Jun He,Jingjing Duan,Huatian Shi,Jian Huang,Jiahong Huang,Lin Yu,Matthias Zeller,Allen D. Hunter,Zhengtao Xu
The major discovery here is a robust and water-stable metal–organic framework (MOF) material capable of reversible binding of the volatile and reactive molecules of ICl and I2. The immobilization of I2 and ICl, as well as their controllable release thus achieved, is to facilitate the wide-ranging applications of these volatile species as catalysts and reagents in chemical and industrial processes. The framework material TMBP·CuI (hereafter TCuI) can be conveniently prepared in quantitative yields by heating CuI and the organic linker TMBP (3,3′,5,5′-tetramethyl-4,4′-bipyrazol) in acetonitrile. The microporous three-dimensional net of TCuI features CuI chains that contribute to efficient and reversible binding of ICl and I2 molecules, to result in the stoichiometrically well-defined adducts of TCuI·ICl and TCuI·I2, respectively. Moreover, the confinement of a volatile compound like ICl within the MOF medium provides unique opportunities to enhance its reactivity and selectivity as a chemical reagent, as is exemplified by the iodination reactions examined herein. With this exemplary study, we intend to stimulate interest in further exploring MOFs and other porous media (e.g., porous polymers) for entrapping ICl and other volatile reagents (e.g., Br2, SCl2, S2Cl2, and SOCl2) and for potentially novel reactivity associated with the porous medium.
Sulphonated poly(ether ether ketone) (SPEEK) exhibits excellent mechanical properties as a proton exchange membrane. However, its proton conductivity remains insufficient for practical applications. To address this limitation, a covalent incorporation of proton-conductive functional groups into the SPEEK matrix is proposed to establish continuous proton transport channels. Herein, through an iodination reaction of N-iodosuccinimide with SPEEK, we have successfully synthesised iodinated sulphonated poly(ether ether ketone) (I-SPEEK) with an iodination efficiency of 71.0% as confirmed by ion chromatography. This work proposes tentative reactivity positions and mechanistic hypotheses for the sulphonation of poly(ether ether ketone) and the subsequent iodination of SPEEK. Effective introduction of iodine is confirmed by Fourier-transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopies. Meanwhile, I-SPEEK serves as a precursor that provides grafting sites for hydrophilic groups (e.g. vinyl-silanes via the Heck reaction), offering a novel strategy for subsequent studies to introduce proton-conductive moieties.
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