He Jun, Huang Jian, He Yonghe, Cao Peng, Zeller Matthias, Hunter Allen D, Xu Zhengtao
School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou, 510006, Guangdong, P.R. China.
Department of Chemistry, Youngstown State University, One University Plaza, Youngstown, OH, 44555, USA.
Chemistry. 2016 Jan 26;22(5):1597-601. doi: 10.1002/chem.201504941. Epub 2016 Jan 8.
A new avenue for making porous frameworks has been developed by borrowing an idea from molecularly imprinted polymers (MIPs). In lieu of the small molecules commonly used as templates in MIPs, soft metal components, such as CuI, are used to orient the molecular linker and to leverage the formation of the network. Specifically, a linear dicarboxylate linker with thioether side groups reacted simultaneously with Ln(3+) ions and CuI, leading to a bimetallic net featuring strong, chemically hard Eu(3+) -carboxylate links, as well as soft, thioether-bound Cu2 I2 clusters. The CuI block imparts water stability to the host; with the tunable luminescence from the lanthanide ions, this creates the first white-emitting MOF that is stable in boiling water. The Cu2 I2 block also readily reacts with H2 S, and enables sensitive colorimetric detection while the host net remains intact.
通过借鉴分子印迹聚合物(MIPs)的理念,开发出了一种制备多孔框架的新途径。代替MIPs中常用作模板的小分子,诸如碘化亚铜(CuI)之类的软金属组分被用于使分子连接体定向,并促进网络的形成。具体而言,一种带有硫醚侧基的线性二羧酸连接体与Ln(3+)离子和CuI同时发生反应,生成一种双金属网络,其具有强的、化学性质硬的Eu(3+) -羧酸盐连接,以及软的、硫醚键合的Cu2 I2簇。CuI模块赋予主体水稳定性;由于镧系离子具有可调节的发光特性,这就产生了首个在沸水中稳定的白色发光金属有机框架(MOF)。Cu2 I2模块也易于与硫化氢(H2 S)发生反应,并在主体网络保持完整的同时实现灵敏的比色检测。