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.