Li Zhongyu, Wang Yanjie, Baryshnikov Gleb, Shen Shen, Zhang Man, Zou Qi, Ågren Hans, Zhu Liangliang
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai, China.
Division of Theoretical Chemistry and Biology School of Biotechnology, KTH Royal Institute of Technology, Stockholm, Sweden.
Nat Commun. 2021 Feb 10;12(1):908. doi: 10.1038/s41467-021-21253-w.
It is crucial and desirable to develop green and high-efficient strategies to regulate solid-state structures and their related material properties. However, relative to solution, it is more difficult to break and generate chemical bonds in solid states. In this work, a rubbing-induced photoluminescence on the solid states of ortho-pyridinil phenol family was achieved. This rubbing response relied on an accurately designed topochemical tautomerism, where a negative charge, exactly provided by the triboelectric effect of a rubber, can induce a proton transfer in a double H-bonded dimeric structure. This process instantaneously led to a bright-form tautomer that can be stabilized in the solid-state settings, leading to an up to over 450-fold increase of the fluorescent quantum yield of the materials. The property can be repeatedly used due to the reversibility of the tautomerism, enabling encrypted applications. Moreover, a further modification to the structure can be accomplished to achieve different properties, opening up more possibilities for the design of new-generation smart materials.
开发绿色高效的策略来调控固态结构及其相关材料性能至关重要且十分必要。然而，相对于溶液而言，在固态中破坏和生成化学键更加困难。在这项工作中，实现了邻吡啶基苯酚家族固态的摩擦诱导光致发光。这种摩擦响应依赖于精确设计的拓扑化学互变异构，其中橡胶的摩擦电效应精确提供的负电荷可在双氢键二聚体结构中诱导质子转移。这一过程瞬间导致一种亮形式互变异构体，其可在固态环境中稳定存在，使材料的荧光量子产率提高多达450倍以上。由于互变异构的可逆性，该性能可重复使用，从而实现加密应用。此外，可以对结构进行进一步修饰以实现不同性能，为新一代智能材料的设计开辟更多可能性。
