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(L(2))2(BDC)0.5]{(CH3)2NH2} decreased a little less than that of IIc [Zn4O(L(2))2(2,6-NDC)0.5]{(CH3)2NH2}; however, its selectivity of CO2 toward CH4 increased by almost two times.