摘要：

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.

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