CN111072439A - 一种发光材料及其合成方法及应用 - Google Patents

一种发光材料及其合成方法及应用 Download PDF

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CN111072439A
CN111072439A CN201911168029.XA CN201911168029A CN111072439A CN 111072439 A CN111072439 A CN 111072439A CN 201911168029 A CN201911168029 A CN 201911168029A CN 111072439 A CN111072439 A CN 111072439A
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李冰石
黄光熙
江玉卿
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Shenzhen University
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Abstract

一种发光材料及其合成方法及应用。本发明提供一种发光材料，其同时具有力致发光和聚集诱导发光性质，同时还提供了该发光材料的合成方法，其力致发光的性能可以在应力传感器、防伪标识等领域具有很好的应用前景。

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一种发光材料及其合成方法及应用
技术领域
本发明涉及有机材料合成技术领域，具体的是一种发光材料及其合成方法及应用。
背景技术
在外界机械力(研磨、摩擦、刮划、切割、剪切、粉碎，挤压等)刺激下能够直接发射荧光或磷光的材料称为力致发光(Mechanoluminescence)或摩擦发光(Triboluminescence)材料。力致发光材料在传感、监测、照明和防伪等领域有巨大的应用前景(Chem 2018,4,943)。力致发光材料可分为无机材料、金属有机配合物材料和纯有机材料。纯有机力致发光材料具有合成简单、成本低廉、毒性较小、发光范围容易调节等优点。但是，普通有机发光材料的荧光在固体状态下往往存在聚集猝灭效应(Aggregation-InducedEmission,ACQ)，影响材料的发光效率。因此，开发具有高的发光效率、应力敏感度和力致发光强度的有机力致发光材料是非常有意义的一个研究方向。
聚集诱导发光现象(Aggregation-Induced Emission,AIE)能够克服有机化合物的聚集猝灭效应，实现聚集状态下的高效发光(Chem.Commun.2001,1740；Chem.Rev.2015,115,11718)。如果在外力诱导下使具有聚集诱导发光特性的有机发光材料获得较高的力致发光强度，则能够拓宽该类材料的应用场景。
发明内容
本发明的目的之一在于提供一种发光材料，其同时具有力致发光和聚集诱导发光性质。
上述目的是采用如下方案实现的：
一种发光材料，其特征在于，其包含单体的分子结构为通式(I)或通式(II)所示：
Figure BDA0002287981450000011
其中，通式(I)中R为非芳香取代基；通式(II)中Ar为芳杂环基团。
本发明的另一目的，是提供上述具有聚集诱导发光性质的有机力致发光材料的合成方法。
该目的是采用如下方案实现的：
一种发光材料的合成方法，利用Suzuki偶联反应把单取代苯硼酸与溴代三苯乙烯反应得到通式(I)的产物，或利用Suzuki偶联反应把芳杂环硼酸与溴代三苯乙烯反应得到通式(II)的产物，其中通式(I)和通式(II)的结构式如下：
Figure BDA0002287981450000021
本发明的第三目的，是提供上述聚集诱导发光性质的有机力致发光材料在应力传感、防伪标识的应用。
本发明和已知技术相比，本发明的发光材料，其同时具有很明显的发光性能，且在外力诱导下使具有聚集诱导发光特性，且聚集诱导发光特性可以使得发光强度可调节，其在商业防伪标识、应力传感等方面具有很好的应用前景。
附图说明
图1为实施例1～3制备得到的目标化合物的聚集诱导发光照片图。
图2为实施例1～3制备得到的目标化合物的力致发光现象。
图3是本发明实施例1产物所制备的防伪原型示意图。
图4是本发明实施例1产物所制备的防伪原型照片。
图5是本发明实施例1产物所制备的防伪原型在黑暗中刮擦时的力致发光照片。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本申请提供了一种发光材料，其同时具有力致发光和聚集诱导发光的性质。
在一种实施例中，该发光材料包含的单体具有以下分子结构通式：
Figure BDA0002287981450000022
其中，在通式(I)中，R为非芳香取代基。
其中，R的位置可以是邻位、间位或对位中的任意一种。
更具体的，通式(I)选自如下结构式的任意一种，
Figure BDA0002287981450000031
其中，通式(I)的获得，是利用Suzuki偶联反应把单取代苯硼酸与溴代三苯乙烯反应得到，其反应式如下：
Figure BDA0002287981450000032
其中，单取代苯硼酸的取代基可以为CH3、OH、OCH3、CN、C≡CH、NO2、N(CH3)2、F或Cl中的任意一种。
在另一实施例中，该发光材料包含的单体具有以下分子结构通式：
Figure BDA0002287981450000033
其中，通式(II)中，Ar为芳杂环取代基。
进一步的，Ar为吡啶、呋喃或噻吩基。
更具体的，(II)中的Ar为以下取代基中的任意一种：
Figure BDA0002287981450000041
*表示结合位点。
其中，通式(II)的获得，是利用Suzuki偶联反应把芳杂环硼酸与溴代三苯乙烯反应得到，其反应式如下：
Figure BDA0002287981450000042
在上述的两种结构通式中，通式(I)和通式(II)其基于非共平面螺旋桨结构的芳基取代三苯乙烯为骨架构件，同时具有力致发光和聚集诱导发光性质，合成的力致发光材料发光效率、应力敏感度和力致发光强度高，非常适合于传感器、防伪标识领域的应用。
以下结合具体的实施例做进一步的阐述。
实施例1
目标化合物p-CN(属结构通式I)的合成：
溴代三苯乙烯(3.35g，10mmol)、4-氰基苯硼酸(2.2g，15mmol)和0.18g四(三苯基膦)钯置于100mL两口圆底烧瓶中，反应体系除氧。15mL K2CO3(6.21g，45mmol)水溶液与45mL四氢呋喃除氧后注入圆底烧瓶，氮气保护下回流反应20个小时。反应结束后冷却至室温，加入100mL水，用二氯甲烷萃取(100mL×3)，合并有机相。有机相用无水硫酸钠干燥后过滤，减压旋蒸得到粗产物。将粗产物用硅胶柱层析提纯，石油醚和二氯甲烷为洗脱剂得到白色粉末3.03g，产率为85％。
合成路线如下：
Figure BDA0002287981450000051
实施例2
目标化合物m-CN(属结构通式I)的合成：
参照实施例1的方法，以3-氰基苯硼酸替代4-氰基苯硼酸，合成目标化合物，得到白色粉末，产率为83％。
合成路线如下：
Figure BDA0002287981450000052
实施例3
目标化合物p-OH(属结构通式I)的合成：
参照实施例1的方法，以4-羟基苯硼酸替代4-氰基苯硼酸，合成目标产物，得到白色粉末，产率为88％。
合成路线如下：
Figure BDA0002287981450000053
实施例4
目标化合物m-NO2(属结构通式I)的合成：
参照实施例1的方法，以3-硝基苯硼酸替代4-氰基苯硼酸，合成目标产物，得到黄色粉末，产率为80％。
合成路线如下：
Figure BDA0002287981450000061
实施例5
目标化合物m-py(属结构通式II)的合成：
参照实施例1的方法，以3-吡啶硼酸替代4-氰基苯硼酸，合成目标产物，得到黄色粉末，产率为80％。
合成路线如下：
Figure BDA0002287981450000062
将实施例1～3的合成的目标化合物进行性能测试，主要考察目标化合物的聚集诱导发光以及力致发光性能。检测目标化合物的聚集诱导发光性能的方法是，将目标化合物分别溶解在四氢呋喃溶液以及含水量为99％的水/四氢呋喃混合溶液中，对比其发出荧光的强弱。
如图1，图中，图1A、1D、1G分别为实施例1～3的目标化合物在四氢呋喃溶液中的表现，图1B、1E、1H分别为实施例1～3的目标化合物在含水量为99％的水/四氢呋喃混合溶液中的表现，图1C、1F、1I分别为实施例1～3的目标化合物在固态条件下的荧光表现。由图1可知，实施例1～3的目标化合物的四氢呋喃溶液均表现出发光很弱的现象，而在含水量为99％的水/四氢呋喃混合溶液中均发出很强的荧光，同时，这些目标化合物在固态条件下均具有很强的荧光。这说明实施例1～3的化合物均具有聚集诱导发光的特性。
检测目标化合物的力致发光性能的方法是，将目标化合物制成的发光材料粉末，在铁勺的轻轻刮擦下的发光情况。
如图2，是实施例1～3的化合物其粉末样品在铁勺的轻轻刮擦下，即可发出荧光(均为蓝色)，说明实施例1～3的化合物均具有力致发光的特性。
进一步，对实施例1还进一步做了在防伪标识技术的应用。
具体操作为，将实施例1所获得的目标化合物采用两层双面胶进行封装，制成力致发光层，然后将力致发光层的一侧贴合保护层，该保护层可以是具有透光性质的称量纸、包装纸或其他具有韧性的纸张，而将力致发光层的另一侧贴合在商品的外包装上，该外包装可以是具有一定硬度材料，如玻璃瓶、纸盒等，如图3和图4。
上述应用，可进行防伪识别检测。检测方法是，在黑暗环境中，使用手指甲或硬物轻刮防伪标识，力致发光层受到应力的作用而发光，如图5所示，从而判断产品真伪。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应该以权利要求的保护范围为准。

Claims (8)

1.一种发光材料，其特征在于，其包含单体的分子结构为通式(I)或通式(II)所示：
Figure FDA0002287981440000011
其中，通式(I)中R为非芳香取代基；通式(II)中Ar为芳杂环基团。
2.根据权利要求1所述的发光材料，其特征在于，所述通式(I)中的R选自CH3、OH、OCH3、CN、C≡CH、NO2、N(CH3)2、F或Cl中的任意一种；
R的位置是邻位、间位或对位中的任意一种。
3.根据权利要求1所述的发光材料，其特征在于，所述通式(II)中Ar选自以下结构中的任意一种：
Figure FDA0002287981440000012
其中，*表示结合位点。
4.根据权利要求1～3任一所述的发光材料的合成方法，其特征在于，利用Suzuki偶联反应把单取代苯硼酸与溴代三苯乙烯反应得到通式(I)的产物，或利用Suzuki偶联反应把芳杂环硼酸与溴代三苯乙烯反应得到通式(II)的产物。
5.根据权利要求4所述的发光材料的合成方法，其特征在于，所述单取代苯硼酸中的取代基为CH3、OH、OCH3、CN、C≡CH、NO2、N(CH3)2、F或Cl中任意一种，取代基的位置位置是邻位、间位或对位。
6.根据权利要求4所述的的合成方法，其特征在于，所述芳杂环为吡啶基，吡啶基与三苯乙烯基的连接位为2-位或3-位或4-位。
7.根据权利要求4所述的发光材料的合成方法，其特征在于，所述芳杂环为呋喃基或噻吩基，呋喃基或噻吩基与三苯乙烯基的连接位为2-位或3-位。
8.根据权利要求1或2或3所述的发光材料，其在应力传感器、防伪标识领域的应用。
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