Li Jian-Rong, Tao Ying, Yu Qun, Bu Xian-He, Sakamoto Hirotoshi, Kitagawa Susumu
Department of Chemistry, Nankai University, Tianjin 300071, PR China.
Chemistry. 2008;14(9):2771-6. doi: 10.1002/chem.200701447.
A new multifunctional di-topic tetrazolate-based ligand, 2,3-di-1H-tetrazol-5-ylpyrazine (H(2)dtp) has been designed and synthesized. The solvothermal reaction of this ligand with ZnCl(2) gave a robust guest-free three-dimensional zeolite-like chiral metal-organic framework (MOF) complex, [Zn(dtp)], which crystallized in chiral space group P6(1) and possessed chiral open channels with nitrogen-rich walls and the diameter of approximately 4.1 A. This framework presents a unique uniform etd (8,3) topology, is the first example of its type in MOFs, and exhibits high thermal stability with the decomposition temperature above 380 degrees C and permanent porosity. It is interesting that this material is able to selectively adsorb O(2) and CO(2) over N(2) gas, being a rare example in MOFs. In addition, C(2)H(2) and MeOH adsorption results show that although the framework channel holds nitrogen-rich walls that may provide H-bonding sites, no NH H-bond effect between the guest molecules and microporous surface was observed.
一种新型的基于双主题四唑的多功能配体，即2,3 - 二 - 1H - 四唑 - 5 - 基吡嗪（H₂dtp）已被设计并合成。该配体与ZnCl₂的溶剂热反应生成了一种坚固的无客体三维类沸石手性金属有机框架（MOF）配合物[Zn(dtp)]，其在手性空间群P6₁中结晶，拥有富含氮的壁且直径约为4.1 Å的手性开放通道。该框架呈现出独特的均匀etd(8,3)拓扑结构，是MOF中此类结构的首个实例，并且具有高于380℃的分解温度和永久孔隙率，展现出高热稳定性。有趣的是，这种材料能够在N₂气体之上选择性吸附O₂和CO₂，这在MOF中是一个罕见的例子。此外，C₂H₂和MeOH的吸附结果表明，尽管框架通道具有富含氮的壁，可能提供氢键位点，但未观察到客体分子与微孔表面之间的NH氢键效应。
