Predesign and Systematic Synthesis of 11 Highly Porous Coordination Polymers with Unprecedented Topology

We propose and validate a simple strategy of vertex connection that can be used for framework design and pore size/type modulation to prepare a mother structure and another 10 highly porous isoreticular frameworks with unprecedented topology. Importantly, the potential accessible pore volumes (57–71%), pore sizes (6.8–11. 2 Å; 17.0–29.0 Å; 12.5–22.8 Å; 11.9–24.5 Å), and the pore shapes of this series of highly porous frameworks were simultaneously and systematically tuned. Interestingly, the pore size of IIa [Zn4O­(L2)2(BDC)0.5]­{(CH3)2NH2} decreased a little less than that of IIc [Zn4O­(L2)2(2,6-NDC)0.5]­{(CH3)2NH2}; however, its selectivity of CO2 toward CH4 increased by almost two times.我们提出并验证了一种简便的顶点连接策略，该策略可用于框架设计与孔径、孔型调控，借此制备出一种母结构以及另外10种具有前所未有的拓扑结构的高孔隙率等网多孔框架（isoreticular frameworks）。尤为关键的是，该系列高孔隙率框架的潜在可及孔体积（57%~71%）、孔径（6.8~11.2埃；17.0~29.0埃；12.5~22.8埃；11.9~24.5埃）以及孔形均实现了同步且系统的调控。值得注意的是，IIa [Zn₄O(L₂)₂(BDC)₀.₅]·{(CH₃)₂NH₂}的孔径降幅略小于IIc [Zn₄O(L₂)₂(2,6-NDC)₀.₅]·{(CH₃)₂NH₂}，但其对CO₂相较于CH₄的选择性提升了近两倍。