy storage systems.

AB - Herein, we demonstrate a working prototype of a conjugated proton crane, a reversible tautomeric switching molecule in which truly intramolecular long-range proton transfer occurs in solution at room temperature. The system consists of a benzothiazole rotor attached to a 7-hydroxy quinoline stator. According to the experimental and theoretical results, the OH proton is delivered under irradiation to the quinolyl nitrogen atom through a series of consecutive proton transfer and twisting steps. The use of a rigid rotor prevents undesired side processes that decrease the switching performance in previously described proton cranes and provides an unprecedented switching efficiency and fatigue resistance. The newly designed system confirms the theoretical concept for the application of proton transfer-initiated intramolecular twisting as the switching mechanism, developed more than 10 years ago, and provides unique insights for the further development of tautomeric molecular switches and motors, molecular logic gates, and new molecular-level energy storage systems.

U2 - 10.1021/jacs.3c10789

DO - 10.1021/jacs.3c10789

M3 - Journal article

C2 - 38214997

AN - SCOPUS:85182571429

VL - 146

SP - 2043−2053

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 3

ER -