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.

本研究提出并验证了一种简明的顶点连接策略，该策略可应用于框架设计与孔径大小及类型调节，以制备母结构及其它十种具有创新拓扑结构的高孔隙率等网状框架。值得注意的是，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 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。尤为引人注目的是，IIa [Zn4O(L2)2(BDC)0.5]­{(CH3)2NH2} 的孔径较 IIc [Zn4O(L2)2(2,6-NDC)0.5]­{(CH3)2NH2} 略有减小；然而，其对 CO2 相对于 CH4 的选择性几乎提高了两倍。