Metal-Organic Conjugated Microporous Polymers
Metal-Organic Conjugated Microporous Polymers
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DOI：
10.1002/anie.201005864
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发表时间：
2011-01-01
影响因子：
16.6
通讯作者：
Cooper, Andrew I.
中科院分区：
文献类型：
--
作者：
Jiang, Jia-Xing;Wang, Chao;Cooper, Andrew I.
微孔材料在分子分离、气体吸附和催化等领域具有潜在的应用价值。[1]诸如金属有机框架（MOFs），[2]共价有机框架（COFs），[3]微孔有机聚合物[4]和多孔有机分子固体[5]等材料都含有有机官能团，原则上可以允许显着的合成多样化。微孔有机聚合物[4]的一个特别优点是有可能将一系列有用的化学官能团引入孔中。[6]这源于这些网络的化学和热稳定性，其促进了各种化学转化。共轭微孔聚合物（CMP）[4a]可以表现出扩展的π-共轭，并且已经成为最近非常感兴趣的主题。已经开发了各种CMP（和密切相关的结构）。[4a将金属位点结合到CMP中可以开辟具有有用的组合化学和物理性质（例如催化活性、导电性或光吸收/发射）的第二代多孔材料。[8]例如，金属化CMP材料可能在多相催化或电催化中感兴趣，其中高表面积将是有益的。然而，很少有在分子水平上用金属对CMP网络进行官能化的证明。已经证明了将金属纳米颗粒结合到微孔网络中。[4e此外，最近描述了显示出非常高的H2吸附的锂化CMP，但是在分子水平上金属结合的精确性质不清楚。[9b]另一个最近的报道详细描述了卟啉衍生的微孔有机聚合物，其对硫醇的氧化显示出高催化活性。[10]除此之外，没有关于金属官能化CMP的有目的合成的报道。在这里，我们报告了两个通用的策略，用于制备金属有机CMP（MO-CMP）。与MOFs不同，[2]所得的含金属共轭聚合物是无定形的。另一个显著的区别是金属位点不需要是网络中的节点，而是也可以侧接于聚合物链，从而允许
Microporous materials have potential applications in areas including molecular separation, gas sorption and catalysis.[1] Materials such as metal–organic frameworks (MOFs),[2] covalent organic frameworks (COFs),[3] microporous organic polymers,[4] and porous organic molecular solids [5] all contain organic functionalities which, in principle, can allow significant synthetic diversification. A particular advantage of microporous organic polymers [4] is the potential to introduce a range of useful chemical functionalities into the pores.[6] This stems from the chemical and thermal stability of these networks which facilitates a variety of chemical transformations.Conjugated microporous polymers (CMPs)[4a] can exhibit extended π-conjugation and have been the subject of much recent interest. A variety of CMPs (and closely related structures) have been developed.[4a, 7] The incorporation of metal sites into CMPs could open up second-generation porous materials with useful combined chemical and physical properties such as catalytic activity, electrical conductivity, or light-absorption/emission.[8] For example, metalated CMP materials might be of interest in heterogeneous catalysis or photocatalysis, where high surface areas would be beneficial. There are, however, few demonstrations of the functionalization of CMP networks with metals at the molecular level. The incorporation of metal nanoparticles into microporous networks has been demonstrated.[4e, 7e, 9a] Also, a lithiated CMP showing very high H2 sorption was described recently but the precise nature of the metal incorporation at the molecular level was not clear.[9b] Another recent report details a porphyrin-derived microporous organic polymer which shows high catalytic activity for the oxidation of thiols.[10] Beyond this, there are no reports on the purposeful synthesis of metal-functionalized CMPs. Here, we report two versatile strategies for preparing metal–organic CMPs (MO-CMPs). Unlike MOFs,[2] the resulting metal-containing conjugated polymers are amorphous. Another significant difference is that the metal sites need not be nodes in the network but can also be attached pendant to the polymer chains, thus allowing