Extending Rectangular Metal-Organic Frameworks to the Third Dimension: Discrete Organometallic Boxes for Reversible Trapping of Halocarbons Occurring with Conservation of the Lattice
Extending Rectangular Metal-Organic Frameworks to the Third Dimension: Discrete Organometallic Boxes for Reversible Trapping of Halocarbons Occurring with Conservation of the Lattice
复制标题
将矩形金属有机框架扩展到第三维：用于可逆捕获卤代烃的离散有机金属盒，同时保持晶格守恒
DOI：
10.1002/anie.200805949
复制
发表时间：
2009-01-01
影响因子：
16.6
通讯作者：
Jin, Guo-Xin
中科院分区：
文献类型：
--
作者：
Han, Ying-Feng;Jia, Wei-Guo;Jin, Guo-Xin
在过去的十年中，在以三角形、正方形和其他多边形为基本单元的功能金属超分子结构的合理设计以及三维笼形和多面体的构建方面取得了重大进展。金属超分子由于其能够将客体部分封装在不同尺寸和形状的空腔中，在分离过程、催化、选择性识别和传感器技术中表现出巨大的应用潜力。[1]在已报道的主-客体体系中，金属杂环化合物具有很高的形状和尺寸选择性。[2]金属-有机骨架也属于这类材料，尽管它们通常是高度刚性的，但它们在各种应力下保持其结构，例如温度变化、化学反应、客体交换或其他物理刺激。[3]有关堆积分子环状排列以形成空穴和孔的相关研究相当少见。[4]这种可以与某些客体分子相互作用的主体框架的设计和合成对于先进材料的产生具有意义，因为它们具有许多特征性特征，包括将客体分子限制在具有深的货车德瓦尔斯型势能阱的腔中。对目标分子的高选择性识别、容纳和分离依赖于空腔的大小与客体分子的分子尺寸之间的关系。[5]然而，单体主体框架可以通过超分子相互作用，如π-π堆积相互作用、C_3H··· π相互作用和C_3H··· X（X= F，Cl，Br，I）相互作用来构建更高维度的结构。[5g具有在角处的金属中心和两对不同的相对配体“边缘”的平面分子矩形可以由具有紧密结合的刚性间隔基和配位位点的双核络合物组装，以通过第二类型的线性构建单元连接两个这样的分子。[1]我们最近报道，邻氨基苯甲酸和氯冉酸桥联的双核物种不仅是矩形的合适单元，而且也适用于棱柱和笼的上述建设原则。[7]我们想知道，我们是否可以通过将矩形结构的间隔区延伸到第三维来调整这样的分子矩形，以形成大的空腔，从而模拟金属有机框架（MOFs）对可溶性化合物的锁定特性。以6，11-二羟基-5，12-萘并二酮（H2 dhnq）和吡嗪为间隔配体，采用半夹心铱角，构建了一种具有选择性和可逆性的CH 2Cl 2吸附性能的分子有机金属盒，
During the last decade, significant progress has been made in the rational design of functional metallasupramolecular architectures with triangles, squares, and other polygons as basic units and, furthermore, the construction of threedimensional cages and polyhedra. Owing to their capability of encapsulating guest moieties within cavities of different sizes and shapes, metallasupramolecules have demonstrated great potential in the applications of separation processes, catalysis, selective recognition, and sensor technologies.[1] Among the reported host–guest systems, the metallacycles exhibit high shape and size selectivity.[2] Metal–organic frameworks also belong to this class of materials and, even though they are normally highly rigid, they retain their structures upon various stresses, such as temperature changes, chemical reactions, guest exchanges, or other physical stimuli.[3] Related studies for packing molecular cyclic arrangements to form cavities and pores are quite rare.[4] The design and synthesis of such host frameworks that can interact with certain guest molecules have implications for the generation of advanced materials, because they have many characteristic features, including the confinement of guest molecules in the cavity with a deep, van der Waals-type, potential energy well. The high selectivity recognition, accommodation, and separation of the target molecules depends on the relationship between the size of the cavity and the molecular dimensions of the guest molecules.[5] However, the monomer host frameworks can be used to build up higher dimensional structures by supramolecular interactions, such as π–π stacking interactions, CÀH··· π interactions, and CÀH··· X (X= F, Cl, Br, I) interactions.[5g, 6]Planar molecular rectangles with metal centers at the corners and two pairs of differing opposite ligand “edges” can be assembled from a binuclear complex possessing a tightly binding rigid spacer and coordination sites to connect two such molecules by a second type of linear building unit.[1] We recently reported that oxalato and chloranilate bridged dinuclear species are suitable units not only for rectangles, but also for prisms and cages by the aforementioned construction principles.[7] We wondered if we could tune such molecular rectangles by extending the spacers of the rectangular structure into the third dimension to form large cavities, thus simulating the caging properties of metal–organic frameworks (MOFs) for soluble compounds. Based on 6, 11-dihydroxy-5, 12-naphthacenedione (H2dhnq) and pyrazine spacing ligands, and half-sandwich iridium corners, we built up a molecular organometallic box, which exhibited selective and reversible CH2Cl2 adsorption properties while