Dunning Samuel G, Gupta Nishesh Kumar, Reynolds Joseph E, Sagastuy-Breña Mónica, Flores J Gabriel, Martínez-Ahumada Eva, Sánchez-González Elí, Lynch Vincent M, Gutiérrez-Alejandre Aída, Aguilar-Pliego Julia, Kim Kwang-Soo, Ibarra Ilich A, Humphrey Simon M
Department of Chemistry, The University of Texas at Austin, Welch Hall 2.204, 105 CE. 24th St. Stop A5300, Austin Texas 78712-1224, United States.
Laboratorio de Fisicoquímica y Reactividad de Superficies (LaFReS), Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Circuito Exterior s/n, CU, Coyocán, 04510 Ciudad de México, Mexico.
Inorg Chem. 2022 Sep 26;61(38):15037-15044. doi: 10.1021/acs.inorgchem.2c02012. Epub 2022 Sep 9.
The environmentally benign metal-organic framework (MOF) CUK-1 based on 2,4-pyridine dicarboxylate has been prepared for the first time using Mn(II) as the inorganic node and water as the only solvent. Mn-CUK-1 shows reversible and efficient capture of HO, SO, and HS. Compared to previously studied Co(II) and Mg(II) versions of the same MOF, Mn-CUK-1 also exhibited unique temperature-induced structural flexibility due to organic linker torsion, as detailed by variable-temperature single-crystal X-ray diffraction studies. Owing to this inherent solid-state flexibility, Mn-CUK-1 showed stepwise adsorption for polar gases, which induce structural deformations upon adsorption, while the nonpolar guest adsorbates were reversibly sorbed in a more classical manner. Notably, Mn-CUK-1 demonstrates the highest reported HS capacity-to-surface area ratio among MOFs that are chemically stable toward this reactive acidic molecule. Moreover, Mn-CUK-1 displays exceptional structural stability in the presence of high relative humidity and corrosive gases and shows soft crystalline behavior triggered by changes in both the adsorption temperature and guest molecule identity.
首次以Mn(II)作为无机节点、水作为唯一溶剂制备了基于2,4 -吡啶二羧酸酯的环境友好型金属有机框架（MOF）CUK - 1。Mn - CUK - 1对HO、SO和HS具有可逆且高效的捕获能力。与之前研究的相同MOF的Co(II)和Mg(II)版本相比，如通过变温单晶X射线衍射研究所详述的，由于有机连接体扭转，Mn - CUK - 1还表现出独特的温度诱导结构灵活性。由于这种固有的固态灵活性，Mn - CUK - 1对极性气体表现出逐步吸附，这些极性气体在吸附时会引起结构变形，而非极性客体吸附质则以更经典的方式被可逆吸附。值得注意的是，在对这种反应性酸性分子化学稳定的MOF中，Mn - CUK - 1展现出了报道中最高的HS容量与表面积比。此外，Mn - CUK - 1在高相对湿度和腐蚀性气体存在的情况下表现出卓越的结构稳定性，并在吸附温度和客体分子特性变化时展现出软晶体行为。
