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由 Y(III)、Na(I) 和手性灵活-非手性刚性二羧酸组装的金属有机骨架。

Metal organic frameworks assembled from Y(III), Na(I), and chiral flexible-achiral rigid dicarboxylates.

机构信息

Departamento de Química Física, Universidad de Oviedo, 33006 Oviedo, Spain.

出版信息

Inorg Chem. 2010 Sep 6;49(17):7917-26. doi: 10.1021/ic100867w.

Abstract

New chiral metal organic frameworks, assembled from Y(III), Na(I), and chiral flexible-achiral rigid dicarboxylate ligands, formulated as [NaY(Tart)(BDC)(H(2)O)(2)] (1) and [NaY(Tart)(biBDC)(H(2)O)(2)] (2) (H(2)Tart = Tartaric acid; H(2)BDC = Terephthalic acid; H(2)biBDC = Biphenyl-4,4'-dicarboxylic acid), were obtained as single phases under hydrothermal conditions. Their structures were solved by single-crystal X-ray diffraction (XRD), and characterized by (13)C CPMAS NMR, thermal analyses (thermogravimetry-mass spectrometry (TG-MS) and differential scanning calorimetry (DSC)), and X-ray thermodiffractometry. Both compounds crystallize in the orthorhombic chiral space group C222(1) with a = 6.8854(2) A, b = 30.3859(7) A, c = 7.4741(2) A for 1, and a = 6.8531(2) A, b = 39.0426(8) A, c = 7.4976(2) A for 2. 1 and 2 are layered structures whose three-dimensional stability is ensured by strong hydrogen bond interactions. The dehydration of both compounds is accompanied by phase transformation, while the spontaneous rehydration process is characterized by different kinetics, fast in the case of 1 and slow for 2.

摘要

新型手性金属有机骨架,由 Y(III)、Na(I)和手性柔性-非手性刚性二羧酸配体组装而成,可表示为NaY(Tart)(BDC)(H2O)2NaY(Tart)(biBDC)(H2O)2(H2Tart = 酒石酸;H2BDC = 对苯二甲酸;H2biBDC = 联苯-4,4'-二羧酸),在水热条件下作为单相获得。它们的结构通过单晶 X 射线衍射(XRD)解决,并通过(13)C CPMAS NMR、热分析(热重-质谱(TG-MS)和差示扫描量热法(DSC))和 X 射线热分析法进行了表征。这两种化合物都结晶为正交手性空间群 C222(1),其中 a = 6.8854(2)A,b = 30.3859(7)A,c = 7.4741(2)A 用于 1,a = 6.8531(2)A,b = 39.0426(8)A,c = 7.4976(2)A 用于 2。1 和 2 是层状结构,其三维稳定性由强氢键相互作用保证。两种化合物的脱水都伴随着相变,而自发的再水合过程具有不同的动力学,1 较快,2 较慢。

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