Theoretical Study on the Reactivity and Regioselectivity of the Diels–Alder Reaction of Fullerene: Effects of Charges and Encapsulated Lanthanum on the Bis-Functionalization of C70

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• 作者：Cheng-Xing CuiYa-Jun Liu ; Yu-Ping Zhang ; Ling-Bo Qu ; Zhao-Pei Zhang
• 刊名：Journal of Physical Chemistry A
• 出版年：2017
• 出版时间：January 19, 2017
• 年：2017
• 卷：121
• 期：2
• 页码：523-531
• 全文大小：510K
• ISSN：1520-5215

文摘

Bis-adducts of fullerenes are important for both material and biological science. The first added substituent greatly impacts the reactivity and regioselectivity of fullerene. What determines the bond reactivity and how to control the regioselectivity are two crucial questions in synthesizing bis-adduct of C₇₀. Recently, an unexpected 12 o’clock isomer of anthracene bis-adduct of C₇₀ was prepared with high yield by the Diels–Alder (DA) reaction although three possible isomers (12, 2, and 5 o’clock isomers) may be formed. In the current study, the beneath mechanism is systematically investigated by density functional theory methods. Moreover, effects of charges and encapsulated lanthanum atom on the regioselectivity are reported. The computational results successfully rationalize experimental observations by Venkata et al. A possible way to change the regioselectivity of DA reaction is put forward. The kinetical promotion effect of an encapsulated La atom on the 12 o’clock reaction is elucidated.