CN113429382B - 1,1’-([2,2’-二噻吩]-3,3’-二基)双(乙-1-酮)及制备与应用 - Google Patents

1,1’-([2,2’-二噻吩]-3,3’-二基)双(乙-1-酮)及制备与应用 Download PDF

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CN113429382B
CN113429382B CN202110736900.2A CN202110736900A CN113429382B CN 113429382 B CN113429382 B CN 113429382B CN 202110736900 A CN202110736900 A CN 202110736900A CN 113429382 B CN113429382 B CN 113429382B
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梁文娟
荆补琴
卢珍
晋卫军
冯锋
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Abstract

本发明属于高分子材料合成技术领域，具体涉及一种1,1’‑([2,2’‑二噻吩]‑3,3’‑二基)双(乙‑1‑酮)及制备与应用。所述1,1'‑（[2,2'‑二噻吩]‑3,3'‑二基）双（乙‑1‑酮）的结构式为：
Figure 100004_DEST_PATH_IMAGE001
。通过采用控制分子转子构象弛豫和共轭的方法，合成了1,1'‑（[2,2'‑二噻吩]‑3,3'‑二基）双（乙‑1‑酮）分子转子，并***地研究了它的主要性质。不同扭转角度和共轭程度的转子产生不同的发光颜色。另外，氢键刺激可以很容易地克服扭转构象和***面构象之间的旋转能垒。在合成过程中，分离副产物有一定的技术难度。

Description

1,1’-([2,2’-二噻吩]-3,3’-二基)双(乙-1-酮)及制备与 应用
技术领域
本发明属于高分子材料合成技术领域，具体涉及一种1,1'-（[2,2'-二噻吩]-3,3'-二基）双（乙-1-酮）及其制备方法与应用。
背景技术
刺激响应型发光材料（SRLMs）在显示器、传感器、存储器等领域有着广阔的应用前景，其设计一直是一个研究热点。SRLMs在适当的化学和物理因素（如化学物质、机械力、光或磁辐射等）的刺激下表现出发光行为的变化。
2018年，McCoy等报告了通过控制光物理过程（如系间窜越（ISC）过程）构建高灵敏度开关机械SRLMs的设计方法[D. E. McCoy, T. Feo, T. A. Harvey and R. O. Prum,Nat. Commun., 2018, 9, 1.]。同年，Yang等通过控制固态二聚体间分子堆积模式的转变，构建了一种基于延迟荧光的SRLM[Y. Yang, X. Yang, X. Fang, K.-Z. Wang and D.Yan, Adv. Sci., 2018, 5, 1801187.]。
除了上述模式外，调节分子的构象和共轭度也是一种常见的方法。2011年，Luo等报道了具有较小扭转角和较大共轭构象的机械变色铝酸盐化合物具有更红的发射[X.Luo, J. Li, C. Li, L. Heng, Y. Q. Dong, Z. Liu, Z. Bo and B. Z. Tang, Adv.Mater., 2011, 23, 3261–3265.]。
由于分子转子含有可旋转的单键，分子的构象和共轭程度处于基态或激发态的转子分子可以通过外部刺激因子进行调节。具有分子转子性质的联苯及其衍生物的基态和激发态之间的构象关系，即在没有旋转势垒的情况下，垂直激发态（Franck-Condon态）发生构象弛豫，达到平面激发态。这种现象意味着在外界刺激下，通过改变转子的构象和共轭程度，很容易实现对转子发光行为的调节。因此，基于激发态的构象弛豫，设计转子基荧光团的SRLMs应该是一个很好的方法。
发明内容
本发明提供了一种1,1'-（[2,2'-二噻吩]-3,3'-二基）双（乙-1-酮）及其制备方法与应用。
本发明由如下技术方案实现的：一种1,1'-（[2,2'-二噻吩]-3,3'-二基）双（乙-1-酮），所述1,1'-（[2,2'-二噻吩]-3,3'-二基）双（乙-1-酮）的结构式为：
Figure 100002_DEST_PATH_IMAGE001
。
制备所述的1,1'-（[2,2'-二噻吩]-3,3'-二基）双（乙-1-酮）的方法，具体步骤如下：
正丁基锂浓度为2.5M的正丁基锂的正己烷溶液36mL，N2置换后，溶液冷却至-78℃，加入300mL无水四氢呋喃；0.8-1.2小时内逐滴加入30 mmol 3,3'-二溴-2,2'-联噻吩的四氢呋喃70 ml；完成后，混合物在-78℃再搅拌2小时，然后滴加入95 mmol N-甲氧基-N-甲基乙酰胺，使反应溶液自然升温到室温并反应过夜；通过液质联用检测反应完成后，加入水淬灭反应，然后用250 ml乙酸乙酯萃取，乙酸乙酯同样条件下萃取3次，得到的有机相依次用50 mL水和50 mL饱和食盐水洗涤，Na2SO4干燥，过滤并浓缩得到粗产物；粗产物通过快速柱层析法纯化，快速柱层析为硅胶柱，用20%石油醚/乙酸乙酯洗脱，得到浅黄色固体1,1'-（[2,2'-二噻吩]-3,3'-二基）双（乙烷-1-酮），得率为42.7%；液相色谱-质谱 (ESI): 250.9(M + 1)+；1H NMR (400 MHz, CD3OD) δ: 7.58 (d, J = 4.0, 2H), 7.56 (d, J = 4.0,2H), 2.30 (s, 6H)。
本发明通过采用控制分子转子构象弛豫和共轭的方法，合成了1,1'-（[2,2'-二噻吩]-3,3'-二基）双（乙-1-酮）分子转子，并***地研究了它的主要性质。不同扭转角度和共轭程度的转子产生不同的发光颜色。另外，氢键刺激可以很容易地克服扭转构象和***面构象之间的旋转能垒。在合成过程中，分离副产物有一定的技术难度。
附图说明
图1为本发明合成路线图；
图2为所得化合物的HNMR-CDCL3图；
图3为所得化合物的液相色谱-质谱联用即LC-MS图；
图4为所得1,1'-（[2,2'-二噻吩]-3,3'-二基）双（乙-1-酮）的聚合物膜在紫外线-365nm辐射下，对水的响应照片。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例；基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
在1L三颈烧瓶中，将正丁基锂（36mL，2.5M，90mmol）的正己烷溶液，N2置换后，冷却至-78℃，并添加无水四氢呋喃（300mL）。在0.8-1.2小时的过程中，逐滴添加3,3'-二溴-2,2'-联噻吩（9.65 g，30 mmol）的THF溶液（70 ml）。然后在-78℃下将混合物再搅拌2小时，随后再滴加N-甲氧基-N-甲基乙酰胺（9.8g，95 mmol），之后使反应溶液自然升温至室温且反应过夜。通过液质联用检测反应完后，加入水淬灭反应，然后用250 ml乙酸乙酯萃取，乙酸乙酯同样条件下萃取3次，得到的有机相依次用50 mL水和50 mL饱和食盐水洗涤，Na2SO4干燥，过滤并浓缩得到粗产物；粗产物通过快速柱层析法纯化，快速柱层析为硅胶柱，用20%EA/PE（石油醚/乙酸乙酯）洗脱，得到浅黄色固体形式的1,1'-（[2,2'-二噻吩]-3,3'-二基）双（乙烷-1-酮）（3.2 g，42.7%）。具体合成路线如图1所示。检测所得化合物的HNMR-CDCL3图如图2所示，LC-MS图如图3所示。液相色谱-质谱 (ESI): 250.9 (M + 1)+。1H NMR (400MHz, CD3OD) δ: 7.58 (d, J = 4.0, 2H), 7.56 (d, J = 4.0, 2H), 2.30 (s, 6H)。
本发明合成了双噻吩转子衍生物，以应用控制分子转子构象弛豫和共轭的策略，不同扭转角和共轭度的转子产生不同的发光颜色。氢键刺激可以很容易地克服扭转构象和***面构象之间的旋转能垒。在双噻吩的一侧引入醛基作为氢键位点，实现了在氢键刺激下驱动转子转动的发光响应。1,1'-（[2,2'-二噻吩]-3,3'-二基）双（乙-1-酮）的荧光对氢键比较敏感。为了便于刺激响应材料的应用，将该双噻吩衍生物掺杂到聚乙烯吡咯烷酮(PVP)基体中，通过浇铸形成聚合物膜。我们对聚合物薄膜对水的刺激响应进行了研究。如图4所示，薄膜在UV-365 nm辐射下，在495 nm处呈现蓝色荧光。当用水在薄膜上写字时，带有土黄色荧光字迹清晰显示。在膜上滴加水后，荧光从495 nm到498 nm发生红移，这是由于氢键的形成，激发态稳定化，由***面构象控制。滴水的薄膜在80摄氏度的烤箱中烘干3小时，然后土黄色荧光消失并返回到先前的蓝色发射。这表明薄膜对水具有可逆反应，可用于信息加密、环保可擦写、智能传感等材料的刺激响应行为。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (2)

1.一种1,1'-（[2,2'-二噻吩]-3,3'-二基）双（乙-1-酮），其特征在于：所述1,1'-（[2,2'-二噻吩]-3,3'-二基）双（乙-1-酮）的结构式为：
Figure DEST_PATH_IMAGE001
。
2.如权利要求1所述的1,1'-（[2,2'-二噻吩]-3,3'-二基）双（乙-1-酮）在信息加密、环保可擦写、智能传感材料的刺激响应行为中的应用，所述1,1'-（[2,2'-二噻吩]-3,3'-二基）双（乙-1-酮）对水可逆反应，具体制备步骤如下：
正丁基锂浓度为2.5M的正丁基锂的正己烷溶液36mL，N2置换后，溶液冷却至-78℃，加入300mL无水四氢呋喃；0.8-1.2小时内逐滴加入30 mmol 3,3'-二溴-2,2'-联噻吩的四氢呋喃70 ml；完成后，混合物再搅拌2小时，然后滴加入95 mmol N-甲氧基-N-甲基乙酰胺，使反应溶液自然升温到室温并反应过夜；通过液质联用检测反应完后，加入水淬灭反应，然后用250 ml乙酸乙酯萃取，乙酸乙酯同样条件下萃取3次，得到的有机相依次用50 mL水和50 mL饱和食盐水洗涤，Na2SO4干燥，过滤并浓缩得到粗产物；粗产物通过快速柱层析法纯化，快速柱层析为硅胶柱，用20%石油醚/乙酸乙酯洗脱，得到浅黄色固体1,1'-（[2,2'-二噻吩]-3,3'-二基）双（乙烷-1-酮）。
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