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Chemoselective Phototransformation of CH Bonds on a Polymer Surface through a Photoinduced Cerium Recycling Redox Reaction
Author(s) -
Huang Zhenhua,
Wu Zhengfang,
Yang Peng,
Yang Wantai
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201402786
Subject(s) - redox , cerium , chemistry , photochemistry , polymer , radical , alkyl , substrate (aquarium) , polymerization , surface modification , polymer chemistry , aqueous solution , molecule , inorganic chemistry , organic chemistry , oceanography , geology
It is generally accepted that Ce 4+ is unable to directly oxidize unreactive alkyl CH bonds without the assistance of adjacent polar groups. Herein, we demonstrate in our newly developed confined photochemical reaction system that this recognized issue may be challenged. As we found, when a thin layer of a CeCl 3 /HCl aqueous solution was applied to a polymeric substrate and the substrate subjected to UV irradiation, Ce 3+ was first photooxidized to form Ce 4+ in the presence of H + , and the in situ formed Ce 4+ then performs an oxidation reaction on the CH bonds of the polymer surface to form surface‐carbon radicals for radical graft polymerization reactions and functional‐group transformations, while reducing to Ce 3+ and releasing H + in the process. This photoinduced cerium recycling redox (PCRR) reaction behaved as a biomimetic system in an artificial recycling reaction, leading to a sustainable chemical modification strategy for directly transforming alkyl CH bonds on polymer surfaces into small‐molecule groups and polymer brushes. This method is expected to provide a green and economical tool for industrial applications of polymer‐surface modification.