Cao Liping, Wang Pinpin, Miao Xiaran, Duan Honghong, Wang Heng, Dong Yunhong, Ma Rui, Zhang Ben, Wu Biao, Li Xiaopeng, Stang Peter J
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, National Demonstration Center for Experimental Chemistry Education, College of Chemistry and Materials Science , Northwest University , Xi'an 710069 , P. R. China.
Shanghai Synchrotron Radiation Facility , Shanghai Institute of Applied Physics, Chinese Academy of Sciences , Shanghai 201204 , P. R. China.
Inorg Chem. 2019 May 6;58(9):6268-6275. doi: 10.1021/acs.inorgchem.9b00484. Epub 2019 Apr 19.
Supramolecular coordination has been developed as an efficient tool to construct a variety of discrete metallacycles and metallacages with well-defined shapes and sizes. However, its application in framework construction has been barely exploited. In this paper, we report the direct synthesis of two diamondoid frameworks from a simple tetrahedral precursor, tetra(4-(4-pyridinyl)phenyl)methane, and two linear difunctional platinum(II) ligands via one-step supramolecular coordination. Controlled by the specific angularity and geometry of the tetrahedral and linear subunits, these frameworks possess a well-defined diamondoid topology with highly regulated periodicity and three-dimensional porosity. Moreover, these rigid frameworks can be directly changed into a metallogel when prepared in DMSO at high concentrations. Interestingly, these diamondoid frameworks exhibit a cationic nature and stimuli-responsive behavior, which potentially endow them with the selective adsorption and controlled release for anionic dyes and drugs in aqueous environments. Thus, this study demonstrates that supramolecular coordination is a facile and efficient approach for the preparation of functional framework materials containing predesigned and well-defined supramolecular coordination assemblies as molecular skeletons.
超分子配位已发展成为一种有效的工具，用于构建各种具有明确形状和尺寸的离散金属环和金属笼。然而，其在框架构建中的应用却几乎未被开发。在本文中，我们报道了通过一步超分子配位，由一种简单的四面体前体四（4-（4-吡啶基）苯基）甲烷和两种线性双功能铂（II）配体直接合成两种类金刚石框架。受四面体和线性亚基的特定角度和几何形状控制，这些框架具有明确的类金刚石拓扑结构，具有高度规整的周期性和三维孔隙率。此外，当在二甲基亚砜中高浓度制备时，这些刚性框架可直接转变为金属凝胶。有趣的是，这些类金刚石框架表现出阳离子性质和刺激响应行为，这可能使它们在水性环境中对阴离子染料和药物具有选择性吸附和可控释放能力。因此，本研究表明，超分子配位是一种简便有效的方法，可用于制备以预先设计且明确的超分子配位组装体作为分子骨架的功能性框架材料。
