Metal-Organic Conjugated Microporous Polymers
Metal-Organic Conjugated Microporous Polymers
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金属有机共轭微孔聚合物
DOI：
10.1002/ange.201005864
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发表时间：
2010
影响因子：
--
通讯作者：
Jiang J
中科院分区：
文献类型：
--
作者：
Jiang J
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前景。[1]金属有机框架（MOF）、[2]共价有机框架（COF）、[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，原则上可以实现显着的合成多样化。微孔有机聚合物[4]的一个特殊优点是可以将一系列有用的化学功能引入孔中。[6]这源于这些网络的化学和热稳定性，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，并且已成为最近备受关注的主题。已经开发出多种 CMP（以及密切相关的结构）。[4a, 7] 将金属位点纳入 CMP 可以开发出具有有用的综合化学和物理特性（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 材料可能对多相催化或光催化感兴趣，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 网络进行功能化的论证。金属纳米粒子并入微孔网络已得到证实。[4e, 7e, 9a] 此外，最近描述了一种显示出非常高的 H2 吸附的锂化 CMP，但金属在分子水平上掺入的确切性质尚不清楚。[9b] 最近的另一份报告详细介绍了一种卟啉衍生的微孔有机聚合物，它对硫醇的氧化显示出高催化活性。 [10]除此之外，还没有关于金属功能化 CMP 的有目的地合成的报道。在这里，我们报告了两种制备金属有机 CMP（MO-CMP）的通用策略。与 MOF 不同，[2] 所得的含金属共轭聚合物是无定形的。另一个显着区别是金属位点不必是网络中的节点，但也可以悬挂在聚合物链上，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