Zheng Yongshen, Han Xiao, Cheng Puxin, Jia Xiaodi, Xu Jialiang, Bu Xian-He
School of Materials Science and Engineering, National Institute for Advanced Materials, Nankai University, 300350 Tianjin, P. R. China.
J Am Chem Soc. 2022 Sep 14;144(36):16471-16479. doi: 10.1021/jacs.2c05063. Epub 2022 Sep 5.
Chiral hybrid organic-inorganic metal halides (HOMHs) with intrinsic noncentrosymmetry have shown great promise for broad applications in chiroptoelectronics, spintronics, and ferroelectronics. However, the construction strategies for chiral HOMHs often involve chiral building blocks in their frameworks, which greatly limit their chemical diversity. Here, we take advantage of a chiral induction approach and have successfully constructed a series of chiral HOMHs, (DMA = dimethylammonium, M = Sb or Bi, X = Cl or Br), based on achiral precursors. The resulting chiral products demonstrate a clear enantioenrichment, as confirmed by single-crystal X-ray diffraction analysis and solid-state circular dichroism (CD) spectroscopy. The induction of chiral HOMHs enables superior nonlinear optical performances with very high thermal stability and laser resistance. The successful employment of such a chiral induction approach might facilitate the construction of libraries of chiral HOMH crystals from diverse achiral precursors, in particular those into which it is not easy to introduce intrinsic chiral centers, and would thus pave a new way for rational preparation and application of chiral HOMH materials.
具有固有非中心对称性的手性有机-无机杂化金属卤化物（HOMHs）在旋光电子学、自旋电子学和铁电子学等广泛应用中显示出巨大潜力。然而，手性HOMHs的构建策略通常在其框架中涉及手性结构单元，这极大地限制了它们的化学多样性。在此，我们利用手性诱导方法，基于非手性前体成功构建了一系列手性HOMHs，（DMA = 二甲基铵，M = Sb或Bi，X = Cl或Br）。通过单晶X射线衍射分析和固态圆二色性（CD）光谱证实，所得手性产物表现出明显的对映体富集。手性HOMHs的诱导实现了具有非常高的热稳定性和抗激光性的优异非线性光学性能。这种手性诱导方法的成功应用可能有助于从各种非手性前体构建手性HOMH晶体库，特别是那些不容易引入固有手性中心的前体，从而为手性HOMH材料的合理制备和应用开辟一条新途径。
