CN107793377A - 一种全彩超长有机磷光材料及其制备方法和应用 - Google Patents
一种全彩超长有机磷光材料及其制备方法和应用 Download PDFInfo
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- C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
- C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
- C07D279/18—[b, e]-condensed with two six-membered rings
- C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
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- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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Abstract
本发明属于纯有机超长磷光材料的制备领域，公开了一种全彩超长有机磷光材料及其制备方法和应用，具体是将吩噻嗪发色团引入到吸电子基团上而实现激发光源依赖的纯有机超长磷光材料。该材料具有以下特点：(1)原料廉价，合成方法简便；(2)合成的材料磷光寿命长，量子效率高；(3)通过改变激发光源的波长，实现从蓝光到红光的全彩超长有机磷光发射。由于这种材料具有特殊的光学性质，使得其在数据加密及全彩显示领域具有潜在的应用价值。
Description
技术领域
本发明属于超长有机磷光材料领域，具体涉及一类激发光源依赖的全彩超长有机磷光材料，并涉及该类材料在数据加密或防伪方面的应用。
技术背景
纯有机磷光材料是一类从三线态通过辐射跃迁到基态而发光的化合物，由于其具有长寿命和高的量子效率，使得磷光材料在有机发光二极管(OLEDs)，传感，信息存储以及数据加密等方面有潜在的应用。然而，由于从单线态到三线态跃迁的自旋轨道禁阻，并且三线态激子通过分子的振动、转动和热扰动等非辐射跃迁途径失活，使得纯有机磷光材料的发光在室温下很难用肉眼观察到。
近几年，很多增强室温磷光的策略与机理不断被提出，并且实现了室温超长有机磷光发射，使得移除光源后能持续发光数秒甚至几十秒。目前实现室温磷光的策略主要基于以下两个方面，一是通过向分子体系引入重原子(如Cl，Br，I)和杂原子(如N，O，S)来提高系间穿越速率，另一个是抑制三线态激子的非辐射跃迁，例如通过构建晶体工程，主客体掺杂，掺入聚合物中和H型聚集等刚性环境。然而，目前的研究主要集中于提高磷光发射的量子效率和寿命，很少有研究调控磷光的发光颜色，尤其是单组份的全彩纯有机磷光材料。
到目前为止，大多数的全彩发光材料主要是无机物，例如量子点(QDs)和碳点(CDs)，纯有机化合物还很稀少。相比于无机化合物，有机材料有很多优点，例如毒性低、价格便宜以及很好的合成与调控性，因此有机磷光材料在全彩发光应用方面具有更大的吸引力。
在有机分子中，具有柔性的分子结构(例如分子内单键旋转、顺反异构化和构型变化)是实现全彩发光的关键因素。此前也有一些研究报道了奇特的激发波长依赖的光致发光现象，但目前这些全彩的发光都局限于荧光发射，还没有全彩磷光发射的相关报道。基于目前的现状，激发光依赖的纯有机磷光材料具有很好的光学性质及应用前景。
发明内容
本发明的目的在于提供一种能全彩发光的超长有机磷光材料，由于其具有激发光依赖的特点，使得这种材料能够实现从蓝光到红光的全色域发光。
本发明的另一目的是提供一种激发光依赖的超长有机磷光材料的制备方法。
本发明还有一个目的是提供该类材料在数据加密与防伪上的应用。
一种全彩超长有机磷光材料，该材料具有如下结构：
中，R的结构如下：
-CnH2n+1，n＝1～8
中心T的结构如下：
R1的结构如下：
-CnH2n+1或-NHCnH2n+1或-OCnH2n+1或-SCnH2n+1或-H
-PhCnH2n+1或-PhNHCnH2n+1或-PhOCnH2n+1或-PhSCnH2n+1；
其中，n＝1～8。
R2的结构如下：
-CnH2n+1或-NHCnH2n+1或-OCnH2n+1或-SCnH2n+1或-H
-PhCnH2n+1或-PhNHCnH2n+1或-PhOCnH2n+1或-PhSCnH2n+1；
其中，n＝1～8。
中心M的结构如下：
R3的结构如下：
-CnH2n+1或-NHCnH2n+1或-OCnH2n+1或-SCnH2n+1或-H
-PhCnH2n+1或-PhNHCnH2n+1或-PhOCnH2n+1或-PhSCnH2n+1
其中，n＝1～8。
中的S元素可以被氧化成
上述全彩超长有机磷光材料，随着激发波长的变化，其磷光发射也变化，从而实现单组份全彩发光，并且在晶体状态下具有超长磷光寿命达0.14s，磷光量子效率达29％。上述全彩超长有机磷光材料可在实现数据加密和和防伪中应用。
上述材料的制备过程通式可以如下：
通式1：
或通式2：
或通式3：
本发明通过核磁共振(NMR)、单晶X射线衍射表征了磷光材料的结构；通过紫外吸收光谱、荧光发射光谱以及磷光寿命的测量，详细研究这一系列超长有机磷光材料在溶液状态和聚集状态下的光物理性质。
由于这种材料具有特殊的激发光依赖的光物理性质，可以在防伪应用上面有潜在的实用价值。相比于传统的超长有机磷光材料TCzCl2，它不具有激发光依赖的性质，因此在改变激发波长的时候，其超长磷光发色的颜色不变。而本发明中的这种磷光材料，在改变激发波长的同时，超长磷光发射的颜色也在改变，使得其具有特殊的光学信号，若是将其应用于商标或是防伪码上，可明显的鉴别商品的真伪而轻松地与仿冒商品区分开来。
附图说明
图1.化合物1在溶液下的吸收和发射光谱；
图2.化合物1的晶体在不同激发波长下的磷光光谱图；
图3.化合物1在不同发射波长的寿命衰减图；
图4.化合物1应用于防伪应用的图片。
具体实施方式
以下通过具体实施例对本发明进行进一步说明：
化合物1的合成方法：
化合物2的合成方法：
化合物3的合成方法：
化合物4的合成方法：
化合物5的合成方法：
化合物6的合成方法：
对比化合物结构：
实施例1：
化合物1的合成：将吩噻嗪溶解于无水THF中，并于冰水浴下逐渐加入0.4gNaH，在室温下搅拌反应30min，然后再向反应液中加入碘甲烷溶液并搅拌反应2h。反应结束后，向反应液中加入去离子水猝灭反应，然后用二氯甲烷萃取，有机相用无水硫酸钠干燥并减压浓缩。最后，通过层析柱纯化后得到白色固体产物，产率为87％。1H NMR(400MHz,DMSO)δ7.19(t,1H),7.13(d,1H),6.93(t,2H),3.28(s,1H).13C NMR(101MHz,DMSO)δ145.79,128.24,127.25,122.95,122.55,115.06。
实施例2：
化合物2的合成：将吩噻嗪溶解于无水THF中，并于冰水浴下逐渐加入0.4gNaH，在室温下搅拌反应30min，然后再向反应液中加入碘甲乙烷溶液并搅拌反应2h。反应结束后，向反应液中加入去离子水猝灭反应，然后用二氯甲烷萃取，有机相用无水硫酸钠干燥并减压浓缩。最后，通过层析柱纯化后得到白色固体产物，，该产物的产率为90％。1H NMR(400MHz,CDCl3)δ7.21(t,2H),7.16(d,2H),7.06(t,1H),3.10(t,2H),1.14(t,1H).13C NMR(101MHz,CDCl3)δ144.74,128.49,126.52,123.28,122.82,116.08,45.68,13.31。
实施例3：
化合物3的合成：将吩噻嗪，1,3,5-三氯苯，碘化亚铜，18-冠-6和碳酸钾加入到单口圆底烧瓶中，密封然后氮气保护，再加入邻二氯苯溶解并搅拌，在185℃条件下回流反应24h。反应结束后，向反应液中加入去离子水猝灭反应，然后用二氯甲烷萃取，有机相用无水硫酸钠干燥并减压浓缩。最后，通过层析柱纯化后得到白色固体产物，产率为31％。1H NMR(400MHz,CDCl3)δ7.21(t,1H),7.20(d,2H),7.16(t,2H),6.97(t,1H),6.49(s,1H).13C NMR(101MHz,CDCl3)δ149.87,141.45,127.11,126.62,124.39,122.70,115.73,108.87。
实施例4：
化合物4的合成：将吩噻嗪，4,6-二氯-2-苯基-嘧啶，碘化亚铜，18-冠-6和碳酸钾加入到单口圆底烧瓶中，密封然后氮气保护，再加入邻二氯苯溶解并搅拌，在185℃条件下回流反应24h。反应结束后，向反应液中加入去离子水猝灭反应，然后用二氯甲烷萃取，有机相用无水硫酸钠干燥并减压浓缩。最后，通过层析柱纯化后得到白色固体产物，产率为31％。1H NMR(400MHz,CDCl3)δ8.36(t,2H),7.50(d,1H),7.21(d,2H),7.20(t,1H),7.16(d,1H),6.97(d,1H),5.12(s,1H).13C NMR(101MHz,CDCl3)δ161.06,153.32,140.80,136.07,129.76,129.57,128.57,128.36,127.06,123.76,121.76。
实施例5：
化合物5的合成：将吩噻嗪，1,3-二氯氯苯，碘化亚铜，18-冠-6和碳酸钾加入到单口圆底烧瓶中，密封然后氮气保护，再加入邻二氯苯溶解并搅拌，在185℃条件下回流反应24h。反应结束后，向反应液中加入去离子水猝灭反应，然后用二氯甲烷萃取，有机相用无水硫酸钠干燥并减压浓缩。最后，通过层析柱纯化后得到白色固体产物，产率为43％。1H NMR(400MHz,CDCl3)δ7.35(t,1H),7.27(d,2H),7.21(t,1H),7.13(d,1H),6.97(t,2H),6.83(s,1H),6.72(d,2H).13C NMR(101MHz,CDCl3)δ148.94,141.45,128.79,127.11,126.61,124.39,124.32,122.70,115.73,108.47。
实施例6：
化合物6的合成：化合物4的合成：将吩噻嗪，2-氯-6苯基吡啶，碘化亚铜，18-冠-6和碳酸钾加入到单口圆底烧瓶中，密封然后氮气保护，再加入邻二氯苯溶解并搅拌，在185℃条件下回流反应24h。反应结束后，向反应液中加入去离子水猝灭反应，然后用二氯甲烷萃取，有机相用无水硫酸钠干燥并减压浓缩。最后，通过层析柱纯化后得到白色固体产物，产率为31％。1H NMR(400MHz,CDCl3)δ8.04(d,1H),7.55(d,2H),7.49(s,1H),7.35(t,1H),7.25(t,1H),7.16,(d,1H),7.07(s,1H),6.97(d,2H),6.36(d,1H).13C NMR(101MHz,CDCl3)δ158.58,156.00,140.80,137.96,137.27,130.26,129.57,128.22,127.87,127.05,123.76,121.76,119.83,117,33。
实施例7：
防伪图案的制作：
称取按照实施例1方法制备得到的化合物1和TCzCl2白色固体50mg于研钵中，再加入适量的芦荟胶，将两者分别与芦荟胶混合研磨均匀，得到粘度合适的乳白色粘稠物。将该白色粘稠物涂抹在丝网印刷的模板上进行印刷，得到蝴蝶形状的图案。在365nm灯激发下并关闭后，化合物1的磷光颜色蓝色的，TCzCl2的磷光颜色是黄绿色的；当用450nm的灯激发并关闭后，化合物1的磷光颜色是橙黄色的，TCzCl2的磷光颜色依然是黄绿色的。在不同的激发光源下，两种物质表现出不同的发光颜色，因此，化合物1这一类激发光依赖的智能材料可用于防伪及加密应用领域。
Claims (5)
1.一种全彩超长有机磷光材料，其特征在于该材料含有如下结构：
中，R的结构如下：
-CnH2n+1，n＝1～8
中心T的结构如下：
R1的结构如下：
-CnH2n+1或-NHCnH2n+1或-OCnH2n+1或-SCnH2n+1或-H-PhCnH2n+1或-PhNHCnH2n+1或-PhOCnH2n+1或-PhSCnH2n+1；
其中，n＝1～8。
R2的结构如下：
-CnH2n+1或-NHCnH2n+1或-OCnH2n+1或-SCnH2n+1或-H-PhCnH2n+1或-PhNHCnH2n+1或-PhOCnH2n+1或-PhSCnH2n+1；
其中，n＝1～8。
中心M的结构如下：
R3的结构如下：
-CnH2n+1或-NHCnH2n+1或-OCnH2n+1或-SCnH2n+1或-H-PhCnH2n+1或-PhNHCnH2n+1或-PhOCnH2n+1或-PhSCnH2n+1；
其中，n＝1～8。
2.根据如权利要求1所述的全彩超长有机磷光材料，其特征在于，所述的中的S元素被氧化成
3.如权利要求1所述的全彩超长有机磷光材料，其特征在于该材料的制备方法如下：
4.如权利要求1所述的全彩超长有机磷光材料，其特征在于该全彩超长有机磷光材料在晶体状态下具有超长磷光寿命达0.14s，磷光量子效率达29％。
5.权利要求1所述的全彩超长有机磷光材料在实现数据加密和和防伪中的应用。
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| CN110386905A (zh) * | 2019-08-08 | 2019-10-29 | 吉林大学 | 一种室温磷光化合物、组合物及其应用 |
| CN112321531A (zh) * | 2020-11-06 | 2021-02-05 | 天津大学 | 一种有机室温磷光材料及其制备方法和应用 |
| CN115611826A (zh) * | 2022-07-27 | 2023-01-17 | 武汉大学 | 吩噻嗪衍生物、及其制备方法和应用 |
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| CN112321531A (zh) * | 2020-11-06 | 2021-02-05 | 天津大学 | 一种有机室温磷光材料及其制备方法和应用 |
| CN115611826A (zh) * | 2022-07-27 | 2023-01-17 | 武汉大学 | 吩噻嗪衍生物、及其制备方法和应用 |
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