X-ray and UV Dual Photochromism, Thermochromism, Electronchromism and Amine-Selective Chemochromism in an Anderson-like Zn7 Cluster Based 7-Fold Interpenetrated Framework,Journal of the American Chemical Society

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X-ray and UV Dual Photochromism, Thermochromism, Electronchromism and Amine-Selective Chemochromism in an Anderson-like Zn7 Cluster Based 7-Fold Interpenetrated Framework
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2019-07-21 , DOI: 10.1021/jacs.9b04930
Shi-Li Li ₁ , Min Han ₁ , Yan Zhang ₁ , Guo-Ping Li ₂ , Mei Li ₁ , Gang He ₂ , Xian-Ming Zhang _{1,

3}

Affiliation

Smart materials are highly desirable over the recent decade due to the growing demand on complicated nature. Stable stimuli-responsive smart materials exhibit widespread potential for applications in smart windows, sensors, separators, chemical valves and release platforms but are rare. In spite of being good candidates, viologen-based multifunctional smart materials are still a challenging task for chemists. To obtain such materials, the judicious strategy is to introduce polynuclear metal-carboxylate clusters as electron donors into stable framework to increase chromic sensitivity. Towards this endeavor, we have synthesized a novel viologen-based polymer with a unique Anderson-like metal-carboxylate cluster, namely [Zn7(bpybc)3(o-BDC)6]•2NO3•6H2O (bpybc = 1,1'-bis(4-carboxyphenyl)- 4,4'-bipyridinium, o-BDC = o-benzenedicarboylic acid) (1), which is a particular 7-fold interpenetrated framework with 3D pcu network in which bpybc ligand as linker and Zn7O30C12 second building unit (Zn7 SBU) as 6-connected nodes. More importantly, it shows excellent chromic behavior in response to multiple external stimuli especially soft X-ray and UV dual light, temperature, electricity and organic amines, which stand out in the viologen-based polymers. Interestingly, the coloration process of 1 from "core" to "edge" is observed upon heating at the appropriate temperature, which has not yet been found in other reported thermochromic materials. Of particular interest for 1 is the couple of quaternary stimuli sensitive abilities because it simultaneously meets the following condition: (i) the capability of withstanding high light, higher temperature, extreme of pH, and other harsh conditions; (ii) the high sensitivity to external stimuli keeping away from photodegradation, thermal relaxation, side reactions and so on. To be noted, 1 has the high thermal stability and chemical stability, which are the excellent advantages as smart materials. To further develop possible practical utilization, 1 has been doped into the polymer matrices to construct a hybrid film, which not only keep the response to external stimuli but also significantly improve the repeatability of the photochromic process, indicating that a new smart device with multistimuli-responsive functions will emerge successively in future.

中文翻译：

基于 7 重互穿框架的类 Anderson Zn7 簇中的 X 射线和紫外线双重光致变色、热致变色、电子致变色和胺选择性化学变色

由于对复杂性质的需求不断增长，智能材料在最近十年非常受欢迎。稳定的刺激响应智能材料在智能窗户、传感器、分离器、化学阀门和释放平台中具有广泛的应用潜力，但很少见。尽管是很好的候选者，但基于紫精的多功能智能材料对化学家来说仍然是一项具有挑战性的任务。为了获得这样的材料，明智的策略是将多核金属羧酸盐簇作为电子供体引入稳定的框架中，以提高铬敏感性。为此，我们合成了一种新型紫精基聚合物，其具有独特的类安德森金属羧酸盐簇，即 [Zn7(bpybc)3(o-BDC)6]•2NO3•6H2O (bpybc = 1,1'-双(4-羧基苯基)-4,4'-联吡啶鎓，o-BDC = o-benzodiacarboylic acid) (1)，这是一个特殊的 7 重互穿框架，具有 3D pcu 网络，其中 bpybc 配体作为连接器，Zn7O30C12 第二个构建单元 (Zn7 SBU) 作为 6 连接节点。更重要的是，它在响应多种外部刺激时表现出优异的变色行为，尤其是软 X 射线和紫外线双光、温度、电和有机胺，这在紫精类聚合物中脱颖而出。有趣的是，在适当的温度下加热时观察到 1 从“核心”到“边缘”的着色过程，这在其他报道的热致变色材料中尚未发现。对 1 特别感兴趣的是四元刺激敏感能力，因为它同时满足以下条件：(i) 承受强光的能力，更高的温度、极端的 pH 值和其他恶劣条件 (ii) 对外部刺激高度敏感，避免光降解、热弛豫、副反应等。需要注意的是，1具有较高的热稳定性和化学稳定性，这是作为智能材料的优良优势。为了进一步开发可能的实际应用，将 1 掺杂到聚合物基质中以构建混合膜，不仅保持对外部刺激的响应，而且显着提高了光致变色过程的可重复性，表明具有多重刺激的新型智能设备响应功能将陆续出现。需要注意的是，1具有较高的热稳定性和化学稳定性，这是作为智能材料的优良优势。为了进一步开发可能的实际应用，将 1 掺杂到聚合物基质中以构建混合膜，不仅保持对外部刺激的响应，而且显着提高了光致变色过程的可重复性，表明具有多重刺激的新型智能设备响应功能将陆续出现。需要注意的是，1具有较高的热稳定性和化学稳定性，这是作为智能材料的优良优势。为了进一步开发可能的实际应用，将 1 掺杂到聚合物基质中以构建混合膜，不仅保持对外部刺激的响应，而且显着提高了光致变色过程的可重复性，表明具有多重刺激的新型智能设备响应功能将陆续出现。

更新日期：2019-07-21

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