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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Syntheses, structures and properties of cadmium benzenedicarboxylate metal-organic frameworks
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Syntheses, structures and properties of cadmium benzenedicarboxylate metal-organic frameworks

机译：苯二甲酸镉金属-有机骨架的合成，结构与性能

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The products isolated from the reaction between Cd(NO3)(2) center dot 4H(2)O and 1,4-benzenedicarboxylic acid (H(2)bdc) in DMF are very dependent on the conditions. At 115 degrees C, the reaction gives [Cd( bdc)(DMF)](infinity) 1, which has a three-dimensional network structure, whereas at 95 degrees C, 1 is formed alongside [Cd-3(bdc)(3)(DMF)(4)](infinity) 2, which has a two-dimensional network structure. When the reaction is carried out under pressure, it yields [ Cd3( bdc) 3( DMF) 4]8 3, which is a supramolecular isomer of 2. The structure of 3 differs from that of 2 regarding the way the Cd-3( O2CR)(6) units are interlinked to form layers. When the reaction was carried out in DMF that had undergone partial hydrolysis, the only isolated product was {(NMe2H2)(2)[ Cd(bdc)(2)] center dot 2DMF}(infinity) 4. Compound 4 has a three-dimensional triply-interpenetrated diamondoid structure, with dimethylammonium cations and DMF molecules included within the pores. The reaction between Cd(NO3)(2) center dot 4H(2)O and H(2)bdc in DEF gave [ Cd( bdc)( DEF)]8 5, regardless of the solvent quality. Compound 5 has a three-dimensional network structure. The reaction of Cd(NO3)(2) center dot 4H(2)O and 1,3-benzenedicarboxylic acid (H(2)mbdc) in DMF gave [Cd( mbdc)(DMF)](infinity) 6 which has a bilayer structure. The thermal properties of the new materials have been investigated, and the coordinated DEF molecules from 5 can be removed on heating to 400 degrees C without any change in the powder X-ray diffraction pattern. The H-2 sorption isotherm for the desolvated material shows marked hysteresis between adsorption and desorption, and less adsorption than predicted by simulations. Kinetic data indicate that the hysteresis is not due to mass transfer limitations, and the most likely explanation for this behaviour lies in partial collapse of the framework to an amorphous phase under the conditions of activation.
机译：从Cd（NO3）（2）中心点4H（2）O和1,4-苯二甲酸（H（2）bdc）在DMF中的反应中分离出的产物非常取决于条件。在115摄氏度下，反应生成具有三维网络结构的[Cd（bdc）（DMF）]（无穷大）1，而在95摄氏度下，与[Cd-3（bdc）（3）一起形成1 ）（DMF）（4）]（无穷大）2，它具有二维网络结构。当在压力下进行反应时，会产生[Cd3（bdc）3（DMF）4] 8 3，它是2的超分子异构体。3的结构与2的结构不同，关于Cd-3（ O2CR）（6）单元互连形成层。当反应在已部分水解的DMF中进行时，唯一分离出的产物是{（NMe2H2）（2）[Cd（bdc）（2）]中心点2DMF}（无穷大）4。化合物4具有三个一维三重互穿的类金刚石结构，孔中包含二甲基铵阳离子和DMF分子。 Cd（NO3）（2）中心点4H（2）O和H（2）bdc在DEF中的反应得到[Cd（bdc）（DEF）] 8 5，无论溶剂质量如何。化合物5具有三维网络结构。 Cd（NO3）（2）中心点4H（2）O与1,3-苯二甲酸（H（2）mbdc）在DMF中的反应得到[Cd（mbdc）（DMF）]（无穷大）6双层结构。已经研究了新材料的热性能，并且可以在加热至400摄氏度的情况下从5中去除配位的DEF分子，而粉末X射线衍射图没有任何变化。脱溶剂化材料的H-2吸附等温线在吸附和解吸之间显示出明显的滞后现象，并且吸附量比模拟预测的要少。动力学数据表明，滞后不是由于传质限制引起的，对此行为最可能的解释是在活化条件下骨架部分塌陷为非晶相。

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