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Stable Crystalline Nanohoop Radical and Its Self-Association Promoted by van der Waals Interactions |
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| Authors: | Bingxia Hou Dr. Ke Li Huijie He Jinlian Hu Zhuofan Xu Dr. Qin Xiang Peng Wang Prof. Dr. Xing Chen Prof. Dr. Zhe Sun |
| Affiliation: | 1. Institute of Molecular Plus, Department of Chemistry and Haihe Laboratory of Sustainable Chemical Transformations, Tianjin university, 92 Weijin Road, Tianjin, 300072 China These authors contributed equally to this work.;2. Institute of Molecular Plus, Department of Chemistry and Haihe Laboratory of Sustainable Chemical Transformations, Tianjin university, 92 Weijin Road, Tianjin, 300072 China |
| Abstract: | A stable nanohoop radical (OR3) combining the structures of cycloparaphenylene and an olympicenyl radical is synthesized and isolated in the crystalline state. X-ray crystallographic analysis reveals that OR3 forms a unique head-to-tail dimer that further aggregates into a one-dimensional chain in the solid state. Variable-temperature NMR and concentration-dependent absorption measurements indicate that the π-dimer is not formed in solution. An energy decomposition analysis indicates that van der Waals interactions are the driving force for the self-association process, in contrast with other olympicenyl derivatives that favor π-dimerization. The physical properties in solution phase have been studied, and the stable cationic species obtained by one-electron chemical oxidation. This study offers a new molecular design to modulate the self-association of organic radicals for overcoming the spin-Peierls transition, and to prepare novel nanohoop compounds with spin-related properties. |
| Keywords: | Cation Nanohoop Olympicenyl Radical Self-Association |