Two- and three-dimensional cadmium-organic frameworks with trimesic acid and 4,4'-trimethylenedipyridine.
Two- and three-dimensional cadmium-organic frameworks with trimesic acid and 4,4'-trimethylenedipyridine.
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DOI：
10.1021/ic049523o
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发表时间：
2004-05
影响因子：
4.6
通讯作者：
F. A. Almeida Paz;J. Klinowski
中科院分区：
文献类型：
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作者：
F. A. Almeida Paz;J. Klinowski
以1,3,5-苯三羧酸阴离子（HXBTC(x-3)）和4,4'-三甲基二吡啶（TMD）为原料，水热合成了三种新型镉有机骨架（HXBTC(x-3)），并利用单晶x射线衍射、热分析、元素分析、红外光谱和拉曼光谱对其进行了表征：[Cd(HBTC)(TMD)(H(2)O)]、[Cd(HBTC)(TMD)（H(2)O）、[Cd(2)(BTC)(TMD)(2)(NO(3))]。3H(2)O (III)，结构I和II被分离为晶体的混合物。结构1包含一个波动的无限二维[Cd(HBTC)(TMD)(2)]框架，具有（4,4）拓扑结构和矩形孔隙，截面约为3.4 x 11.0 a，呈人字形分布。I的晶体结构是通过在ABAB中对二维骨架进行平行填充得到的。时尚。化合物II具有多孔的三维金刚石框架，其通道在单元胞的几个方向上运行，从而允许发生2倍的互穿。最突出的通道沿c轴呈砖墙状分布，横截面约为3.2 x 13.2 a。结构III可以被看作是双核次级建筑单元（SBU）的三维组装，它导致了一个紧凑、中性、协调键合的八连接框架[Cd(2)(BTC)(TMD)(2)(NO(3))]，呈现出不寻常的3(6)4（22）拓扑结构。TMD配体的灵活性增加（由两个4-吡啶环之间的三个亚甲基带来）可以导致相同的反应体系产生各种各样的晶体结构。
Three novel cadmium-organic frameworks built-up from 1,3,5-benzenetricarboxylate anions (HXBTC(x-3)) and 4,4'-trimethylenedipyridine (TMD) have been hydrothermally synthesized, and characterized using single-crystal X-ray diffraction, thermoanalytical measurements, elemental analysis, and IR and Raman spectroscopies: [Cd(HBTC)(TMD)(2)].8.5H(2)O (I), [Cd(HBTC)(TMD)(H(2)O)].4.5H(2)O (II), and [Cd(2)(BTC)(TMD)(2)(NO(3))].3H(2)O (III), with structures I and II being isolated as a mixture of crystals. Structure I contains an undulating infinite two-dimensional [Cd(HBTC)(TMD)(2)] framework, with a (4,4) topology and rectangular pores, ca. 3.4 x 11.0 A in cross-section, distributed in a herringbone manner. The crystal structure of I is obtained by parallel packing of this 2D framework in an [ABAB.] fashion. Compound II has a porous 3D diamondoid framework with channels running in several directions of the unit cell, which allows 2-fold interpenetration to occur. The most prominent channels are distributed in a brick-wall fashion along the c axis and have a cross-section of ca. 3.2 x 13.2 A. Structure III can be seen as the three-dimensional assembly of binuclear secondary building units (SBU), which leads to a compact, neutral, and coordinatively bonded eight-connected framework, [Cd(2)(BTC)(TMD)(2)(NO(3))], exhibiting an unusual 3(6)4(22) topology. The increased flexibility of the TMD ligands (brought about by the three methylene groups between the two 4-pyridyl rings) can lead, for the same reactive system, to a large variety of crystal architectures.