Fullerene as Photocatalyst: Visible-Light Induced Reaction of Perfluorinated α,ω-Diiodoalkanes with C60

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• 作者：Andrey Kh. VorobievRuslan R. Gazizov ; Andrey Ya. Borschevskii ; Vitaliy Yu. Markov ; Vitaliy A. Ioutsi ; Victor A. Brotsman ; Lev N. Sidorov
• 刊名：Journal of Physical Chemistry A
• 出版年：2017
• 出版时间：January 12, 2017
• 年：2017
• 卷：121
• 期：1
• 页码：113-121
• 全文大小：456K
• ISSN：1520-5215

文摘

Solution phase photochemical reaction of fullerene with perfluorinated alkyldiiodides I–R_F–I can be efficiently initiated by visible range irradiation that targets solely the fullerene component. Photoinduced electron transfer from fullerene onto the diiodide component effects dissociative formation of alkyl radicals R_FI^• subsequently consumed by C₆₀ to give the principal detectable radical intermediate C₆₀R_FI^•. Experimentally established second-order kinetics with respect to the fullerene concentration evidence that fullerene plays its two roles of photocatalyst and reactant in a decoupled fashion, which suggests its catalytic ability to be of potential use in more complex photochemical systems. The main final product of the photochemical transformation observed is the singly linked dimer of the intermediates, I–R_F–C₆₀–C₆₀–R_F–I. Side reactions of C₆₀R_FI^• with the environment lead to quenching of the unpaired electron density by ortho- or para- attachment of hydrogen or iodine. The outlined kinetic findings are discussed in detail.