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.