Rigid Tether Directed Regioselective Synthesis and Crystallographic Characterization of Labile 1,2,3,4-Bis(triazolino)[60]fullerene and Its Thermolized Derivatives

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• 作者：Dr. Muqing Chen ; Dr. Lipiao Bao ; Prof. Ping Peng ; Dr. Shushu Zheng ; Prof. Yunpeng Xie and Prof. Xing Lu
• 刊名：Angewandte Chemie
• 出版年：2016
• 出版时间：September 19, 2016
• 年：2016
• 卷：128
• 期：39
• 页码：12066-12070
• 全文大小：948K
• ISSN：1521-3757

文摘

Labile bis-triazoline adducts of C₆₀ are supposed to be the precursors of bis-azafulleroids, but the formation mechanism is still unclear because of the incomplete isolation of the thermolized products and the lack of X-ray structures. A rigid-tethered reagent 1,2-bis(azidomethyl)benzene (1) was used to regioselectively synthesize the labile 1,2,3,4-bis(triazolino)[60]-fullerene (2), the structure of which was determined by single-crystal X-ray crystallography. Further thermolysis of 2 produces four products (3 a–3 d), which were all characterized by X-ray crystallography. Although 3 a and 3 b have traditional bis-azafulleroid structures, as proposed previously, 3 c and 3 d show unprecedented structures with either the coexistence of [5,6]-open and [6,6]-closed patterns or an oxidized structure with an 11-membered ring on the cage. A thermolysis mechanism is proposed to clarify long-term confusion about the transformation process from bis-triazoline adducts to bis-azafulleroids of C₆₀.