交叉共轭控制杂氮杂环光开关的稳定性和光物理性质,Organic & Biomolecular Chemistry

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交叉共轭控制杂氮杂环光开关的稳定性和光物理性质
Organic & Biomolecular Chemistry ( IF 2.9 ) Pub Date : 2021-12-28 , DOI: 10.1039/d1ob02026a
Daniel M Adrion ₁ , Steven A Lopez ₁

Affiliation

偶氮烯光开关是多功能分子，可通过光从E异构体转换为Z异构体。偶氮苯是一种典型的光开关，但其衍生物可能很不适合体内应用，例如光药理学，因为紫外线促进了不希望的光化学反应和Z异构体的相对较短的半衰期 ( t _1/2 ) (2 天) . 实验和计算研究表明，这些性质（E异构体的λ ^max和Z的t _1/2-异构体）是负相关的。我们从 1540 种偶氮芳烃的高通量筛选研究中鉴定出异构偶氮二噻吩和偶氮二呋喃作为光开关候选物，相对于偶氮苯具有改进的λ ^max和t _1/2值。我们使用密度泛函理论来预测2,2-和3,3-取代的偶氮二噻吩和偶氮二呋喃的E-和Z-异构体的活化自由能和垂直激发能。半衰期取决于杂环是π共轭还是与重氮π键交叉共轭。2,2-取代的偶氮芳烃均具有t _1/21 小时尺度上的值，而 3,3-类似物计算的半衰期为 40 年和 230 年（分别为噻吩和呋喃）。与它们的 3,3-取代类似物相比，2,2-取代的杂偶氮芳烃具有显着更高的λ ^max吸收：偶氮呋喃为 76 nm，偶氮噻吩为 77 nm。

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Cross-conjugation controls the stabilities and photophysical properties of heteroazoarene photoswitches

Azoarene photoswitches are versatile molecules that interconvert from their E-isomer to their Z-isomer with light. Azobenzene is a prototypical photoswitch but its derivatives can be poorly suited for in vivo applications such as photopharmacology due to undesired photochemical reactions promoted by ultraviolet light and the relatively short half-life (t_1/2) of the Z-isomer (2 days). Experimental and computational studies suggest that these properties (λ^max of the E isomer and t_1/2 of the Z-isomer) are inversely related. We identified isomeric azobisthiophenes and azobisfurans from a high-throughput screening study of 1540 azoarenes as photoswitch candidates with improved λ^max and t_1/2 values relative to azobenzene. We used density functional theory to predict the activation free energies and vertical excitation energies of the E- and Z-isomers of 2,2- and 3,3-substituted azobisthiophenes and azobisfurans. The half-lives depend on whether the heterocycles are π-conjugated or cross-conjugated with the diazo π-bond. The 2,2-substituted azoarenes both have t_1/2 values on the scale of 1 hour, while the 3,3-analogues have computed half-lives of 40 and 230 years (thiophene and furan, respectively). The 2,2-substituted heteroazoarenes have significantly higher λ^max absorptions than their 3,3-substituted analogues: 76 nm for azofuran and 77 nm for azothiophene.

更新日期：2022-01-11

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