1基于咪唑和苯并噻唑类二芳烯的合成及 性质研究2主 要 内 容一、研究背景及立体依据二、已完成的研究内容三、结论 四、下一步工作计划五、阶段性科研成果六、致谢3a)b)c)d)优越的抗疲劳性 良好的热稳定性 较高的灵敏性 快速响应能力光致变色(Photochromism)一、研究背景及立体依据h1h24分子合成分类各类桥头结构 各类芳杂环在末端引入不同 的基团5二芳基乙烯类化合物的特性1、量子产率2、热稳定性3、抗疲劳性J. Am. Chem. Soc 1995, 60(25), 8305-8309 J. Am. Chem. Soc 1994, 116(22): 10141-10151Chemical Reviews, 2014, 114(24) ： 12174-12277.6二芳基乙烯化合物应用研究2、细胞成像1、无损读取3、分子开关Chem. Commun. 2013, 49, 8036 8038.Chem. Commun., 2012, 48, 3745.J. Am. Chem. Soc 2004, 126(45): 14843-14849.7Shouzhi Pu*, Hui Li, et al., Tetrahedron Letters, 2010, 51, 35753579. thermal stability of both isomers of the diarylethene can be improvedshift the max of the closed-ring isomer to shorter wavelengths?课题提出8课题提出咪唑上的氮原子含有未共用电子对，使得咪唑同时具有弱碱性和氧化还原性离子响应酸碱效应 Mater. Interfaces 2013, 5, 56235629SAA, 2015,138, 4414469课题提出苯并噻唑是一类荧光团离子响应酸碱效应 J. Org. Chem. 2012, 77, 90729080J. Mater. Chem. C, 2013, 1, 47264739102、 已完成的研究内容2.1、末端连不同芳香环咪唑类短波长二芳烯的合成及性质研究2.2、末端连不同取代基咪唑类短波长二芳烯的合成及性质研究2.3、含苯并噻唑类二芳烯化合物的合成及其性质研究11112.1、末端连不同芳香环咪唑类短波长二芳烯的合成及性质研究Scheme 1 Synthesis of diarylethenes 1o5o.1212Figure 1 (A-D) Absorption spectral and color changes of 1o4o with stimulation of light in acetonitrile (2.0 105 mol L1). Figure 2 (A-D) Photoswitching of 1o4o showing changes in absorbance flollwing alternate exposures to UV and Visible light in acetonitrile (2.0 105 mol L1).1313Entryo,maxa/nmc,maxb/nmcPR(/Lmol-1 cm-1)a(/L mol-1 cm-1)ao-cc-o(%)1240 (2.78 104)334(9.76 103)0.060.00020402269 (3.10 104)372 (1.12 104)0.110.00146373265 (2.41 104)373 (8.17 103)0.110.00015484268 (4.35 104)382 (1.37 104)0.150.0004044Table 1 Absorption spectral properties of diarylethenes 14 in acetonitrile (2.0 10-5 mol L-1) at room temperature. a Absorption maxima of open-ring isomers. b Absorption maxima of closed-ring isomers. c Quantum yields of cyclization reaction (o-c) and cycloreversion reaction (c-o), respectively. 1414Figure 3 Emission spectral changes and photos of diarylethenes 1o4o by photoirradiation in acetonitrile (C = 2.0 105 mol L1) at room temperature: (A) 1o, excited at 335 nm, (B) 2o, (C) 3o and (D) 4o, excited at 400nm.Figure 4 Emission changes in the fluorescence of 4o induced by the addition of (A) various metal ions (4 equiv.) in acetonitrile (2.0 105mol L1); (B) 100 equiv TFA. Insert: photographs of the color changes in fluorescence.15CompoundsexaembIfc(fold) dfc1c335446383.29.00.00442c400501680.26.60.00563c4004882069.078.80.01384c400502632.911.00.0092Table 2 Fluorescence parameters of diarylethenes 1c4c in acetonitrile (2.0 10-5 mol L-1) at room temperature. a Excitation peak. b Emission peak. cEmission intensity in the photostationary. d Fluorescence enhanced fold in the photostationary state. 16Graphic Abstract1717Scheme 1. Photochromism of diarylethenes 68 2.2、末端连不同取代基咪唑类短波长二芳烯的合成及性质研究1818Scheme 2. Synthetic route for diarylethenes 6o8o. 1919(A)Fig. 1 (A-D) Absorption spectral and color changes of 6o8o with stimulation of light in acetonitrile (2.0 105 mol L1).(A)(B)(C)(D)2020(A)Fig 2. Thermal fading of diarylethene 6c at various temperature and 6c-8c at room temperature in acetonitrile.(B)2121Fig 3. The photoconversion ratios of diarylethenes 68 in the photostationary state by HPLC analysis.2222Table 1. Absorption spectral properties of diarylethenes 68 in acetonitrile (2.0 10-5 mol L-1) at room temperature.Compoundo,max/nma (/L mol-1 cm-1)c,max/nmb (/L mol-1 cm-1)cConversion at PSS in hexane(%)acetonitrileacetonitrileo-cc-o6268 (2.30 104)377 (2.30 104)0.110.0041327272 (2.28 104)371 (1.81 104)0.0840.0014428285 (2.81 104)375 (3.94 104)0.120.002835a Absorption maxima of open-ring isomers.b Absorption maxima of closed-ring isomers.c Quantum yields of cyclization reaction ( o-c) and cycloreversion reaction (c-o), respectively.23(A)(B)(C)Fig 4. Absorption spectral changes of 6c8c in acetonitrile solution after the addition of 5 equiv TFA. 2424(A)(B)Fig 5. ORTEP drawings (ellipsoids are drawn at 30% level): (A) 6o; (B) 7o; (C) 8o. (C)2525(C) Fig 7. Emission intensity and fluorescence changes of diarylethenes 13 by photoirradiation in acetonitrile (2.0 10-5 mol L-1) at room temperature: (A) for 1, (B) for 2, (C) for 3.(A)(B)(C)Fig 6. Emission intensity and fluorescence changes of diarylethenes 68 by photoirradiation in acetonitrile (2.0 10-5 mol L-1) at room temperature: (A) for 6, (B) for 7, (C) for 8. 26262.3、含苯并噻唑类二芳烯化合物的合成及其性质研究Scheme 1. Photochromism of diarylethenes 910. 2727(A) (B) DT 9o 性 质Fig. 1. Absorption spectrum (A) and fluorescence spectrum (B) changes in acetonitrile (2.0 10-5 mol L-1) upon alternating irradiation with UV-vis light at room temperature.2828DT 9o 性 质Fig. 2. Fluorescence spectrum changes of DT9o induced by the addition of various metal ions (5 equiv.) in acetonitrile (2.0 10-5 mol L-1).Fig. 3. Changes in fluorescence of DT - 9o i