Porous organic-inorganic assemblies constructed from Keggin polyoxometalate anions and calix[4]arene-Na+ complexes: structures and guest-sorption profiles.
Porous organic-inorganic assemblies constructed from Keggin polyoxometalate anions and calix[4]arene-Na+ complexes: structures and guest-sorption profiles.
复制标题
DOI：
10.1002/anie.200453693
复制
发表时间：
2004-05
影响因子：
--
通讯作者：
Yusuke Ishii;Yasumasa Takenaka;K. Konishi
中科院分区：
文献类型：
--
作者：
Yusuke Ishii;Yasumasa Takenaka;K. Konishi
多分子组分的自组织合理设计结晶固体是超分子化学中一个有趣的课题，因为它允许组分有明确的空间排列，并形成各种具有独特功能的三维结构特别是有机化合物和无机金属团簇的结合是有趣的，因为它们具有固有的不同性质和在晶格中可能的协同效应。多金属氧酸盐是一种阴离子型的早期过渡金属氧化物簇，由于其离散的结构和显著的酸碱、氧化还原和光化学性质，是一种有吸引力的无机建筑材料，具有广泛的应用前景。[2,3]本文报道了两个由Keggin多氧钨酸钠盐（Na3PW12O40）和杯状[4]芳烃衍生物（1,2）通过有机宿主与钠离子之间的主客体相互作用组装而成的多孔杂化物我们还展示了这些多孔材料的客体吸附能力。将1在CHCl3中的溶液和Na3PW12O40在MeOH中的溶液混合，并在室温下放置，得到3:1组装体[1- na] 3 [PW12O40]的单晶(3)。x射线晶体学研究揭示了无限离子晶体与立方晶体系统的形成，其中包含一个首尾相连的1-Na+配合物柱状阵列作为基本成分。如图1a所示，柱沿a、b和c轴向三个方向传播，并以正交构型交替堆叠，形成三维网格状框架，作为α-[PW12O40] 3À阴离子的支架。一个阴离子被6个1- na +单元包围，因此没有观察到钠和簇氧原子之间的键相互作用（图1b）每个杯形芳烃单元的侧面与阴离子发生弱的分子间相互作用（如范德华力）以这种方式将阳离子和阴离子组分填塞，留下微孔作为剩余空间。如图1a和c所示，在四个杯状[4]芳烃单元之间形成尺寸约为6.9的空腔，这些空腔沿a轴延伸形成通道。通道是
The rational design of crystalline solids by self-organization of multiple molecular components is one of the interesting subjects in supramolecular chemistry, as it allows a defined spatial arrangement of the components and the formation of a diverse range of three-dimensional structures with unique functions.[1] In particular, the combination of organic compounds and inorganic metal clusters is interesting owing to their inherently different natures and possible synergetic effects in the crystal lattice. Polyoxometalates, anionic early transition metal oxide clusters, are attractive inorganic building blocks because of their discrete structures and notable acid/base, redox, and photochemical properties, which lead to a vast range of applications.[2, 3] Herein we report two porous hybrids assembled from a Keggin polyoxotungstate sodium salt (Na3PW12O40) and calix [4] arene derivatives (1, 2) by host–guest interaction between the organic hosts and the sodium ion.[4] We also demonstrate the guest-sorption capabilities of these porous materials. Solutions of 1 in CHCl3 and Na3PW12O40 in MeOH were mixed and allowed to stand at room temperature to give single crystals of the 3: 1 assembly [1-Na] 3 [PW12O40](3). X-ray crystallographic studies revealed the formation of an infinite ionic crystal with a cubic crystal system, which contained a head-to-tail columnar array of the 1-Na+ complexes as a fundamental component. As shown in Figure 1 a, the columns propagate in three directions along the a, b, and c axes and are stacked alternately in orthogonal configurations to generate a three-dimensional gridlike framework, which serves as a scaffold for the α-[PW12O40] 3À anions. One anion is surrounded by six 1-Na+ units, whereby no bonding interactions between sodium and cluster oxygen atoms are observed (Figure 1 b).[5] The side faces of each calix [4] arene unit are involved in weak intermolecular interactions with the anions (eg, van der Waals forces).[6] Packing of the cationic and anionic components in this manner leaves micropores as the residual space. As shown in Figure 1 a and c, cavities with sizes of about 6 9 are created between four calix [4] arene units, which extend along the a axis to form channels. Channels are