Gao Ji-Xing, Zhang Wan-Ying, Wu Zheng-Guang, Zheng You-Xuan, Fu Da-Wei
Institute for Science and Applications of Molecular Ferroelectrics, Zhejiang Normal University, Jinhua 321004, People's Republic of China.
School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, People's Republic of China.
J Am Chem Soc. 2020 Mar 11;142(10):4756-4761. doi: 10.1021/jacs.9b13291. Epub 2020 Feb 28.
Materials with circularly polarized luminescence (CPL) activity have immense potential applications in molecular switches, optical sensors, information storage, asymmetric photosynthesis, 3D optical displays, biological probe, and spintronic devices. However, the achiral architectures of most of the luminophores severely limit their practical needs. Within this context, molecular ferroelectrics with striking chemical variability and structure-property flexibility bring light to the assembly of CPL-active ferroelectric materials. Herein, we report organic-inorganic perovskite enantiomorphic ferroelectrics, ()- and ()-3-(fluoropyrrolidinium)MnBr, undergoing a 222F2-type ferroelectric phase transition at 273 K. Their mirror relationships are verified by both single-crystal X-ray diffraction and vibrational circular dichroism (VCD). Furthermore, the corresponding Cotton effect for two chiral crystals was captured by mirror CPL activity. This may be assigned to the inducing interaction between the achiral luminescent perovskite framework and chiral organic components. As far as we know, this is the first molecular ferroelectric with CPL activity. Accordingly, this will inspire intriguing research in molecular ferroelectrics with CPL activity and holds great potential for the development of new optoelectronic devices.
具有圆偏振发光（CPL）活性的材料在分子开关、光学传感器、信息存储、不对称光合作用、3D光学显示、生物探针和自旋电子器件等方面具有巨大的潜在应用。然而，大多数发光体的非手性结构严重限制了它们的实际需求。在此背景下，具有显著化学变异性和结构-性质灵活性的分子铁电体为CPL活性铁电材料的组装带来了曙光。在此，我们报道了有机-无机钙钛矿对映体铁电体，（）-和（）-3-（氟吡咯烷鎓）溴化锰，在273 K时经历222F2型铁电相变。它们的镜像关系通过单晶X射线衍射和振动圆二色性（VCD）得到验证。此外，通过镜像CPL活性捕捉到了两种手性晶体相应的科顿效应。这可能归因于非手性发光钙钛矿框架与手性有机组分之间的诱导相互作用。据我们所知，这是第一种具有CPL活性的分子铁电体。因此，这将激发对具有CPL活性的分子铁电体的有趣研究，并为新型光电器件的开发具有巨大潜力。
