Xie Huidong, Xiao Zuo, Song Yixiao, Jin Ke, Liu Hongxing, Zhou Erjun, Cao Jing, Chen Jiangzhao, Ding Junqiao, Yi Chenyi, Shen Xingxing, Zuo Chuantian, Ding Liming
Center for Excellence in Nanoscience, Key Laboratory of Nanosystem and Hierarchical Fabrication (CAS), National Center for Nanoscience and Technology, Beijing 100190, China.
University of Chinese Academy of Sciences, Beijing 100049, China.
J Am Chem Soc. 2024 May 1;146(17):11978-11990. doi: 10.1021/jacs.4c01347. Epub 2024 Apr 16.
Tethered nonplanar aromatics (TNAs) make up an important class of nonplanar aromatic compounds showing unique features. However, the knowledge on the synthesis, structures, and properties of TNAs remains insufficient. In this work, a new type of TNAs, the tethered aromatic lactams, is synthesized via Pd-catalyzed consecutive intramolecular direct arylations. These molecules possess a helical ladder-type conjugated system of up to 13 fused rings. The overall yields ranged from 3.4 to 4.3%. The largest of the tethered aromatic lactams, , demonstrates a guest-adaptive hosting capability of TNAs for the first time. When binding fullerene guests, the cavity of became more circular to better accommodate spherical fullerene molecules. The host-guest interaction is thoroughly studied by X-ray crystallography, theoretical calculations, fluorescence titration, and nuclear magnetic resonance (NMR) titration experiments. shows stronger binding with C than with C due to the better convex-concave π-π interaction. and enantiomers of all tethered aromatic lactams show distinct and persistent chiroptical properties and demonstrate the potential of chiral TNAs as circularly polarized luminescence (CPL) emitters.
束缚型非平面芳烃（TNAs）构成了一类具有独特特性的重要非平面芳香族化合物。然而，关于TNAs的合成、结构和性质的知识仍然不足。在这项工作中，通过钯催化的连续分子内直接芳基化反应合成了一种新型的TNAs，即束缚型芳香内酰胺。这些分子拥有一个由多达13个稠环组成的螺旋梯型共轭体系。总产率在3.4%至4.3%之间。最大的束缚型芳香内酰胺首次展示了TNAs的客体自适应容纳能力。当结合富勒烯客体时，的空腔变得更加圆形，以更好地容纳球形富勒烯分子。通过X射线晶体学、理论计算、荧光滴定和核磁共振（NMR）滴定实验对主客体相互作用进行了深入研究。由于更好的凹凸π-π相互作用，与C60的结合比与C70更强。所有束缚型芳香内酰胺的对映体都表现出独特且持久的手性光学性质，并展示了手性TNAs作为圆偏振发光（CPL）发射体的潜力。
