Fu Kuo, Qu Da-Hui, Liu Guofeng
Shanghai Key Laboratory of Chemical Assessment and Sustainability, School of Chemical Science and Engineering, Advanced Research Institute, Tongji University, Shanghai 200092, P. R. China.
Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. China.
J Am Chem Soc. 2024 Dec 11;146(49):33832-33844. doi: 10.1021/jacs.4c12211. Epub 2024 Nov 28.
Constructing circularly polarized luminescence (CPL) materials that exhibit dynamic handedness inversion and emissive color modulation for multimodal information encryption presents both a significant challenge and a compelling opportunity. Here, we have developed a pyridinethiazole acrylonitrile-cholesterol derivative (Z-PTC) that exhibits wavelength-dependent photoisomerization and photocyclization, enabling dynamic handedness inversion and emissive color modulation in supramolecular assemblies with decent CPL activity. Coordination with Ag ions form the Z-PTC Ag supramolecular polymer (SP), which assembles into nanotubes displaying enhanced positive yellow-green CPL. Irradiation at 454 nm transforms SP into nanospheres of a mixture supramolecular polymer (SP) of Z/E-PTC Ag, displaying inverted supramolecular chirality and emitting negative orange-yellow CPL. Reheating SP to 343 K restores the original nanotube structure via excellent reversible photoisomerization. Exposure to 365 nm light also induces CPL inversion from positive to negative and triggers morphological changes from SP to SP. Prolonged irradiation causes further transformation into irregular supramolecular aggregate, shifting the emission color to blue and eliminating CPL. These dynamic properties of the multicolor CPL system, including reversible handedness inversion, can also be realized in the semisolid state, exhibiting promising potential for multimodal information encryption applications with enhanced security and complexity.
构建具有动态手性反转和发射颜色调制功能的圆偏振发光（CPL）材料用于多模态信息加密，既带来了重大挑战，也提供了极具吸引力的机遇。在此，我们开发了一种吡啶并噻唑丙烯腈 - 胆固醇衍生物（Z - PTC），它表现出波长依赖性的光异构化和光环化作用，能够在具有良好CPL活性的超分子组装体中实现动态手性反转和发射颜色调制。与银离子配位形成Z - PTC Ag超分子聚合物（SP），其组装成纳米管，显示出增强的正性黄绿CPL。在454 nm处照射可将SP转变为Z/E - PTC Ag混合超分子聚合物（SP）的纳米球，呈现反转的超分子手性并发射负性橙黄CPL。将SP重新加热至343 K可通过出色的可逆光异构化恢复原始的纳米管结构。暴露于365 nm光下也会诱导CPL从正性变为负性，并引发从SP到SP的形态变化。长时间照射会进一步转变为不规则的超分子聚集体，使发射颜色变为蓝色并消除CPL。这种多色CPL系统的这些动态特性，包括可逆的手性反转，在半固态中也能实现，在具有更高安全性和复杂性的多模态信息加密应用中展现出广阔的潜力。
