Li Yang, Wang Kai, Feng Rui, Wang Jingtian, Xi Xiao-Juan, Lang Feifan, Li Quanwen, Li Wei, Zou Bo, Pang Jiandong, Bu Xian-He
School of Materials Science and Engineering, Smart Sensing Interdisciplinary Science Center, TKL of Metal and Molecule-Based Material Chemistry, Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin, 300350, P. R. China.
State Key Laboratory of Structure Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002 Fujian, China.
Angew Chem Int Ed Engl. 2024 May 27;63(22):e202403646. doi: 10.1002/anie.202403646. Epub 2024 Apr 5.
Organic piezochromic materials that manifest pressure-stimuli-responses are important in various fields such as data storage and anticounterfeiting. The manipulation of piezofluorochromic behaviors for these materials is promising but remains a great challenge. Herein, a non-luminous components regulated strategy is developed and organic molecular cages (OMCs), a burgeoning class of crystalline organic materials with structural dynamics, are first explored for the design of piezofluorochromic materials with tunable luminescence. A series of OMCs based on aggregation-induced emission (AIE) chromophores, termed Cage 1-3, are synthesized and their piezofluorochromic behaviors are investigated by diamond anvil cell technique. Due to the sufficient voids between its flexible chromophores offered by the OMC structure, Cage 1 exhibits thermofluorochromic and piezofluorochromic properties. Moreover, the piezofluorochromic performance of this OMC could be further promoted by replacing its non-luminous components with improved flexibilities, and a remarkable luminescence peak shift by 150 nm together with a response sensitivity of 13.8 nm GPa was achieved upon hydrostatic compression. The cage structure plays a vital role in facilitating efficient and reversible piezofluorochromic behaviors. This study has shed light on the rational design and exploitation of OMCs as an exceptional platform to accomplish customizable piezofluorochromic behaviors and enlarge their potential applications in pressure-based luminescence.
表现出压力刺激响应的有机压致变色材料在数据存储和防伪等各个领域都很重要。对这些材料的压致荧光变色行为进行调控具有广阔前景，但仍然是一项巨大挑战。在此，我们开发了一种非发光组分调控策略，并首次探索了有机分子笼（OMCs）——一类具有结构动力学的新兴结晶有机材料——用于设计具有可调发光的压致荧光变色材料。合成了一系列基于聚集诱导发光（AIE）发色团的OMCs，命名为Cage 1-3，并通过金刚石对顶砧技术研究了它们的压致荧光变色行为。由于OMC结构提供的柔性发色团之间存在足够的空隙，Cage 1表现出热致荧光变色和压致荧光变色特性。此外，通过用具有更高柔韧性的非发光组分替代，可以进一步提升这种OMC的压致荧光变色性能，在静水压力下实现了150 nm的显著发光峰位移以及13.8 nm GPa的响应灵敏度。笼状结构在促进高效且可逆的压致荧光变色行为方面起着至关重要的作用。这项研究为合理设计和开发OMCs作为实现可定制压致荧光变色行为的特殊平台以及扩大其在基于压力的发光方面的潜在应用提供了思路。
