title: Radical Polymerization of Vinyl Monomers in Porous Organic Cages.
abstract: The radical polymerization of vinyl monomers was performed in a tetrahedral imine-linked organic cage with extrinsic porosity (CC3). Because of its dynamic and responsive packing structure, CC3 endowed the polymerization with specific behaviors. The adsorption of styrene triggered a change in the CC3 assembly, resulting in a monomer arrangement that was suitable for polymerization within the host matrix. The polymerization reaction was strongly dependent on the crystallinity of CC3 and was promoted by amorphization of the host in a cooperative manner, which is not possible with conventional rigid porous materials. Furthermore, CC3 can recognize the polarity of substrates, and thus polar monomers, such as methyl methacrylate and acrylonitrile, could not induce the structural changes in CC3 that are required for polymerization. This monomer specificity governed by the flexibility of CC3 is useful to the prevent incorporation of unfavorable monomers into the polymeric products.
authors.affiliation: Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto, 615-8510, Japan. uemura@sbchem.kyoto-u.ac.jp.|CREST Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi, Saitama, 332-0012, Japan. uemura@sbchem.kyoto-u.ac.jp.
authors.forename: Takashi
authors.initials: T
authors.lastname: Uemura
authors.affiliation: Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto, 615-8510, Japan.
authors.forename: Ryo
authors.initials: R
authors.lastname: Nakanishi
authors.affiliation: Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto, 615-8510, Japan.
authors.forename: Shuto
authors.initials: S
authors.lastname: Mochizuki
authors.affiliation: Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto, 615-8510, Japan.|Institute for Integrated Cell-Material Sciences (WPI-iCeMS), Kyoto University, Yoshida, Sakyo-ku, Kyoto, 606-8501, Japan.
authors.forename: Susumu
authors.initials: S
authors.lastname: Kitagawa
authors.affiliation: Department of Chemistry, Graduate School of Natural Science & Technology, Kanazawa University, Kakuma, Kanazawa, Ishikawa, 920-1192, Japan.
authors.forename: Motohiro
authors.initials: M
authors.lastname: Mizuno
keywords: cage compounds; host-guest systems; microporous materials; polymerization; radical reactions