CN110372734B - 一种单取代紫精基杂化光致变色材料及其制备方法 - Google Patents
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Abstract
本发明涉及一种单取代紫精基杂化光致变色材料的制备方法，是将Cd(NO3)2·4H2O，23.6mg,0.1mmol；1‑[(3,5‑二甲酸二甲酯)苄基]‑4,4'‑联吡啶溴化物(LBr)，41mg，0.1mmol；NaOH溶液，2mL，0.1mmol/L和H2O，6mL封入带有聚四氟乙烯内衬的20mL不锈钢反应釜中，于130℃加热3天，随后冷至室温，得到块状黄色晶体。其结构式为[Cd(L)(Br)(H2O)]·4H2O。本发明制备的变色材料光响应范围变宽，响应速度加快，灵敏度提高。
Description
技术领域
本发明涉及光致变色材料领域，具体涉及一种单取代紫精基杂化光致变色材料及其制备方法。
背景技术
光致变色材料广泛应用于传感器、光开关、数据存储、无墨打印介质等领域。无机光致变色化合物WO3、V2O5和MoO3以及有机光致变色化合物如螺吡喃、二芳基乙烯和紫精等引起了广泛关注。紫精是4,4’-联吡啶氮原子上的单或双取代产物。在特定波长的光照下，缺电子的紫精阳离子发生氧化还原反应，形成紫精自由基，颜色由无色变为紫色。一般来说，由于还原态紫精自由基对氧化剂高度敏感，导致着色态是厌氧的，不稳定。另外传统的有机紫精毒性大，抗疲劳性差，且光致变色行为多发生在溶液中，固态的光致变色过程难以实现。
目前，为了得到稳定的固态光致变色紫精体系，有效的方法是引入金属离子构筑紫精基无机-有机杂化材料。紫精基配位聚合物正是在这样的背景下发展起来的。金属离子可以通过配位键调节紫精配体的排列，从而影响电子转移路径。然而，从配位作用的角度考虑，紫精配体中氮原子的正电荷在其表面产生电场，这对自组装过程不利，所以难以得到预期的紫精基杂化材料。再者，已报道的紫精基杂化光致变色材料，合成条件苛刻，光致变色效率低。例如，李付安等人报道的紫精-Cd(II)配合物需要在有毒的有机溶剂甲醇和乙腈混合物中反应，采用0.1℃/min的冷却速度程序降温，以获得结晶良好的产物。产物变色效率较低，需在300W氙灯光照15min才达到饱和，颜色仅由淡黄色变为浅蓝色，变色较慢，灵敏度低。
发明内容
本发明要提供一种单取代紫精基杂化光致变色材料的制备方法，以克服现有技术存在的制备方法难和变色效率低的问题。
一种单取代紫精基杂化光致变色材料的制备方法，是将Cd(NO3)2·4H2O，23.6mg,0.1mmol；1-[(3,5-二甲酸二甲酯)苄基]-4,4'-联吡啶溴化物(LBr)，41mg，0.1mmol；NaOH溶液，2mL，0.1mmol/L和H2O，6mL封入带有聚四氟乙烯内衬的20mL不锈钢反应釜中，于130℃加热3天，随后冷至室温，得到块状黄色晶体。
进一步的，其结构式为[Cd(L)(Br)(H2O)]·4H2O。
与现有技术相比，本发明的优点如下：
1、采用羧基功能化的单取代紫精，且以溴离子为抗衡离子。一方面，羧基减弱了正电荷的影响并增强了紫精的配位能力。另一方面，溴离子具有较强的给电子能力，是良好的电子供体，有利于电子转移过程。不仅如此，单取代的紫精中未经取代的富电子吡啶环可以稳定紫精自由基，从而使产物的光响应范围变宽，响应速度加快，灵敏度提高。
2、本发明提供的制备方法路线简单，产率高，可达到45％。由于所采用的配体原料不用水解，而是在水热合成过程中加入NaOH，使配体直接水解并配位，所述步骤少，且用水做溶剂，绿色无毒，成本低。
3、不但对紫外光有响应，对阳光和手机灯光也响应迅速，颜色变化灵敏，稳定性好，光致变色性能优异。仅需6W紫外灯照射3s，即可由黄色变为深蓝色，1min后趋于饱和。阳光照射只需2min即可变色。
附图说明
图1为本发明紫精基光致变色材料中Cd(II)的配位环境图；
图2为本发明紫精基光致变色材料的晶体结构图；
图3为本发明紫精基光致变色材料的紫外可见漫反射光谱。
具体实施方式
下面通过具体实施方式结合附图对本发明作进一步详细说明。其中不同实施方式中类似元件采用了相关联的类似的元件标号。在以下的实施方式中，很多细节描述是为了使得本申请能被更好的理解。然而，本领域技术人员可以毫不费力的认识到，其中部分特征在不同情况下是可以省略的，或者可以由其他元件、材料、方法所替代。
一种单取代紫精基杂化光致变色材料的制备方法，包括下述步骤：
首先是要合成配体1-[(3,5-二甲酸二甲酯)苄基]-4,4'-联吡啶溴化物(LBr)，合成方法如下：
然后用水热法合成材料[Cd(L)(Br)(H2O)]·4H2O：
将Cd(NO3)2·4H2O(23.6mg,0.1mmol)、LBr(41mg，0.1mmol)、NaOH溶液(2mL，0.1mmol/L)和H2O(6mL)封入带有聚四氟乙烯内衬的不锈钢反应釜中(20mL)，于130℃加热3天，随后冷至室温，得到块状黄色晶体，产率45％。
在本发明给出的水热合成中加入NaOH溶液(2mL，0.1mmol/L)，使配体1-[(3,5-二甲酸二甲酯)苄基]-4,4'-联吡啶溴化物的酯基在水热合成过程中水解。
上述制备方法制得的单取代紫精基杂化光致变色材料的晶体数据及结构精修参数见表1
表1晶体数据和结构精修参数
aR1＝Σ||Fo|-|Fc||/Σ|Fo|.bwR2＝{Σ[w(Fo 2-Fc 2)2]/Σw(Fo 2)2]}1/2.
重要键长和键角见表2：
表2重要键长
和键角(°)
对称代码:#1-x+3,y-1/2,-z+1/2；#2x-1,y,z。
参见图1：
光致变色材料[Cd(L)(Br)(H2O)]·4H2O结晶于单斜晶系，P21/c空间群。晶胞参数
α＝90.00(°)，β＝92.620(4)(°)，γ＝90.00(°)，
光致变色材料晶体结构的不对称单元包含一个Cd(II)离子，一个L阴离子，一个溴离子，一个配位水和四个游离水分子。Cd(II)与三个L阴离子，一个溴离子和一个水分子配位，形成畸变八面体配位构型。
参见图2：
L阴离子的两个羧基分别以单齿和双齿螯合方式将Cd(II)连接成波浪状二维(2D)层。从拓扑学的角度看，L阴离子和Cd(II)可以被还简化为3连接的节点，2D层可以被表示为(63)网络。
参见图3：材料在紫外灯(365nm，6W，室温空气中)照射3秒或阳光照射2min后，颜色从黄色变为深蓝色。约1分钟后，着色过程趋于饱和。
紫外-可见漫反射光谱显示，初始黄色样品在300nm处出现强吸收带。光照后，在410nm左右出现弱肩峰，630nm处出现宽的强峰，这是紫精自由基的特征吸收峰。随着光照时间的延长，吸收带峰值变大。当在100℃下加热10分钟或在黑暗中放置4小时后，蓝色着色态产物变为黄色，并显示与初始未着色样品相同的光谱。
以上所述，仅为本发明的较佳实施例而已，并非用于限定本发明的保护范围。
Claims (1)
1.一种单取代紫精基杂化光致变色材料的制备方法，其特征在于，包括下述步骤：
首先是要合成配体1-[(3,5-二甲酸二甲酯)苄基]-4,4'-联吡啶溴化物(LBr)，合成方法如下：
然后用水热法合成所述光致变色材料，合成方法如下：
将23.6mg, 0.1mmol 的Cd(NO3)2·4H2O；41mg，0.1mmol 的LBr；2mL，0.1mmol/L 的NaOH溶液和6mL的 H2O封入带有聚四氟乙烯内衬的20mL不锈钢反应釜中，于130 °C加热3天，随后冷至室温，得到块状黄色晶体，该晶体数据及结构精修参数如下：
分子式：C19H23BrCdN2O9，单斜晶系，空间群：P21/c，a (Å)：10.0743(4)，b (Å)：25.3923(10)，c (Å)：8.5537(4)，α(°)： 90.00，β(°)：92.620(4)，γ(°)：90.00。
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