Brouillac Clément, Dureau Elodie, Jeannin Olivier, Rault-Berthelot Joëlle, Poriel Cyril, Quinton Cassandre
Univ Rennes, CNRS, ISCR-UMR CNRS 6226, F-35000 Rennes, France.
J Am Chem Soc. 2025 Apr 2;147(13):11267-11276. doi: 10.1021/jacs.4c18293. Epub 2025 Mar 20.
We report herein the synthesis and characterization of four donor-acceptor nanohoops incorporating fluorenone and carbazole as electron-poor and electron-rich units, respectively. The well-known platinum-mediated cyclization reaction here provides, in high yields, a mixture of four nanohoops possessing different and unexpected molecular arrangements. The four nanohoops have been isolated and characterized, and the impact of the number and arrangement of the carbazole and fluorenone moieties has been studied by spectroscopic and electrochemical analyses. Thanks to the intramolecular charge transfer resulting from the interaction between the carbazole and fluorenone units, their fluorescence was significantly red-shifted by 100 nm compared with a cyclic 2,7-tetracarbazole. This work highlights the singularity of the platinum-mediated cyclization reaction to construct donor-acceptor nanohoops with molecular arrangements, which are challenging to reach by other synthetic methods.
我们在此报告了四种供体-受体纳米环的合成与表征，这些纳米环分别将芴酮和咔唑作为缺电子单元和富电子单元。此处著名的铂介导环化反应以高产率提供了具有不同且意想不到分子排列的四种纳米环的混合物。这四种纳米环已被分离和表征，并且通过光谱和电化学分析研究了咔唑和芴酮部分的数量及排列的影响。由于咔唑和芴酮单元之间相互作用导致的分子内电荷转移，与环状2,7-四咔唑相比，它们的荧光显著红移了100纳米。这项工作突出了铂介导环化反应在构建具有特定分子排列的供体-受体纳米环方面的独特性，而通过其他合成方法很难实现这种分子排列。
