Department of Chemistry, Seoul National University, Seoul 151-747, Republic of Korea.
Chemistry. 2011 Jun 20;17(26):7251-60. doi: 10.1002/chem.201003376. Epub 2011 May 10.
A doubly interpenetrating porous metal-organic framework (SNU-77) has been synthesized from the solvothermal reaction of the extended carboxylic acid tris(4'-carboxybiphenyl)amine (H(3)TCBPA) and Zn(NO(3))(2)⋅6H(2)O in N,N-dimethylacetamide (DMA). SNU-77 undergoes single-crystal-to-single-crystal transformations during various activation processes, such as room-temperature evacuation, supercritical CO(2) drying, and high temperature evacuation, to afford SNU-77R, SNU-77S, and SNU-77H, respectively. These guest-free MOFs exhibited different fine structures with different window shapes and different effective window sizes at room temperature. Variable-temperature synchrotron single-crystal X-ray analyses reveal that the guest-free structure is also affected by changes in temperature. Despite the different fine structures, SNU-77R, SNU-77S, and SNU-77H show similar gas sorption properties due to the nonbreathing nature of the framework and an additional structural change upon cooling to cryogenic gas sorption temperature. SNU-77H exhibits a large surface area (BET, 3670 m(2) g(-1)), a large pore volume (1.52 cm(3) g(-1)), and exceptionally high uptake capacities for N(2), H(2), O(2), CO(2), and CH(4) gases.
一种双重互穿多孔金属有机骨架（SNU-77）是通过溶剂热反应，将伸展羧酸三（4'-羧基联苯）胺（H(3)TCBPA）和 Zn(NO(3))(2)⋅6H(2)O 在 N,N-二甲基乙酰胺（DMA）中合成的。SNU-77 在各种活化过程中，如室温抽空、超临界 CO(2)干燥和高温抽空，会发生单晶到单晶的转变，分别得到 SNU-77R、SNU-77S 和 SNU-77H。这些无客体的 MOFs 在室温下表现出不同的精细结构，具有不同的窗口形状和不同的有效窗口尺寸。变温同步辐射单晶 X 射线分析表明，无客体结构也受到温度变化的影响。尽管精细结构不同，但 SNU-77R、SNU-77S 和 SNU-77H 由于框架的非呼吸性质和冷却到低温气体吸附温度时的额外结构变化，表现出相似的气体吸附性能。SNU-77H 具有大的比表面积（BET，3670 m(2) g(-1))、大的孔体积（1.52 cm(3) g(-1))，对 N(2)、H(2)、O(2)、CO(2) 和 CH(4)气体具有极高的吸附容量。
