Mix and Match Tuning of the Conformational and Multistate Redox Switching Properties of an Overcrowded Alkene,Journal of the American Chemical Society

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Mix and Match Tuning of the Conformational and Multistate Redox Switching Properties of an Overcrowded Alkene
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2024-09-13 , DOI: 10.1021/jacs.4c08284
Robert Hein ₁ , Charlotte N Stindt ₁ , Ben L Feringa ₁

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Overcrowded alkenes have received considerable attention as versatile structural motifs in a range of optical switches and light-driven unidirectional motors. In contrast, their actuation by electrochemical stimuli remains underexplored, even though this alternative energy input may be preferred in various applications and enables additional control over molecular switching states and properties. While symmetric bistricyclic overcrowded enes (BAEs) containing two identical halves based on either thioxanthene (TX) or acridine (Acr) motifs are known to be reversible conformational redox switches, their redox potentials are generally too high or low, respectively, thereby preventing wider applications. Herein, we demonstrate that the “mixed” TX-Acr switch possesses redox properties that lie between those of its parent symmetric analogs, enabling interconversion between three stable redox and conformational states at mild potentials. This includes the neutral anti-folded, the dicationic orthogonal, and a unique twisted monoradical cation state, the latter of which is only accessible in the case of the mixed TX-Acr switch and in a pathway-dependent manner. Consequently, with this multistate redox switch, a myriad of molecular properties, including geometry, polarity, absorbance, and fluorescence, can be modulated with high fidelity and reversibility between three distinct stable states. More generally, this study highlights the versatility of the “mix and match” approach in rationally designing redox switches with specific (redox) properties, which in turn is expected to enable a myriad of applications ranging from molecular logic and memory to actuators and energy storage systems.

中文翻译：

过度拥挤的烯烃的构象和多态氧化还原开关特性的混合和匹配调整

过度拥挤的烯烃作为一系列光开关和光驱动单向电机中的多功能结构图案而受到了相当大的关注。相比之下，它们通过电化学刺激的驱动仍然未得到充分探索，尽管这种替代能源输入在各种应用中可能是首选，并且可以对分子开关状态和性质进行额外控制。虽然已知包含基于噻杂蒽（TX）或吖啶（Acr）基序的两个相同半的对称双三环过度拥挤烯（BAE）是可逆构象氧化还原开关，但它们的氧化还原电位通常分别过高或过低，从而阻止了更广泛的应用。在此，我们证明了“混合”TX-Acr 开关具有介于其母体对称类似物之间的氧化还原特性，从而能够在温和电位下在三种稳定的氧化还原和构象状态之间相互转换。这包括中性反折叠、等对交和独特的扭曲单自由基阳离子态，后者仅在混合 TX-Acr 开关的情况下以通路依赖性方式访问。因此，通过这种多态氧化还原开关，可以在三种不同的稳定状态之间以高保真度和可逆性调节无数分子特性，包括几何形状、极性、吸光度和荧光。更一般地说，这项研究强调了“混合搭配”方法在合理设计具有特定（氧化还原）特性的氧化还原开关方面的多功能性，这反过来有望实现从分子逻辑和存储器到执行器和储能系统的无数应用。

更新日期：2024-09-13

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