Post-Synthetic Modification of Tagged Metal-Organic Frameworks
Post-Synthetic Modification of Tagged Metal-Organic Frameworks
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DOI：
10.1002/anie.200802908
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发表时间：
2008-01-01
影响因子：
16.6
通讯作者：
Richardson, Christopher
中科院分区：
文献类型：
--
作者：
Burrows, Andrew D.;Frost, Christopher G.;Richardson, Christopher
金属有机框架（MOFs）目前吸引了相当多的关注，[1]主要是因为它们的多孔性潜力，以及它们在气体储存，[2]催化，[3]分离，[4]和药物输送等各种应用中的后续用途。[5]第一代MOFs是通过将金属中心与简单的市售桥接配体连接在一起形成的，例如1，4-苯二甲酸酯（bdc），[6]但此后越来越多地转向更复杂的结构和增加的功能。例如，已经报道和研究了其中孔含有可接近的氢键基团、[7]不饱和金属中心、[8]或手性[9]的M0 F，并且已经探索了能够经历客体诱导的转化或重整的动态多孔材料的制备。[10]形成官能化网络的另一种方法是在预成型的MOF上进行反应，将一种固态材料转化为另一种。将另外的官能团（“标签”）并入连接配体中提供了形成结构的机会，其中该基团在MOF合成期间被保留，从而允许其突出到网络结构的孔或通道中。我们将“标签”定义为在M0 F形成期间稳定且无害（即，非结构限定）但可通过合成后修饰转化的基团或官能团。图1示意性地显示了这种方法。类似的标记概念最近也应用于药物化学。[第十一届]
Metal–organic frameworks (MOFs) are currently attracting considerable attention,[1] largely because of their potential for porosity, and their consequent use in applications as diverse as gas storage,[2] catalysis,[3] separations,[4] and drug delivery.[5] The first generation of MOFs were formed by linking together metal centers with simple, commercially available bridging ligands, such as 1, 4-benzenedicarboxylate (bdc),[6] but there has since been an increasing shift towards more complex structures and increased functionality. For example, MOFs in which the pores contain accessible hydrogenbonding groups,[7] unsaturated metal centers,[8] or chirality [9] have been reported and studied, and the preparation of dynamic porous materials, capable of undergoing guestinduced transformations or reformations, has been explored.[10]Another approach to forming functionalized networks is to undertake reactions on preformed MOFs, converting one solid state material into another. The incorporation of an additional functional group, a “tag”, into a linking ligand offers the opportunity to form structures in which this group is preserved during the MOF synthesis, allowing it to project into the pores or channels of the network structure. We define a “tag” as a group or functionality that is stable and innocent (that is, non-structure-defining) during MOF formation, but that can be transformed by a post-synthetic modification. This approach is shown schematically in Figure1. A similar concept of tagging has also recently been applied in medicinal chemistry.[11]