CN107987061A - 一种动态可调的纯有机长余辉材料及其制备方法和应用 - Google Patents
一种动态可调的纯有机长余辉材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于纯有机长余辉材料领域，具体涉及一类动态可调的纯有机长余辉材料及其制备方法，并涉及该类材料在数据加密的应用。该材料具有以下特点：(1)亲核反应合成材料，原料廉价，合成方法简便；(2)合成的材料余辉寿命长；(3)材料的余辉寿命可以通过外界刺激例如光照，加热等来调节；(4)利用动态可调有机长余辉发光实现对信息的多重加密应用。利用本发明的材料用于数据加密方面获得了令人满意的结果。可以预期，该类有机发光材料将是一类有巨大商业化潜力的新型长余辉材料。
Description
技术领域
本发明属于纯有机长余辉材料领域，具体涉及一类动态可调的纯有机长余辉材料及其制备方法，并涉及该类材料在数据加密的应用。
背景技术
当受到外界的刺激，如光、电、热、湿度、压力以及磁场等时，材料的一些光物理性质如自旋跃迁、电荷转移以及激发态的性质可能发生改变。这样的智能响应型材料在很多领域例如信息存储、防伪以及分子机器等存在着巨大的应用价值。例如光诱导分子结构的改变可以使分子具有动态的双稳态特性，可将其应用于可逆的光开关和光学存储器；在电场作用下，利用智能磷光响应材料的动态特性可以构筑数据存储与加密器件。在材料科学领域，尽管对材料光物理性质实现动态调控已有所发展，但是在开发新型智能响应材料仍然存在着巨大的挑战。
近年来，具有长寿命激发态性质的光电功能材料无论在基础科学研究，还是在显示、应急信号灯、数据加密以及生物成像等领域都备受青睐。但是这种材料目前仅局限于无机材料，无机长余辉材料由于加工条件苛刻、材料来源稀缺以及重金属生物毒性等缺点限制其广泛应用。所以人们利用构建H型聚集体、晶体诱导、主客体掺杂、MOF框架等策略实现一系列有机材料的长余辉发光，来取代无机长余辉发光材料。与无机长余辉材料相比，有机材料具有柔性、易合成与易修饰改性等优点。例如通过简单引入重原子(如卤素以及氘代元素等)或特殊的有机修饰结构单元(含杂原子的芳香基团)增加自旋耦合作用，促进光生激子从单线态到三线态间的系间穿越，实现了长寿命的磷光发射。
迄今为止，有机长余晖磷光材料仅局限于静态长余辉材料即受到紫外光激发后关掉光源，超长的发光会被立刻观察到。然而随着外界的刺激(光、热)作用于材料使其展现出具有动态可调的长余辉的性质有机材料至今还未被开发。
发明内容
本发明的目的在于克服上述不足之处提供一种动态可调的长余辉材料，涉及该材料的超长寿命发光、寿命可通过外界刺激例如紫外光和加热来调节等重要的光物理性质。
本发明的另一目的是提供该智能响应型长余辉材料的制备方法。
本发明还有一个目的是提供该材料在数据加密与多重防伪上的应用。
为了推动纯有机长余辉材料在生活中的广泛应用，本发明设计制备了一系列智能响应型长余辉材料，本发明的目的是通过以下方式实现的：
一种纯有机长余辉材料，该材料具有如下通式结构：
其中，R1为-CnH2n+1，-OCnH2n+1，-SCnH2n+1，-NHCnH2n+1，-N(CH3)2，-O(C6H5)，-NH(C6H5)，-N(C6H5)2或醚链，其中n为1～6；
R2为-CnH2n+1，-OCnH2n+1，-SCnH2n+1，-NHCnH2n+1，-N(CH3)2，-O(C6H5)，-NH(C6H5)，-N(C6H5)2或醚链，其中n为1～6；
R3为刚性的共轭结构，可以为咔唑、吩噻嗪、吖啶、吖啶酮、吲哚酮或吲哚。
其结构具体可为以下结构中的一种：
其中，R2与R1出现时相同或者不同，R1、R2为-CnH2n+1，-OCnH2n+1，-SCnH2n+1，-NHCnH2n+1，-N(CH3)2，-O(C6H5)，-NH(C6H5)，-N(C6H5)2或醚链，n为1～6。
优选R1为-CnH2n+1，-OCnH2n+1，-SCnH2n+1，-NHCnH2n+1；R2为-CnH2n+1，-OCnH2n+1，-SCnH2n+1，-NHCnH2n+1；R3为咔唑；
最优选R1，R2选择相同基团(如R1＝-OCnH2n+1，R2＝-OCnH2n+1)，n为1～6，选择它们时尽量使得烷基链对称。
上述纯有机长余辉材料的光物理性质为：聚集态下通过紫外光激发发光寿命可以实现从1.8到1300ms的调节，并且通过加热材料，余辉寿命可恢复至1.8ms。
上述纯有机长余辉材料的制备方法，以咔唑为原料与三氯三嗪和烷基链亲核反应制备得到。
优选化合物的制备过程通式如下：
其中，X为-CnH2n+1，-OCnH2n+1，-SCnH2n+1，-NHCnH2n+1，-N(CH3)2，-O(C6H5)，-NH(C6H5)，-N(C6H5)2或醚链，n为1～6。
上述纯有机长余辉材料可以通过外界紫外光照射不同时间，产生长余辉发光，并有效应用于多重数据加密。
制备多重加密的图案方法如下：本发明室温长余辉材料的特征在于具有长寿命，而且寿命具有动态可调的特征，不同于先前报道的长余辉材料。利用不同的余辉材料，制备不同的图案，利用不同时间的紫外激发，实现图案的多重加密(附图5)。
本发明通过核磁共振(NMR)、单晶X射线衍射表征了长余辉材料的结构；通过荧光发射光谱、磷光发射光谱以及磷光寿命的测量，详细研究这一系列长余辉材料在聚集状态下的光物理性质；通过引入不同长度的烷基链或改变烷基链与主结构单元的链接方式，改变分子的偶极矩，调控分子的堆积方式，实现光物理性质的理性调控。
应用方式如，一种可以瞬间被激发的长余辉材料MST(结构见附图1)，具有蓝色磷光发射，寿命为1300ms。如选择一种三分钟可以被激发的长余辉材料BST(结构见附图1)，具有蓝色荧光发射，寿命为1200ms。一种十分钟可以被激发的长余辉材料PST(结构见附图1)，具有蓝色荧光发射，寿命为1300ms。将三种材料组合成字母E，可观察到365nm紫外光照射下显示字母“E”，365nm紫外灯关掉时，显示字母“I”，激发三分钟紫外光照射下显示字母“E”，365nm紫外灯关掉时，显示字母“F，激发十分钟紫外光照射下显示字母“E”，365nm紫外灯关掉时，显示字母“E”，将材料置于室温环境下，1.5小时后，365nm紫外光照射下显示数字“E”，365nm紫外灯关掉时，显示字母“L”,3小时后，365nm紫外光照射下显示数字“E”，365nm紫外灯关掉时，显示字母“I”。初步实现了数据的多重加密(见附图5)。
与现有技术相比，本发明的有益效果：
本发明不仅制备方法简单、原料价格低廉，而且这些长余辉材料具有超长发光寿命，并且其寿命可通过外界刺激来调控，可有效应用于多重数据加密。与传统的静态有机长余辉材料相比，动态可调的长余辉材料展现出更加智能的特性，随着外界环境的变化展现出不同的光学信号，材料的余辉寿命可以通过外界刺激例如光照、加热等来调节,更加适合用于多重的数据加密以及防伪等领域。
附图说明
图1：用于多重数据加密的三个材料的结构式。
图2：MST、PST和BST的荧光光谱图。
图3：MST、PST和BST的磷光光谱图。
图4：MST、PST和BST的光活化前后的寿命图。
图5：MST、PST和BST实现的多重加密图片。
具体实施方式
下面结合具体实施例对本发明作进一步说明。
以下通过具体实施例对本发明进行进一步说明：
其中，R1为-CnH2n+1，-OCnH2n+1，-SCnH2n+1，-NCnH2n+1，-N(CH3)2，-O(C6H5),-NH(C6H5),-N(C6H5)2或醚链；
实施例1：
纯有机长余辉材料中间体的合成过程：
称取咔唑1.0g(6.0mmol)，三氯三嗪1.22g(6.6mol)于50mL的烧瓶中，加入干燥的四氢呋喃10mL，冰水浴搅拌15min后。抽取正丁基锂6.6mmol，逐渐滴入上述体系中，于室温下反应2h。层析柱分离，石油醚：二氯甲烷＝2:1，得到的白色固体CDClT，产率为74％，结构表征如下：1H NMR(CDCl3):δ8.83(d,2H),7.98(d,2H),7.52(d,2H),7.44(d,2H)。
实施例:2：
称取0.065g金属钠(3.0mmol)于50mL的烧瓶中，加入干燥的甲醇10mL,室温下搅拌30min制备甲醇钠。称取0.5g(1.5mmol)白色固体CDClT于50mL烧瓶中，加入70mL干燥的四氢呋喃，抽取上述制备的甲醇钠溶液缓慢加入该体系与室温下搅拌20min。石油醚：二氯甲烷＝2:1，层析柱分离，得到的白色固体MST，产率为84％，结构表征如下：1H NMR(CDCl3):δ8.89(d,2H),7.96(d,2H),7.45(t,2H),7.38(t,2H),4.11(s,6H)。
实施例3：
称取0.29g金属钠(12.6mmol)于50mL的烧瓶中，加入干燥的正丙醇10mL,室温下搅拌30min制备丙醇钠。称取2.0g(6.3mmol)白色固体CDClT于50mmL烧瓶中，加入70mL干燥的四氢呋喃，抽取上述制备的丙醇钠溶液缓慢加入该体系与室温下搅拌20min。石油醚：二氯甲烷＝2:1，层析柱分离，得到的白色固体PST，产率为86％，结构表征如下：δ8.95(d,2H),8.01(d,2H),7.49(t,2H),7.38(t,2H),4.50(t,4H),1.89-1.97(m,4H),1.11(t,6H)。
实施例4：
称取0.29g金属钠(12.6mmol)于50mL的烧瓶中，加入干燥的正丁醇10mL,室温下搅拌30min制备丁醇钠。称取2.0g(6.3mmol)白色固体CDClT于50mL烧瓶中，加入70mL干燥的四氢呋喃，抽取上述制备的丁醇钠溶液缓慢加入该体系与室温下搅拌20min。石油醚：二氯甲烷＝2:1，层析柱分离，得到的白色固体BST，产率为86％，结构表征如下：δ8.94(d,2H),8.00(d,2H),7.49(t,2H),7.39(t,2H),4.53(q,4H),1.85-1.93(m,4H),1.52-1.62(m,4H),1.03(t,6H)
实施例5：
多重加密图案制作：
按照附图5中在纸上数字“E”，黑色部分涂上PST材料，深灰色部分涂上MST材料，浅灰色部分涂上BST材料，黑暗的环境下拍摄365nm手提紫外灯照射的照片，关掉灯的照片，紫外灯照射3、和10min后关掉灯的照片以及室温下放置1.5和3.0h后关掉灯的照片。
以上所述，仅是本发明的较佳实施例，并非对本发明作任何形式上的限制，任何熟悉本专业的技术人员，在不脱离本发明技术方案范围内，依据本发明的技术实质，对以上实施例所作的任何简单的修改、等同替换与改进等，均仍属于本发明技术方案的保护范围之内。
Claims (6)
1.一种动态可调的纯有机长余辉材料，其特征在于：该材料具有如下通式结构：
其中，R1为-CnH2n+1，-OCnH2n+1，-SCnH2n+1，-NHCnH2n+1，-N(CH3)2，-O(C6H5)，-NH(C6H5)，-N(C6H5)2或醚链，其中n为1～6；
R2为-CnH2n+1，-OCnH2n+1，-SCnH2n+1，-NHCnH2n+1，-N(CH3)2，-O(C6H5)，-NH(C6H5)，-N(C6H5)2或醚链，其中n为1～6；
R3为具有刚性的共轭结构的咔唑、吩噻嗪、吖啶、吖啶酮、吲哚酮或吲哚。
2.根据权利要求1所述的动态可调的纯有机长余辉材料，其特征在于：该材料为以下结构中的一种：
。
3.根据权利要求1所述的动态可调的纯有机长余辉材料，其特征在于：R1、R2为-OCH3，-OC2H5，-OC3H7，-OC4H9或-OC5H11柔性烷基链中的一种；其中，R1和R2为相同的基团或者不同的基团。
4.根据权利要求1所述的动态可调的纯有机长余辉材料，其特征在于：该材料以咔唑为原料与三氯三嗪和烷基链亲核反应制备得到。
5.根据权利要求1所述的动态可调的纯有机长余辉材料，其特征在于：聚集态下该材料通过紫外光激发发光寿命实现从1.8到1300ms的调节，并且通过加热，余辉材料发光寿命恢复至1.8ms。实现纯有机磷光长余辉的动态可逆调节。
6.权利要求1所述的动态可调的纯有机长余辉材料实现在多重数据加密中的应用。
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