Wu Hongwei, Chi Weijie, Baryshnikov Gleb, Wu Bin, Gong Yifan, Zheng Dongxiao, Li Xin, Zhao Yanli, Liu Xiaogang, Ågren Hans, Zhu Liangliang
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai, 200438, China.
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371, Singapore.
Angew Chem Int Ed Engl. 2019 Mar 22;58(13):4328-4333. doi: 10.1002/anie.201900703. Epub 2019 Mar 6.
Crystal-state luminophores have been of great interest in optoelectronics for years, whereas the excited state regulation at the crystal level is still restricted by the lack of control ways. We report that the singlet-triplet emissive property can be profoundly regulated by crystal conformational distortions. Employing fluoro-substituted tetrakis(arylthio)benzene luminophores as prototype, we found that couples of molecular conformations formed during different crystallizations. The deformable carbon-sulphur bond essentially drove the distortion of the molecular conformation and varied the stacking mode, together with diverse non-covalent interactions, leading to the proportional adjustment of the fluorescence and phosphorescence bands. This intrinsic strategy was further applied for solid-state multicolor emissive conversion and mechanoluminescence, probably offering new insights for design of smart crystal luminescent materials.
多年来,晶体态发光体在光电子学领域备受关注,然而在晶体层面的激发态调控仍因缺乏控制方法而受到限制。我们报道,单重态-三重态发射特性可通过晶体构象畸变得到深刻调控。以氟取代的四(芳硫基)苯发光体为原型,我们发现在不同结晶过程中形成了分子构象对。可变形的碳-硫键本质上驱动了分子构象的畸变并改变了堆积模式,同时伴随着多种非共价相互作用,导致荧光和磷光带的比例调整。这种内在策略进一步应用于固态多色发射转换和机械发光,可能为智能晶体发光材料的设计提供新的见解。