【作者】 薛莹莹；

【导师】 宋锋玲；

【作者基本信息】 大连理工大学 ， 精细化工， 2015， 硕士

【摘要】 二芳基乙烯类光致变色化合物,由于其具有优良的抗疲劳性能、良好的热稳定性、较高的信号对比度等优点,被广泛应用在材料、化学、生物等科学领域。一般的二芳基乙烯衍生物是没有荧光的,或者只有开环异构体发射微弱的荧光。而荧光是一种比较灵敏的检测信号,所以,探索并开发新型的具有荧光的二芳基乙烯光致变色化合物,是一个越来越重要的研究方向。本论文设计并合成了苯并噻吩砜烯桥类的新型二苯并噻吩基乙烯荧光光致变色母体化合物TMl,及其衍生物TM2-TM4。比较了它们与参比化合物BTF6(全氟烯桥)的各种光物理性质。研究结果表明TM1-TM4的光致变色反应进行的要比BTF6更彻底,表现在TM1-TM4开环到闭环的转换率均高于BTF6,其中TM4高达0.86；且TMl(抗劳时间1800 min)比BTF6(抗劳时间1500 min)具有更优越的抗疲劳性能,并将TM1应用到高分子薄膜中也不影响其光致变色性能；最重要的是,TM1-TM4的闭环异构体均具有参比化合物c-BTF6(BTF6的闭环异构体)所不具备的荧光性能,TM1-TM4的闭环异构体分别在577 nm(493 nm激发)、597 nm(375 nm激发)、579 nm(473nm激发)和601 nm(370 nm激发)处有明显的荧光发射,且c-TM2和c-TM4最大发射波长分别比c-TM1红移20 nm和24 nm。闭环异构体中,c-TM2的荧光量子产率(0.005)最高,可能是由于其相对较高的荧光寿命(2.242 ns)造成的；而在开环异构体中,TMl的荧光量子产率最高,比o-BTF6 (BTF6的开环异构体)高出0.002。另外,细胞实验说明TM3可以进入MCF-7细胞,并且有较好的荧光信号,显示出此类化合物在细胞成像乃至超分辨成像应用中的潜力。最后,测试发现TM1-TM4和BTF6开环异构体除氧前后的磷光光谱发生明显变化,说明TM1-TM4的开环异构体和o-BTF6一样,也具有三重态。以上这些研究内容,为以后苯并噻吩砜烯桥的二芳基乙烯类荧光光致变色化合物的进一步研究奠定了理论基础。更多还原

【Abstract】 The photochromic diarylethenes compounds, because of its excellent fatigue resistance, high fatigue resistance and high signal contrast, are widely used in material, chemical, biological and other scientific fields. Generally speaking, diarylethane derivatives have no fluorescence, or weak emission in their open forms, but the fluorescence is a more sensitive detection signal, therefore, exploring and developing a new type of photochromic diarylethylene compounds with fluorescent property, is a more and more important research direction.A fluorescent photochromic matrix compound TM1 with a benzo[b]thiophene-1,1-dioxide bridge and its derivatives TM2-TM4 were synthesized. In order to study TM1-TM4, we choose a reference compound BTF6 (with a perfluorocyclopentene brige), and investigate their spectral properties in ethyl acetate solution. The photochromic reaction of TM1-TM4 respond to more thoroughly than BTF6, performance in the cyclization conversions of TM1-TM4 are higher than BTF6, which of TM4 is even up to 0.86. Meanwhile, the fatigue resistence of TM1 (Fatigue time=1800 min) is superior to that of BTF6 (Fatigue time=1500 min), and a film of TM1 in poly (methyl methacrylate) (PMMA) matrix was prepared, and the result demonstrate a good photochromic behavior of TM1 in polyer film. Most important of all, the closed-forms of TM1-TM4 have distinct fluorescent emission at 577 nm (493 nm excitation),597 nm (375 nm excitation),579 nm (473 nm excitation) and 601 nm (370 nm excitation), respectively, while closed-form of BTF6(c-BTF6) has no emission. And the maximum emission wavelength of c-TM2 and c-TM4 is shift to red (20 nm and 24 nm, respectively), compared to that of c-TM1. Fluorescence quantum yield of c-TM2 (0.005) is highest in the closed-forms maye originates from its relatively high fluorescence lifetime (2.242 ns). And fluorescence quantum yield of o-TM1 is highest in the open-forms, which is higher than o-BTF6 (0.002). Cell experiments demonstrate that TM3 can enter the MCF-7 cell, and has a good fluorescence signal, which shows that this kind of compounds has a good potential in cell imaging and the super resolution imaging applications. The phosphorescence spectra of open-forms of TM1-TM4 and o-BTF6 have a big difference before and after deoxygenation, which proved that open-forms of TM1-TM4 all have a triplet state, like o-BTF6. All these research results make a firm foundation on the further research of fluorescent photochromic compound with a benzo[b]thiophene-1,1-dioxide bridge.更多还原