CN111849455A - 一种含七元瓜环的光致变色材料及其制备方法 - Google Patents
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Abstract
本发明提供了一种含七元瓜环的光致变色材料及其制备方法，属于有机光致变色材料的制备与应用技术领域。该光致变色材料由七元瓜环与紫精化合物通过自组装形成，七元瓜环与紫精化合物的摩尔比为1：1。该光致变色材料制备时，将七元瓜环与紫精化合物按照等摩尔比混合搅拌溶解在水中；二者在溶液中自组装形成主客体化合物；将含有主客体化合物的溶液浓缩干燥，即得光致变色材料。本发明光致变色材料灵敏度高、响应速度快、稳定性与抗疲劳性高，在紫外和可见光照射下可以转变为另一种颜色，可以广泛应用于光信息存储、防护装饰、防伪与鉴伪以及保密等领域。
Description
技术领域
本发明属于有机光致变色材料的制备与应用技术领域，具体涉及一种光致变色材料及其制备方法。
背景技术
光致变色是某一物质在两种物理或化学状态之间的可逆变化，其中至少有一个方向的变化是由光辐射引起的，这可用以下方程表示：
其中A和B分别表示同一物质的两种不同颜色状态；λ1和λ2分别表示两种不同的波长。
光致变色的基本特征是：A和B在一定条件下能稳定存在；A和B有明显的颜色视差。但要实现真正的应用还要满足以下条件：A和B有足够高的稳定性；A和B有足够长的循环寿命；吸收带在可见光区；响应速度快，灵敏度高。但到目前为止，能完全满足上述条件并应用到实际中的光致变色材料十分有限。
光致变色材料包括无机光致变色材料和有机光致变色材料两大类。有机光致变色材料如乙烯吡啶、俘精酸酐、螺吡喃、螺嗪、偶氮、紫精类化合物等研究较多，应用也较为广泛。其中多数有机光致变色材料变色机理属于空间结构异变，而紫精化合物变色机理则是由于其本身的的缺电子结构在光诱导下的发生电子转移，因此生成显色自由基，从而实现光致变色。紫精类化合物光致变色材料普遍存在热稳定性及抗氧化性差，耐疲劳性低等缺点。当紫精化合物被包结进大环化合物空腔，形成主客体化合物时，大环化合物能起到电子供体和稳定紫精化合物的作用。
目前对于瓜环(cucurbit[n]uril,n＝5-8，又称葫芦联脲)系列同系物合成的方法(Day A I,Arnold A P,Blanch R J,(Unisearch Limited,Australia),PCTInt.Appl.2000,WO2000-2000AU412 20000505,112(Priority:AU 99-23219990507))日臻成熟，成本也急剧降低。而甲基紫精可从市场上直接购得，有些紫精化合物(如氯化-1-(4-羧基-苯亚甲基)-4,4’-联吡啶、二氯化-1,1’-二(4-羧基-苯亚甲基)-4,4’-联吡啶等)也可根据文献(Wei Li,Wei Wu,Shou-Tian Zheng and Jie Zhang.CrystEngComm,2008,10,1299-1301及Hao Shi,Kun Zhang,Rui-Lian Lin,Wen-Qi Sun,Xiang-Feng Chu,Xin-HuaLiu and Jing-Xin Liu.Asian Journal of Organic Chemistry 2019,8,339–343.)合成，这为合成可应用的光致变色材料提供方便。
发明内容
本发明的目的在于提供一种灵敏度高、响应速度快、稳定性与抗疲劳性高，在紫外和可见光照射下可以转变为另一种颜色，可以作为光信息存储、防护装饰、防伪与鉴伪和保密等方面应用的系列光致变色材料。
本发明的另一目的在于提供一种所需的原料简单易得，方法简单，操作简便的光致变色材料的制备方法。
本发明提供了一种基于七元瓜环和紫精化合物的有机光致变色材料，主体化合物选择七元瓜环，如通式Ⅰ所示。客体化合物选择系列紫精化合物中的一种，如通式Ⅱ所示。
通式Ⅱ中的X-代表F-,Cl-,Br-,I-,PF6 -等阴离子。R,R’可以是C1-C6烷基，也可以是苯基，苄基，萘基，呋喃基，噻吩基等芳环基，也可以是4-羧基-苯亚甲基等含有羧基的取代基。紫精化合物可以是双边取代，也可以是单边取代。
本发明所述的光致变色材料由主体七元瓜环与客体紫精化合物的一种组成，按摩尔比1:1的比例在弱酸性溶液中生成主客体包结物。
作为一种优化，所述紫精化合物为氯化-1-(4-羧基-苯亚甲基)-4,4’-联吡啶。
作为一种优化，所述紫精化合物为二氯化-1,1’-二(4-羧基-苯亚甲基)-4,4’-联吡啶。
本发明所述的光致变色材料的合成方法包括以下步骤：
(1)本发明采用的原料七元瓜环和各种紫精化合物可以采用文献常规的方法制备，在此不再赘述。
(2)将七元瓜环或者七元瓜环的化合物中的一种和紫精化合物中的一种按照相同的摩尔数溶解在水中混合搅拌均匀得到澄清溶液。
(3)将上述澄清溶液用旋转蒸发仪浓缩干燥，即得光致变色材料。
与现有技术相比，本发明具有以下技术效果：
(1)方法简单，操作简便，需要的工序少，所需要的原料简单易得；
(2)所得的光致变色材料性能优异，除具有灵敏度高、响应速度快以外，还具有稳定性和抗疲劳性高等特点；
(3)所得的光致变色材料最突出的优点在于在可见光区就可发生光致变色现象。
附图说明
图1为实施例1得到的主客体化合物的结构示意图；
如图所示，氯化-1-(4-羧基-苯亚甲基)-4,4’-联吡啶结构的联吡啶基团包结在七元瓜环的疏水空腔中。
图2为实施例1的主客体化合物变色前后的紫外漫反射图；
如图所示，横坐标为波长，纵坐标为吸光度；光照前后，主客体化合物的吸光度发生显著变化。
具体实施方式
下面通过具体实施例对本发明作进一步说明，但本发明不局限于下述实施例。
实施例1
1)分别秤取1.162g的七元瓜环和0.327g的氯化-1-(4-羧基-苯亚甲基)-4,4’-联吡啶(一种紫精化合物)，将它们混合搅拌溶解在约30ml水溶液中；二者在水溶液中能通过自组装方式形成主客体化合物。
2)将上述主客体化合物的溶液用旋转蒸发仪旋干，再放到烘箱彻底干燥，即得基于七元瓜环和氯化-1-(4-羧基-苯亚甲基)-4,4’-联吡啶的光致变色材料。
3)该光致变色材料在太阳光照时，极短时间内(2分钟)即可由白色变为深蓝色。
实施例2
1)分别秤取1.162g的七元瓜环和0.498g的二氯化-1,1’-二(4-羧基-苯亚甲基)-4,4’-联吡啶(一种紫精化合物)，将它们混合搅拌溶解在约30ml水溶液中；二者在水溶液中能通过自组装方式形成主客体化合物。
2)将上述主客体化合物的溶液用旋转蒸发仪旋干，再放到烘箱彻底干燥，即得基于七元瓜环和氯化-1-(4-羧基-苯亚甲基)-4,4’-联吡啶的光致变色材料。
3)该光致变色材料在太阳光照时，极短时间内(2分钟)即可由白色变为深蓝色。
Claims (3)
1.一种含七元瓜环的光致变色材料，其特征在于：该光致变色材料由主体七元瓜环与客体紫精化合物中的一种组成，主体与客体的摩尔比为1︰1；
该光致变色材料的制备包括以下步骤：
(1)将七元瓜环和紫精化合物中的一种按照相同的摩尔数溶解在水中混合搅拌均匀得到澄清溶液，溶液中含有七元瓜环和紫精化合物通过自组装形成的主客体化合物；
(2)将上述自组装形成的主客体化合物的溶液用旋转蒸发仪浓缩干燥，即得光致变色材料。
2.如权利要求1所述的含七元瓜环的光致变色材料，其特征在于，所述紫精化合物为氯化-1-(4-羧基-苯亚甲基)-4,4’-联吡啶。
3.如权利要求1所述的含七元瓜环的光致变色材料，其特征在于，所述紫精化合物为二氯化-1,1’-二(4-羧基-苯亚甲基)-4,4’-联吡啶。
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