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首页> 外文期刊>Chemistry: A European journal >Robust MOFs of “tsg” Topology Based on Trigonal Prismatic Organic and Metal Cluster SBUs: Single Crystal to Single Crystal Postsynthetic Metal Exchange and Selective CO_2 Capture
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Robust MOFs of “tsg” Topology Based on Trigonal Prismatic Organic and Metal Cluster SBUs: Single Crystal to Single Crystal Postsynthetic Metal Exchange and Selective CO_2 Capture

机译：基于Trigonal棱镜有机和金属簇SBUS的“TSG”拓扑结构的强大MOF：单晶与单晶后金属交换和选择性CO_2捕获

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The self-assembly of a rigid and trigonal prismatic triptycene-hexaacid H_6THA with Co(NO_3)_2 or Mn(NO_3)_2 leads to isostructural metal-organic frameworks (MOFs) that are sustained by 6-connecting metal cluster [M_3(μ_3-O)(COO)_6] secondary building units (SBUs). The Co- and Mn-MOFs, constructed from organic and metal-cluster building blocks that are both trigonal prismatic, correspond to the heretofore unknown “tsg” topology. Due to the rigidity and concave attributes of H_6THA, the networks in the Co- and Mn-MOFs are highly porous and undergo 3-fold interpenetration. The interpenetration imparts permanent microporosity and high thermal stability to the MOFs to permit postsynthetic metal exchange (PSME) and gas sorption. The PSME occurs in a single crystal to single crystal fashion when the crystals of Co- or Mn-MOFs are immersed in a solution of Cu(NO_3)_2 in MeOH/H_2O. Further, the isostructural robust MOFs exhibit significant gas sorption and remarkable selectivity for CO_2 over N_2 (ca. 100 fold) at ambient conditions. In fact, the postsynthetically-engineered Cu-THA exhibits better CO_2 sorption than Co-THA and Mn-THA. A composite of effects that include pore dimensions (ca. 0.7 nm), unsaturated metal centers, and basic environments conferred by the quinoxaline nitrogen atoms appears to be responsible for the observed high CO_2 capture and selectivity. The high symmetry and structural attributes of the organic linker seemingly dictate adoption of the trigonal-prismatic metal cluster SBU by the metal ions in the MOFs.
机译：用CO（NO_3）_2或Mn（NO_3）_2的刚性和三角形棱柱替代三核 - 六酸H_6THA的自组装导致由6个连接金属聚类（M_3（μ_3- O）（COO）_6]二级建筑单位（SBUS）。由具有三角形棱柱形的有机和金属簇构建块构成的CO-and MN-MOFS对应于迄今为止未知的“TSG”拓扑结构。由于H_6THA的刚性和凹形属性，CO-and MN-MOF中的网络是高度多孔的并且经过3倍的互通。互通赋予MOF的永久性微孔和高热稳定性，以允许后金属交换（PSME）和气体吸附。当Co-或Mn-Mofs的晶体浸入MeOH / H_2O中的Cu（NO_3）_2的溶液中时，PSME在单晶时出现单晶。此外，在环境条件下，Isostrontuctuct鲁棒MOF对N_2（100倍）的CO_2具有显着的气体吸附和显着的选择性。实际上，后授权的Cu-Tha表现出比CO-THA和MN-TH的更好的CO_2吸附。包括孔尺寸（约0.7nm），不饱和金属中心和由喹喔啉氮原子赋予的基本环境的效果的复合物似乎是观察到的高CO_2捕获和选择性的原因。有机接头的高对称性和结构属性似乎决定了MOF中的金属离子通过金属离子的三角形金属簇SBU。

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