Chem. Eur. J. ：AIE特性的四苯乙烯基四羧酸盐体系：双重离子传感与机械变色

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常州大学肖唐鑫教授研究小组和南京大学王乐勇教授联合开发了一种四苯乙烯基四羧酸盐衍生物。该化合物能够在水中自组装形成单层纳米片，展示出稳定的蓝色荧光发射。特别值得关注的是该分子展现出多功能特性：对Al3+离子表现出荧光比色响应，对Fe3+离子则产生荧光淬灭效应，以及具有机械刺激响应性和自擦除书写功能（图1）。

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图1. TPEC的结构和自组装示意图及其多功能应用示例

超分子自组装的复杂性不仅赋予分子丰富的光物理性质，还为多功能应用开辟了广阔的前景。超分子自组装与聚集诱导发光（AIE）之间的协同效应已成为材料工程领域的前沿课题。自组装过程能够将无序的聚集发光转化为有序的聚集发光，进而引发组装诱导发光现象。通过发挥AIE发光团的独特性质并精确调控分子间的超分子相互作用，研究人员能够设计出光学性质和功能性能可调的材料。因此，超分子自组装为构建复杂纳米结构提供了灵活的途径，而AIE则为在组装态下增强荧光提供了有效机制。这种协同作用不仅使得材料性质的精细调控成为可能，也为开发具有创新功能的先进材料铺平了道路。基于上述考虑，南京大学王乐勇教授课题组和常州大学肖唐鑫课题组联合报道了一种多功能有机分子TPEC，该化合物能够在水相中自组装形成单层纳米片，展示出稳定的蓝色荧光发射（图2）。

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图2. TPEC的AIE行为测试及其自组装结构的表征

TPEC展现出多功能特性。首先，基于羧酸根的金属配位能力，研究了TPEC的金属离子识别能力（图3）。研究表明，TPEC水溶液对Al3+离子表现出荧光比色响应，荧光颜色由蓝色转变为青色；而对Fe3+离子则产生了明显的荧光淬灭效应。此外，TPEC的紫外-可见吸收光谱在Al3+和Fe3+存在下也发生了显著的变化，进一步表明它们与TPEC之间存在协同作用。为了实现更加便捷和高效的金属离子检测，作者制备了浸渍TPEC的试纸，能够快速且精准地检测Al3+离子和Fe3+离子。最后，TPEC成功应用于实际水样的金属离子检测。

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图3. TPEC对的Al3+离子和Fe3+离子的识别

此外，在固态下，TPEC表现出机械变色特性（图4）。通过外力研磨，TPEC粉末的荧光发射颜色由蓝色转变为青色，并且在一定时间内能够自我恢复至蓝色。该过程可循环进行超过10次，且TPEC可在涂覆其的纸张上实现自擦写书写。本研究不仅展示了TPEC在多种应用中的多功能性和高效性，还提出了一种针对特定光学需求设计与合成多功能材料的新策略。这些发现凸显了精准的分子与超分子工程在提升有机分子光物理性能方面的重要优势。

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图4. TPEC的机械变色和自擦除书写示意图


论文信息

Tetraphenylethylene-Derived Tetracarboxylate Featuring AIE Properties for Dual Ion Sensing and Mechanochromic Self-Erasable Writing

Qiaona Zhang, Xiaoman Dang, Fengyao Cui, Zhiying Wu, Zheng-Yi Li, Xiao-Qiang Sun, Tangxin Xiao, Leyong Wang


Chemistry – A European Journal

DOI: 10.1002/chem.202403203

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