Zhou Minghao, Sang Yutao, Jin Xue, Chen Sanxu, Guo Junchen, Duan Pengfei, Liu Minghua
CAS Center for Excellence in Nanoscience, CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, National Center for Nanoscience and Technology, Beijing 100190, People's Republic of China.
University of Chinese Academy of Sciences, Beijing 100049, People's Republic of China.
ACS Nano. 2021 Feb 23;15(2):2753-2761. doi: 10.1021/acsnano.0c08539. Epub 2021 Feb 9.
Enormous attention has been paid to upconverted circularly polarized luminescence (UC-CPL). However, so far, chiral species are still needed in UC-CPL materials, either through the covalent or noncovalent bond. Here, we report a general supramolecular coassembly approach for the fabrication of UC-CPL systems from completely achiral components. We have found that an achiral -symmetric molecule could form a chiral nanohelix through symmetry breaking, which could serve as a general helical platform to endow achiral guests with induced chirality and CPL activity. Two different photon upconversion systems, namely, triplet-triplet annihilation photon upconversion (TTA-UC) donor/acceptor pairs and inorganic lanthanide upconversion nanoparticles (UCNPs), are selected. When these two systems coassembled with the chiral nanohelix made from an achiral -symmetric molecule, hybrid nanohelix structures formed and UC-CPL activity was induced. Through such an approach, we demonstrated that the fabrication of the UC-CPL materials does not require any chiral molecules. Moreover, we have shown that the polarization of UC-CPL can be tuned by the helicity of the nanohelix, which could be controlled through the seeded vortex. Our work provides a general approach for designing tunable UC-CPL materials from completely achiral motifs, which largely expands the research scope of the CPL materials.
上转换圆偏振发光(UC-CPL)已受到极大关注。然而,到目前为止,UC-CPL材料中仍需要手性物种,无论是通过共价键还是非共价键。在此,我们报道了一种从完全非手性组分制备UC-CPL体系的通用超分子共组装方法。我们发现,一个非手性对称分子可以通过对称性破缺形成手性纳米螺旋,该纳米螺旋可作为通用的螺旋平台,赋予非手性客体诱导手性和CPL活性。我们选择了两种不同的光子上转换体系,即三重态-三重态湮灭光子上转换(TTA-UC)供体/受体对和无机镧系上转换纳米粒子(UCNP)。当这两种体系与由非手性对称分子制成的手性纳米螺旋共组装时,形成了混合纳米螺旋结构并诱导了UC-CPL活性。通过这种方法,我们证明了UC-CPL材料的制备不需要任何手性分子。此外,我们还表明,UC-CPL的偏振可以通过纳米螺旋的螺旋度来调节,而螺旋度可以通过种子涡旋来控制。我们的工作为从完全非手性基序设计可调谐UC-CPL材料提供了一种通用方法,这在很大程度上扩展了CPL材料的研究范围。