He Jun, Duan Jingjing, Shi Huatian, Huang Jian, Huang Jiahong, Yu Lin, Zeller Matthias, Hunter Allen D, Xu Zhengtao
School of Chemical Engineering and Light Industry, Guangdong University of Technology , Guangzhou 510006, Guangdong, China.
Inorg Chem. 2014 Jul 7;53(13):6837-43. doi: 10.1021/ic500677t. Epub 2014 Jun 6.
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.
此处的主要发现是一种坚固且水稳定的金属有机框架（MOF）材料，它能够可逆地结合ICl和I₂的挥发性及反应性分子。实现I₂和ICl的固定化及其可控释放，是为了促进这些挥发性物质作为催化剂和试剂在化学及工业过程中的广泛应用。框架材料TMBP·CuI（以下简称TCuI）可通过在乙腈中加热CuI和有机连接体TMBP（3,3',5,5'-四甲基-4,4'-联吡唑）以定量产率方便地制备。TCuI的微孔三维网络具有CuI链，有助于ICl和I₂分子的高效可逆结合，分别形成化学计量明确的TCuI·ICl和TCuI·I₂加合物。此外，将ICl等挥发性化合物限制在MOF介质中，为增强其作为化学试剂的反应性和选择性提供了独特机会，本文研究的碘化反应便是例证。通过这项示例性研究，我们旨在激发人们进一步探索MOF和其他多孔介质（如多孔聚合物）以捕获ICl和其他挥发性试剂（如Br₂、SCl₂、S₂Cl₂和SOCl₂）以及与多孔介质相关的潜在新反应性的兴趣。
