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Theoretical Study on Photoisomerization Effect with a Reversible Nonlinear Optical Switch for Dithiazolylarylene

机译：双偶氮亚乙基可逆非线性光开关光致异构化效应的理论研究

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DFT and TDDFT methods have been performed to investigate the photoisomerization effect for dithiazolylarylene on solution. The weak S center dot center dot center dot N interaction and CH center dot center dot center dot N hydrogen bond restrain the rotation of the side-chain thiazolyl ring in open-isomer la, the higher stability of which prefers to show a high quantum yield of photoisomerization. The calculated UV-Vis spectrum at around 320 nm for open-isomer la is bathochromically shifted to 647 nm for closed-isomer 1b, in excellent agreement with the experimental photochromic phenomenon. The electron transition in ECD (electron circular dichroism) spectra for closed-isomer 1b with two chiral carbon atoms is dominated by ICT (intramolecular charge transition) and LE (local excitation) corresponding to one positive (440 nm) and one negative Cotton effect (650 nm), respectively, where the two chiral carbon atoms play a slight role in these transitions. The PES in the S-1 and S-0 states, respectively, indicates that the cyclization reaction from open-isomer la to closed-isomer 1b is allowed in the photoexcited state with high-conversion quantum efficiency, while it is forbidden in the thermodynamic process. In addition, the second-order nonlinear optical response for closed-isomer 1b is nearly six times larger than that for open-isomer la. It is also confirmed that the photoirradiation evokes the photoisomerization character to show dramatic difference in the second-order NLO response, which can be applied to designing photochromic materials and reversible NLO switches.
机译：已经进行了DFT和TDDFT方法以研究二噻唑基亚芳基在溶液上的光异构化作用。弱的S中心点中心点中心点N相互作用和CH中心点中心点中心点N氢键限制了开放异构体la中侧链噻唑基环的旋转，其较高的稳定性倾向于显示高量子产率异构化。对于封闭异构体1b，计算出的开放异构体Ia在约320 nm处的UV-Vis光谱被红移到647 nm，这与实验性光致变色现象极为吻合。具有两个手性碳原子的闭合异构体1b在ECD（电子圆二色性）光谱中的电子跃迁主要由ICT（分子内电荷跃迁）和LE（局部激发）所控制，对应于一个正离子（440 nm）和一个负棉花效应（ 650 nm），其中两个手性碳原子在这些跃迁中起轻微作用。在S-1和S-0状态下的PES分别表明，在光激发态下，允许从开放异构体1a到封闭异构体1b的环化反应具有高转换量子效率，而在热力学中则被禁止处理。另外，封闭异构体1b的二阶非线性光学响应几乎是开放异构体1a的六倍。还证实了光辐照引起了光异构化特征，从而在二阶NLO响应中显示出显着差异，其可用于设计光致变色材料和可逆NLO开关。

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