Phenylazothiazoles as Visible-Light Photoswitches,Journal of the American Chemical Society

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Phenylazothiazoles as Visible-Light Photoswitches
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-04-12 , DOI: 10.1021/jacs.3c00609
Runze Lin _{1,

2} , P K Hashim _{1,

2} , Saugata Sahu ₁ , Ammathnadu S Amrutha _{1,

2} , Nusaiba Madappuram Cheruthu _{1,

2} , Shakkeeb Thazhathethil _{1,

2} , Kiyonori Takahashi _{1,

3} , Takayoshi Nakamura _{1,

3} , Takashi Kikukawa _{2,

4} , Nobuyuki Tamaoki _{1,

2}

Affiliation

A novel class of photoswitches based on a phenylazothiazole scaffold that undergoes reversible isomerization under visible-light irradiation is reported. The photoswitch, which comprises a thiazole heteroaryl segment directly connected to a phenyl azo chromophore, has very different spectral characteristics, such as a redshifted absorption maximum wavelength and well-separated absorption bands of the trans and cis isomers, than conventional azobenzene and other heteroaryl azo compounds. Substituents at the ortho and para positions of the phenyl ring of the photoswitch resulted in a further shift to longer wavelengths up to 525 nm at the absorption maximum with a small thermal stability compensation. These photoswitches showed excellent photostationary distributions of the trans and cis isomers, thermal half-lives of up to 7.2 h, and excellent reductant stability. The X-ray crystal structure analysis revealed that the trans isomers exhibited a planar geometry and the cis isomers exhibited a T-shaped orthogonal geometry. Detailed ab initio calculations further demonstrated the plausible electronic transitions and isomerization energy barriers, which were consistent with the experimental observations. The fundamental design principles elucidated in this study will aid in the development of a wide variety of visible-light photoswitches for photopharmacological applications.

中文翻译：

苯基偶氮噻唑作为可见光光开关

报道了一类基于苯基偶氮噻唑支架的新型光开关，该支架在可见光照射下进行可逆异构化。该光电开关包含一个直接连接到苯基偶氮发色团的噻唑杂芳基片段，与传统的偶氮苯和其他杂芳基偶氮相比，具有非常不同的光谱特性，例如最大吸收波长红移以及反式和顺式异构体的吸收带分离良好化合物。邻位和对位的取代基光开关苯环的位置导致在吸收最大值处进一步转移到更长的波长，最高可达 525 nm，并具有较小的热稳定性补偿。这些光电开关显示出出色的反式和顺式异构体的光静止分布、长达 7.2 小时的热半衰期以及出色的还原剂稳定性。X 射线晶体结构分析表明，反式异构体呈平面几何结构，顺式异构体呈 T 形正交几何结构。详细的从头计算进一步证明了合理的电子跃迁和异构化能垒，这与实验观察结果一致。本研究阐明的基本设计原则将有助于开发用于光药理学应用的各种可见光光开关。

更新日期：2023-04-12

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