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/孔类型调控，以此制备得到一种母结构以及另外10种具有前所未有的拓扑结构的高多孔同网状骨架。尤为重要的是，该系列高多孔骨架的潜在可访问孔体积（57%~71%）、孔径（6.8~11.2 Å；17.0~29.0 Å；12.5~22.8 Å；11.9~24.5 Å）以及孔形状均可实现同步系统性调控。值得注意的是，IIa [Zn₄O(L₂)₂(BDC)₀.₅]·{(CH₃)₂NH₂}的孔径降幅略小于IIc [Zn₄O(L₂)₂(2,6-NDC)₀.₅]·{(CH₃)₂NH₂}，但其CO₂对CH₄的选择性提升了近两倍。