Molecules have limited mobility in the solid state because of the strong intermolecular interactions, and therefore, applications based on solid-state molecular motions are seldom explored. Herein, by manipulating the solid-state intramolecular motion of tetraphenylethylene (TPE) in a crystallizing polymer matrix, controlled fluorescent patterns with information storage and encoding functionality are developed. The intramolecular mobility of TPE can not only affect the fluorescence intensity but also determine the photocyclization activity, which can be tuned by surrounding polymer rigidity. The soft amorphous region in the semicrystalline polymer facilitates the intramolecular motion to achieve weak blue emission and high photocyclization activity, whereas the rigid crystalline phase restricts the intramolecular motion to give intense blue emission and low photoreactivity. Meanwhile, in the process of crystallization, the dynamic movement of the polymer chain in the crystal growth boundary layer further accelerates the intramolecular motions of TPE, allowing enhanced photoreactivity across crystalline and amorphous regions. The motion-dominated fluorescence allows TPE as a smart molecular robot to generate desired fluorescent patterns triggered by polymer crystallization. Our findings provide a correlation between microscopic molecular motions and macroscopic optical signals.

中文翻译：

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操纵固态分子内运动向受控的荧光模式。

由于强的分子间相互作用，分子在固态中的移动性有限，因此，很少研究基于固态分子运动的应用。在本文中，通过控制结晶聚合物基质中四苯乙烯（TPE）的固态分子内运动，开发了具有信息存储和编码功能的受控荧光图案。TPE的分子内迁移率不仅可以影响荧光强度，而且可以确定光环化活性，这可以通过周围的聚合物刚性来调节。半结晶聚合物中的柔软无定形区域有助于分子内运动，从而实现弱蓝色发射和高光环化活性，而刚性的结晶相限制了分子内的运动，从而产生强烈的蓝光发射和低的光反应性。同时，在结晶过程中，聚合物链在晶体生长边界层中的动态运动进一步加速了TPE的分子内运动，从而增强了晶体和非晶区域之间的光反应性。运动主导的荧光使TPE作为智能分子机器人可以生成由聚合物结晶触发的所需荧光图。我们的发现提供了微观分子运动与宏观光学信号之间的相关性。增强了晶体和非晶区域的光反应性。运动主导的荧光使TPE作为智能分子机器人可以生成由聚合物结晶触发的所需荧光图案。我们的发现提供了微观分子运动与宏观光信号之间的相关性。增强了晶体和非晶区域的光反应性。运动主导的荧光使TPE作为智能分子机器人可以生成由聚合物结晶触发的所需荧光图案。我们的发现提供了微观分子运动与宏观光信号之间的相关性。