A crystalline mesoporous coordination copolymer with high microporosity
A crystalline mesoporous coordination copolymer with high microporosity
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DOI：
10.1002/anie.200705020
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发表时间：
2008-01-01
影响因子：
16.6
通讯作者：
Matzger, Adam J.
中科院分区：
文献类型：
--
作者：
Koh, Kyoungmoo;Wong-Foy, Antek G.;Matzger, Adam J.
由有机连接单元与金属离子或金属簇组装而成的多孔晶体被证明是一类令人兴奋的材料，具有前所未有的性能和在催化，[1]气体储存[2]和分离等应用中的高潜力。[3]从具有多主题配体的给定二级结构单元（SBU）获得的基础结构可以至少事后分析为属于各种网络。[4]在某些情况下，这种方法会产生定义良好的系列，并保留其成员在指标或功能方面有所不同的拓扑结构。[5，6]同时，很明显，即使是在相同反应条件下具有给定金属的单一连接体也可以产生相当大的结构多样性，正如我们最近应用聚合物诱导的异核化来发现基于简单对苯二甲酸连接体/硝酸锌体系的三个新相所示。[7]也许我们应该吸取的一个教训是，目前还没有一个单一的结构预测设计方案，而是一套经验得出的默认行为，通常可以用来合理化的实验结果。在使用具有相同配位功能的两种不同连接剂的情况下，缺乏实验数据，并且没有回答甚至最基本的相组成问题的基础。[8]In从广义上讲，我们可以预期在结晶混合连接体配位聚合物中有两种不同的行为。两种组分结合并允许结晶的默认行为是分离;这种行为形成了结晶纯化的基础。相比之下，当相似反应性的单体组合时的默认行为是无规共聚。因此，有趣的是，考虑在强键可逆地组装框架的多孔晶体中，共聚模式是否占主导地位，或者自分选结晶是否占主导地位。前者代表了发现新的多孔固体的快速途径。为了研究这个问题，我们进行了基于两种不同拓扑结构的有机连接体的多孔晶体的合成，
Porous crystals constructed from the assembly of organic linking units with metal ions or metal clusters are proving to be an exciting class of materials with unprecedented properties and high potential for use in applications such as catalysis,[1] gas storage,[2] and separations.[3] The underlying structure obtained from a given secondary building unit (SBU) with a multitopic ligand can be analyzed, at least with hindsight, as belonging to various nets.[4] In some cases this approach has led to well-defined series with preserved topologies whose members vary in metrics or functionalities.[5, 6] At the same time, it is clear that even a single linker with a given metal under the same reaction conditions can give rise to considerable structural diversity, as is illustrated by our recent application of polymer-induced heteronucleation to the discovery of three new phases based on the simple terephthalic acid linker/zinc nitrate system.[7] Perhaps one lesson to be learned is that there is currently no single structure-predicting design scheme but rather sets of empirically derived default behaviors that can often be used to rationalize the outcome of an experiment. In the case of employing two different linkers possessing the same coordinating functionality, experimental data are lacking, and there is no basis for answering even the most basic question of phase composition.[8]In broad terms we can expect two different behaviors in a crystalline mixed-linker coordination polymer. The default behavior for two components combined and allowed to crystallize is segregation; this behavior forms the basis of purification by crystallization. By contrast, the default behavior when monomers of similar reactivity are combined is random copolymerization. Therefore, it is interesting to contemplate whether in a porous crystal in which strong bonds reversibly assemble the framework, copolymerization patterns will dominate or if self-sorting crystallization will prevail. The former would represent an expeditious route to discover new porous solids. To investigate this question we undertook the synthesis of porous crystals based on two organic linkers of different topologies, namely, terephthalic