Selective NO Trapping in the Pores of Chain-Type Complex Assemblies Based on Electronically Activated Paddlewheel-Type [Ru2II,II]/[Rh2II,II] Dimers
Selective NO Trapping in the Pores of Chain-Type Complex Assemblies Based on Electronically Activated Paddlewheel-Type [Ru2II,II]/[Rh2II,II] Dimers
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DOI：
10.1021/ja4076056
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发表时间：
2013-12-11
影响因子：
15
通讯作者：
Miyasaka, Hitoshi
中科院分区：
文献类型：
--
作者：
Kosaka, Wataru;Yamagishi, Kayo;Miyasaka, Hitoshi
支持信息摘要：设计能够选择性吸附特定分子的多孔材料是多孔配位聚合物或金属有机骨架研究中的关键问题。为了选择性捕获具有电子受体特征的分子如一氧化氮（NO），使用4-氯苯甲醚桥接的桨轮型双金属（II，II）配合物（M = Ru和Rh）和吩嗪（phz）作为链连接体，合成了具有高供体特征的一维链化合物：[M-2（4-Cl-2-OMePhCO 2）（4）（phz）]中心点n（CH 2Cl 2）（M = Ru，1; Rh，2）。这些化合物是同构的，并且由具有[-{M-2}-phz-]重复单元的链和占据链之间的空隙空间的CH 2Cl 2组成。化合物1和2在抽空结晶溶剂（CH 2Cl 2）时变为新相（1-干燥和2-干燥），并且在干燥过程中几乎失去它们的孔：在1-干燥中没有空隙空间，在2-干燥中为31.8埃（3），对应于2.9%的单元体积。然而，这些化合物显示出独特的气体容纳能力。伴随着结构转型（即，第一次闸门打开），
Supporting Information ABSTRACT: The design of porous materials that undergo selective adsorption of a specific molecule is a critical issue in research on porous coordination polymers or metal organic frameworks. For the purpose of the selective capture of molecules possessing an electron-acceptor character such as nitric oxide (NO), one-dimensional chain compounds possessing a high donor character have been synthesized using 4-chloroanisate-bridged paddlewheel-type dimetal(II, II) complexes with M = Ru and Rh and phenazine (phz) as the chain linker: [M-2(4-Cl-2-OMePhCO2)(4)(phz)]center dot n(CH2Cl2) (M = Ru, 1; Rh, 2). These compounds are isostructural and are composed of chains with a [-{M-2}-phz-] repeating unit and CH2Cl2 occupying the void space between the chains. Compounds 1 and 2 change to a new phase (1-dry and 2-dry) upon evacuating the crystallization solvent (CH2Cl2) and almost lose their pores in the drying process: no void space in 1-dry and 31.8 angstrom(3), corresponding to 2.9% of the cell volume, in 2-dry. Nevertheless, the compounds show a unique gas accommodation ability. Accompanied by a structural transformation (i.e., the first gate-opening) at low pressures of