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Large Differences in Carbon Dioxide and Water Sorption Capabilities in a System of Closely Related Isoreticular Cd(II)-based Mixed-Ligand Metal-Organic Frameworks.
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-08-31 , DOI: 10.1021/acs.inorgchem.0c01533
Nolwazi Gcwensa 1 , Clive L Oliver 1
Affiliation  

We report the synthesis of two isoreticular, mixed-ligand metal–organic frameworks (MOFs), [Cd(μ2-mia)(μ2-bpe)]n·n(DMF)0.5·n(H2O)0.5 (1) and [Cd(μ2-nia)(μ2-bpee)]n·nDMF (2), where mia = 5-methoxyisophthalate, nia = 5-nitroisophthalate, bpe = 1,2-bis(4-pyridyl)ethane, bpee = 1,2-bis(4-pyridyl)ethylene, and DMF = N,N′-dimethylformamide. Variable-temperature powder X-ray diffraction studies confirmed that both MOFs remain crystalline with activation at high temperatures. Variable-temperature single-crystal X-ray diffraction studies were performed on 1, 2, and a previously published, isoreticular structure, [Cd(μ2-nia)(μ2-bpe)1.5]n·nDMF0.84 (3). These studies show that upon desolvation that monocrystallinity is retained to significantly higher temperatures for 2 and 3 when compared to 1 for which only a partially desolvated crystal structure could be obtained. Carbon dioxide sorption is negligible for 1 at 195 and 298 K, while it is higher for 2 than 3 at 298 K and reversed at 195 K. Water vapor sorption increases in the order 1, 2, and 3. On the contrary, water liquid sorption was significantly higher for 1 when compared to 2. The variable-temperature structures of the (partially) desolvated forms of 1, 2, and 3 give some insight into the reasons for the remarkably different gas, vapor, and liquid sorption properties.

中文翻译:

在紧密相关的基于等规线Cd(II)的混合配体金属-有机骨架体系中,二氧化碳和吸水能力的较大差异。

我们报告的2 isoreticular,混合配体的金属-有机骨架(MOF)的合成中,[CD(μ 2 -mia)(μ 2 -bpe)] ñ · Ñ(DMF)0.5 · Ñ(H 2 O)0.51)和[CD(μ 2 -nia)(μ 2 -bpee)] ñ · ñ DMF(2),其中MIA = 5-methoxyisophthalate,NIA = 5-硝基,BPE = 1,2-双(4-吡啶基乙烷,bpee = 1,2-双(4-吡啶基)乙烯,DMF = NN′-二甲基甲酰胺。可变温度粉末X射线衍射研究证实,两个MOF在高温下均保持结晶并具有活化作用。变温单晶X射线衍射研究在执行12以前发表的,isoreticular结构,[CD(μ,和2 -nia)(μ 2 -bpe)1.5 ] ñ · Ñ DMF 0.843) 。这些研究表明,在该脱溶剂单结晶被保持到显著更高的温度为23时相比,1为此,只能获得部分去溶剂化的晶体结构。二氧化碳的吸附可忽略不计1在195和298 K,而这是高为23在298 K的顺序,并在195 K.水颠倒蒸汽吸附增加12,和3。相反,与2相比,1的水液体吸附量明显更高。的(部分)的变温结构去溶剂化的形式的12,和3给出一些洞察的原因显着不同的气体,蒸汽和液体吸附性能。
更新日期:2020-09-21
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