Kung Chung-Wei, Otake Ken-Ichi, Drout Riki J, Goswami Subhadip, Farha Omar K, Hupp Joseph T
Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States.
Department of Chemical Engineering, National Cheng Kung University, 1 University Road, Tainan City 70101, Taiwan.
Langmuir. 2023 Apr 11;39(14):4936-4942. doi: 10.1021/acs.langmuir.2c03354. Epub 2023 Mar 30.
Starting with ferrocyanide ions in acidic aqueous solution, cyano-ferrate(II) species are post-synthetically grafted to the nodes of a mesoporous zirconium-based MOF, NU-1000. As indicated by single-crystal X-ray crystallography, grafting occurs by substitution of cyanide ligands by node-based hydroxo and oxo ligands rather than by substitution of node aqua ligands by cyanide ligands as bridges between Fe(II) and Zr(IV). The installed moieties yield a broad absorption band that is tentatively ascribed to iron-to-zirconium charge transfer. Consistent with Fe(III/II) redox activity, a modest fraction of the installed iron complexes are directly electrochemically addressable.
从酸性水溶液中的亚铁氰根离子开始，氰基铁（II）物种在合成后接枝到介孔锆基金属有机框架材料NU-1000的节点上。如单晶X射线晶体学所示，接枝是通过基于节点的羟基和氧代配体取代氰化物配体发生的，而不是通过氰化物配体取代节点水合配体作为铁（II）和锆（IV）之间的桥连。所引入的部分产生了一个宽吸收带，初步归因于铁到锆的电荷转移。与Fe（III/II）的氧化还原活性一致，所引入的铁配合物中有一小部分可直接进行电化学检测。
