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，该策略可用于骨架设计与孔径/孔型调控，用以制备一种母结构以及另外10种具有前所未有拓扑结构的高多孔等网状骨架（isoreticular frameworks）。值得注意的是，该系列高多孔骨架的潜在可及孔容（57%–71%）、孔径（6.8–11.2 Å；17.0–29.0 Å；12.5–22.8 Å；11.9–24.5 Å）以及孔形均得到了同步且系统的调控。有趣的是，IIa型[Zn₄O(L₂)₂(BDC)₀.₅]{(CH₃)₂NH₂}的孔径降幅略小于IIc型[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。