Open AccessFullerene as Photocatalyst: Visible-Light Induced Reaction of Perfluorinated α,ω-Diiodoalkanes with C60
Author(s) -
Andrey Kh. Vorobiev,
Ruslan R. Gazizov,
Andrey Ya. Borschevskii,
Vitaliy Yu. Markov,
Vitaliy Ioutsi,
Victor A. Brotsman,
Lev N. Sidorov
Publication year - 2017
Publication title -
the journal of physical chemistry. a/the journal of physical chemistry. a.
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.756
H-Index - 235
eISSN - 1520-5215
pISSN - 1089-5639
DOI - 10.1021/acs.jpca.6b10718
Subject(s) - chemistry , photochemistry , fullerene , photocatalysis , quenching (fluorescence) , radical , kinetics , visible spectrum , electron transfer , fullerene chemistry , dimer , irradiation , photoinduced electron transfer , catalysis , fluorescence , organic chemistry , physics , optoelectronics , quantum mechanics , nuclear physics
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 F I • subsequently consumed by C 60 to give the principal detectable radical intermediate C 60 R F I • . 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 -C 60 -C 60 -R F -I. Side reactions of C 60 R F I • 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.