CN109232659A - 一种具有信息加密-解密功能的热致发光开关材料、制备方法及其应用 - Google Patents
一种具有信息加密-解密功能的热致发光开关材料、制备方法及其应用 Download PDFInfo
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Abstract
一种具有信息加密‑解密功能的热致发光开关材料、制备方法及其应用,该材料以铂(II)与3‑三甲基硅乙炔基‑1,10‑菲罗啉配体和2‑氯苯乙炔辅助配体形成的配合物。该材料在结合二氯甲烷分子和1,2‑二氯乙烷分子后,得到两种在日光或紫外光下肉眼均无法分辨的样品,其颜色为黄色,发光为绿色。结合二氯甲烷分子的样品在90℃加热后会变为橙红色,而结合二氯乙烷的样品在102℃以上的温度加热时,其颜色和发光才会变为橙红色。根据这两种样品在不同温度下发生颜色和发光变化的特性,可用于实现基于一种起始材料的信息加密‑解密技术。此外该材料具有高灵敏度、高安全性、高稳定性、成本低、可塑性强、易于操作、可循环使用等优势。
Description
技术领域
本发明属于发光开关材料的性质和应用技术领域,具体涉及一种具有热致发光开关性质的材料的研究及其在信息加密-解密技术中的应用。
背景技术
信息安全在人们的日常生活和生产中具有至关重要的意义,对于信息的安全保护越来越受到人们的重视。目前,信息储存材料主要涉及具有对光、电、磁等信号具有特殊响应的物质。由于光学材料具有存储密度大,现象直观等优点,基于发光开关材料的信息存储技术越来越引起了人们的广泛关注。这类发光开关材料在受到特定的外部刺激后,材料的结构和激发态能级会发生改变,宏观上呈现出材料颜色和(或)发光的显著变化,因此可以利用其颜色和(或)发光的变化特征来实现信息的安全存储。与传统的信息记录与储存方法相比,这种利用发光开关材料对信息进行存储和加密的方法具有较高的灵敏度、设备和操作简易、成本低且安全系数高等诸多优势。因此,利用发光开关材料对信息进行安全存储已成最具应用前景的方法之一。此外,在众多的信息安全存储技术中,信息加密-解密技术由于能够有效的将信息藏于背景之中,并且在特定的条件下实现信息的解密,因此被认为是安全性最高的信息存储方法之一。但是由于材料的限制,目前存在的加密-加密技术都是基于双材料体系:用于信息载体的功能材料和与功能材料具有相同光物理性质的背景材料。将功能材料附着在背景材料上时,由于信息和背景具有相同的颜色和发光,因此不论在日光还是紫外灯照射下,信息均无法识别,从而实现信息的加密。在特定条件下,功能材料的颜色和发光会发生改变而背景材料不会,此时信息将被解密并可以读取。但是这种方法存在着背景材料很难选择,操作复杂,信息无法擦除,成本高,并且不可重复使用等缺陷限制了其更加广阔的应用。因此,基于一种起始材料的信息加密-解密技术目前已成为信息安全存储技术的重要前沿课题。
发明内容
本发明的目的在于提供了一种基于热致发光开关性质的二价铂配合物的信息安全存储材料;本发明的另一目的是提供了一种简单的利用温差效应实现的基于一种起始材料的信息加密-解密技术。
本发明的技术方案:
一种具有信息加密-解密功能的热致发光开关材料,该热致发光开关铂配合物以3-三甲基硅乙炔基-1,10-菲罗啉为配体、2-氯苯乙炔为辅助配体的二价铂化合物,该二价铂化合物的化学式为Pt(PhenC≡CTMS)(C≡CC6H4Cl-2)2,其中PhenC≡CTMS为3-三甲基硅乙炔基-1,10-菲罗啉;C≡CC6H4Cl-2为2-氯苯乙炔基,其结构式如下:
一种具有信息加密-解密功能的热致发光开关材料的制备方法,步骤如下:
氮气保护下,将[3-三甲基硅乙炔基-1,10-菲罗啉]二氯化铂与2-5当量的2-氯苯乙炔,0.001-0.10当量的碘化亚铜,在二异丙胺与二氯甲烷(体积比1:10)溶液中室温下搅拌反应1天。再用硅胶柱分离得到产物,产率75-80%。
该材料在分别结合二氯甲烷分子和1,2-二氯乙烷分子后,得到两种在日光或紫外光下肉眼均无法分辨的样品,其颜色为黄色,发光为绿色,发射峰的位置在510nm(540nm,肩峰)。将这两种状态用120℃加热后,其颜色和发光均变为了橙红色,发射峰的位置红移至626nm,说明配合物具有热致发光开关性质。差热分析结果表明,我们发现结合二氯甲烷的样品在85℃处有一个放热峰,而结合1,2-二氯乙烷的样品则在102℃有一个放热峰,均为溶剂丢失的过程。因此该材料的热致发光开关性质是由于失去溶剂引起的堆积结构变化造成的。同时我们发现两种状态的变色温度有一定的差异,结合二氯甲烷的样品在85℃-95℃加热下,其颜色和发光就变为橙红色;此时,结合1,2-二氯乙烷的样品由于未达到其相变温度,颜色和发光不变,仍为绿色发光,因此两者产生了色差。此外,两种结合溶剂的状态之间可以通过吸附相应蒸汽实现可以的互变。这些性质可以使其分别作为功能材料和背景材料来实现基于一种起始材料的加密-解密技术。将结合二氯甲烷的样品附着在纸上,得到密写纸,以1,2-二氯乙烷作为墨水在密写纸上写出需要加密的内容。此时,不论是颜色还是发光均无法识别出所写内容,从而实现了信息的写入和加密。将该加密纸在90℃加热后,结合二氯甲烷的背景的颜色和发光均变为了橙红色。而结合1,2-二氯乙烷样品的信息由于未达到其相变温度,其颜色和发光不会发生变化,从而实现了数据的解密和读取。将加热温度升高到120℃时,1,2-二氯乙烷处理过的样品也丢失溶剂,颜色和发光变为了橙红色,因此可以将录入的信息销毁。而将使用过的密写纸置于二氯甲烷蒸气的环境中便可以实现密写纸的再生,继而重复利用。
本发明的有益效果是:
(1)本发明利用具有热致发光开关性质的铂(II)配合物,通过其两种结合溶剂分子热致发光开关性质响应温度差的特性实现了基于一种起始材料的信息加密-解密功能。
(2)本信息存储材料具有信息输入和加密、信息解密和读取以及信息销毁等功能,并且还具有成本低廉、安全性高、响应快速、可视化、设备小巧易于操作以及无须专业知识等优势。
(3)本信息存储材料具有很好的应用性,可做成信息存储纸张和薄膜,或作为功能性墨水应用于信息加密打印技术。
(4)本信息存储材料具有很好的重复利用性,可多次重复使用,并且易于保存。
附图说明
图1是发光开关材料在不同状态下的吸收光谱(左图)和发射光谱(右图)。
图2是结合二氯甲烷和结合二氯乙烷样品在不同温度下加热时的颜色和发光的照片。
图3是配合物作为唯一的起始材料在数据加密-解密技术中的应用实例。
具体实施方式
以下结合附图和技术方案进一步说明本发明的具体实施方式。
Pt(II)配合物发光开关材料的制备。氮气保护下,将[3-三甲基硅乙炔基-1,10-菲罗啉]二氯化铂与2-5当量的2-氯苯乙炔,0.001-0.10当量的碘化亚铜,在二异丙胺与二氯甲烷(体积比1:10)溶液中室温下搅拌反应1天。再用硅胶柱分离得到产物,产率75-80%。元素分析结果:按C33H24Cl2N2PtSi计算值(%)C53.37,H3.26,N3.77;实测值(%)C53.35,H3.29,N3.75。1H NMR(CDCl3):10.227(s,1H),9.941(d,J(H,H)=5.0Hz,1H),9.224(s,1H),9.050(d,J(H,H)=5.0Hz,1H),8.335(d,J(H,H)=9.0Hz,1H),8.259(dd,J1(H,H)=5.0Hz,J2(H,H)=9.0Hz,1H),8.242(d,J(H,H)=9.0Hz,1H),7.568(d,J(H,H)=8.0Hz,1H),7.482(m,3H),7.294(m,2H),7.226(m,2H),0.349(s,9H)。
步骤2:结合图1和图2说明配合物在不同状态下的吸收和发射光谱。
该热致发光开关材料在结合二氯甲烷和1,2-二氯乙烷分子后,其颜色和发光均完全相同,颜色为黄色,呈现绿色发光,发射光谱的位置在510nm(540nm,肩峰),此时无论肉眼还是紫外灯下均不能将两者区别开来。90℃加热的条件下,结合二氯甲烷分子的样品丢失溶剂分子,颜色和发光变为了橙红色,发射峰位置也移动到了626nm处。而结合1,2-二氯乙烷分子的样品在同样条件下颜色和发光不变,发射光谱仍在510nm(540nm,肩峰)。将加热温度提高到120℃后,结合1,2-二氯乙烷分子的样品也变为同样的橙红色和橙红色发光,发射峰红移到626nm。
步骤3:结合附图3,说明配合物在信息加密-加密技术中的实际操作。
(1)将结合二氯甲烷分子的样品均匀的附着在纸上或做成薄膜材料,然后以二氯乙烷作为墨水在纸上写入信息。此时,不论日光或是在紫外灯下都无法对写入的信息进行识别,这一过程实现了信息的写入和加密。
(2)将写入信息的纸张置于90℃加热时,纸上写入的信息将会显示出来,从而实现信息的解密和读取。
(3)将步骤(2)中已读信息继续置于120℃加热一段时间后,那么写入的信息将会完全消失,从而实现信息的擦除。
(4)将信息销毁后的纸张吸附二氯甲烷蒸气后,能够变回到信息写入之前的状态,从而实现材料的循环使用。反复使用多次对材料的性质不会产生任何影响。
Claims (3)
1.一种具有信息加密-解密功能的热致发光开关铂配合物,其特征在于,该热致发光开关铂配合物以3-三甲基硅乙炔基-1,10-菲罗啉为配体、2-氯苯乙炔为辅助配体的二价铂化合物,该二价铂化合物的化学式为Pt(PhenC≡CTMS)(C≡CC6H4Cl-2)2,其中PhenC≡CTMS为3-三甲基硅乙炔基-1,10-菲罗啉;C≡CC6H4Cl-2为2-氯苯乙炔基,其结构式如下:
2.权利要求1所述的发光开关材料的制备方法,其特征在于,氮气保护下,将[3-三甲基硅乙炔基-1,10-菲咯啉]二氯化铂与2-5当量的2-氯苯乙炔,0.001-0.10当量的碘化亚铜,在体积比为1:10的二异丙胺与二氯甲烷溶液中室温下搅拌反应1天,得到热致发光开关材料Pt(PhenC≡CTMS)(C≡CC6H4Cl-2)2。
3.权利要求1所述的热致发光开关材料在信息加密-解密技术中的应用,其特征在于,该热致发光开关材料分别吸附二氯甲烷和1,2-二氯乙烷蒸气后,其颜色和发光均完全相同,颜色为黄色,呈现绿色发光,此时无论肉眼还是紫外灯下均不能将两者区别开来;在90℃加热时,结合二氯甲烷样品的颜色和发光变为了橙红色,发射峰位置也移动到了626nm处,而结合1,2-二氯乙烷样品的颜色和发光不变;将加热温度提高到120℃后,结合1,2-二氯乙烷样品的颜色和发光也会变为橙红色发光,发射峰红移到626nm;基于上述特性该热致发光开关材料用于制作含有该材料成分的具有加密-解密功能的纸张、薄膜及打印墨水。
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