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腙类分子开关在超分子化学领域有非常重要的应用价值，基于靛红发色团发展出的新型腙类分子开关已被合成。因其具有可见光激发下的顺反异构化特征、衍生物的易合成性及对外界刺激的敏感性，使其在生物化学领域具有重要的应用价值。然而，该新型分子开关的光致异构化机制尚不明确，异构过程是否存在新奇的现象也不得而知。本文采用基于半经验OM2/MRCI的轨迹面跳跃动力学方法，系统地研究了一种名为靛红双氮二苯腙分子开关E-Z异构化过程的光致异构化机理。研究发现该E构型分子开关的S1激发态平均寿命约为 107 fs，该分子开关的E-Z异构化量子产率为16.01%。通过对该分子开关光致异构化过程的计算，明确了两种不同分子开关异构化机制；除围绕C=N键旋转的传统分子开关异构机制之外，阐明了新的异构机制——分子开关转子部分面对面的扭转；通过时间分辨的荧光辐射谱的计算，预测了异构化过程中存在极快的荧光猝灭现象，并且伴随着荧光红移的发生；通过对计算得到的荧光光谱与激发态平均寿命的分析，提出了“暗态”的存在，并对“暗态”存在的原因给出了可能得解释。研究结果可为新型分子开关的设计及应用提供理论指导作用。Hydrazone molecular switches have significant application value in supramolecular chemistry, and new types of hydrazone molecular switches named isatin N2-diphenylhydrazones have been synthesized. Due to its cis-trans isomerization characteristics under visible light excitation, easy synthesis of derivatives, and sensitivity to external stimuli, it has important application value in the field of biochemistry. Due to its forward and backward visible light excitation characteristics, it is considered a class of compounds that are very suitable for molecular switches, and it has extremely wide application value in fields such as biotechnology. In addition, the derivatives compound exhibits strong interactions with negative ions, which enhances its functionality as a molecular switch, making it a four-state molecular switch that can be achieved by a single molecule. However, the photo-induced isomerization mechanism of these new molecular switches is not yet clear, and it is also unknown whether there are novel phenomena in the isomerization process. This article adopts a semi empirical OM2/MRCI based trajectory surface hopping dynamics method to systematically study a photo induced isomerization mechanism based on the E-Z isomerization process of the isatin N2-diphenylhydrazones molecular switch (Fig. 1). Optimization configuration (Fig.2) and the average lifetime (Fig.3) of the first excited S1 state based on the semi-empirical OM2/MRCI method of molecular switch were obtained. It has been found that the average lifetime of the S1 excited state of the E-configuration molecular switch is about 107 fs, and the quantum yield of E-Z isomerization of the molecular switch is 16.01%. By calculating the photo induced isomerization process of the molecular switch, two different isomerization mechanisms of the molecular switch were identified; In addition to the traditional molecular switch isomerization mechanism revolving around the C=N bond (Fig.4(c, d)、Fig5(c, d)), a new isomerization mechanism has been elucidated - the face-to-face twisting of the molecular switch rotor part (Fig.4(a, b)、Fig5(a, b)); By calculating the time-resolved fluorescence radiation spectrum, it was predicted that there would be an extremely fast fluorescence quenching phenomenon occurred in about 75 fs during the isomerization process (Fig 6 (a)), slightly faster than the S1 average decay events (107 fs). The wavelength-resolved decay information in different time were also calculated, reflecting the ultrafast fluorescence quenching process accompanied by the occurrence of fluorescence red shift (Fig.6 (b)), ranging from 2.1 × 104 cm-1 to 3.4 × 104 cm-1; By comparing the calculated fluorescence spectra and the average lifetime of excited states, the existence of "dark states" was proposed, and possible explanations for the existence of "dark states" were provided, and those “dark state” may have some relation with the lower quantum yield. The research results can provide theoretical guidance for the design and application of new molecular switches. The ease of synthesis and sensitivity to external stimuli of its derivatives make those compounds extremely valuable in molecular switching and light measurement applications.
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