Distinct class of photoinduced hydrogen-atom-transfer processes: phototautomerizations in molecules with no intramolecular hydrogen bond in the structure

Lapiński, Leszek; Rostkowska, Hanna; Nowak, Maciej J.

doi:10.1080/0144235x.2022.2030613

Cited by 5 publications

(1 citation statement)

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“…27,43 The mechanism of long-range PT in these compounds upon UV irradiation was revealed, very recently, by using matrix-isolated IR spectroscopy. 45 In the past few years, we have synthesized and studied a series of Schiff bases (7HQ-SB, Scheme 2B), where twist-assisted ESIPT occurs under suitable structural conditions, 46−48 but its efficiency is low due to the flexibility of the rotor, allowing competitive E/Z isomerization of the azomethine bond in the excited state. 49 Thus, all compounds considered so far for switching by means of long-range PT do not allow us to transfer enough molecules for a sufficient time into the on-state to generate a clean and stable switching signal.…”

Section: ■ Introductionmentioning

confidence: 99%

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

Rehhagen,

Argüello Cordero,

Kamounah

et al. 2024

J. Am. Chem. Soc.

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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.

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