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Metalloporphyrinic metal-organic frameworks: Controlled synthesis for catalytic applications in environmental and biological media.
Advances in Colloid and Interface Science ( IF 15.9 ) Pub Date : 2020-01-23 , DOI: 10.1016/j.cis.2020.102108 Sherif A Younis 1 , Dong-Kwon Lim 2 , Ki-Hyun Kim 3 , Akash Deep 4
Advances in Colloid and Interface Science ( IF 15.9 ) Pub Date : 2020-01-23 , DOI: 10.1016/j.cis.2020.102108 Sherif A Younis 1 , Dong-Kwon Lim 2 , Ki-Hyun Kim 3 , Akash Deep 4
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Recently, as a new sub-family of porous coordination polymers (PCPs), porphyrinic-MOFs (Porph-MOFs) with biomimetic features have been developed using porphyrin macrocycles as ligands and/or pillared linkers. The control over the coordination of the porphyrin ligand and its derivatives however remains a challenge for engineering new tunable Porph-MOF frameworks by self-assembly methods. The key challenges exist in the following respects: (i) collapse of the large open pores of Porph-MOFs during synthesis, (ii) deactivation of unsaturated metal-sites (UMCs) by axial coordination, and (iii) the tendency of both coordinated moieties (at peripheral meso- and beta-carbon sites) and the N4-pyridine core to coordinate with metal cations. In this respect, this review covers the advances in the design of Porph-MOFs relative to their counterpart covalent organic frameworks (Porph-COFs). The potential utility of custom-designed porphyrin/metalloporphyrins ligands is highlighted. Synthesis strategies of Porph-MOFs are also illustrated with modular design of hybrid guest@host composites (either Porph@MOFs or guest@Porph-MOFs) with exceptional topologies and stability. This review summarizes the synergistic benefits of coordinated porphyrin ligands and functional guest molecules in Porph-MOF composites for enhanced catalytic performance in various redox applications. This review shed lights on the engineering of new tunable hetero-metals open active sites within (metallo)porphyrin-MOFs as out-of-the-box platforms for enhanced catalytic processes in chemical and biological media.
中文翻译：
金属卟啉金属有机框架：在环境和生物介质中催化应用的受控合成。
近年来，作为多孔配位聚合物（PCP）的一个新的子家族，使用卟啉大环化合物作为配体和/或柱状连接基，开发了具有仿生特征的卟啉-MOF（Porph-MOF）。然而，对于卟啉配体及其衍生物的配位的控制对于通过自组装方法工程设计新的可调式Porph-MOF框架仍然是一个挑战。在以下方面存在主要挑战：（i）合成过程中Porph-MOF的大开口孔的坍塌；（ii）通过轴向配位使不饱和金属位点（UMCs）失活；（iii）两种配位的趋势部分（在外围的中碳和β-碳位点）和N4-吡啶核与金属阳离子配合。在这方面，这篇综述涵盖了Porph-MOFs相对于其对应的共价有机框架（Porph-COFs）的设计进展。强调了定制设计的卟啉/金属卟啉配体的潜在用途。Porph-MOF的合成策略还通过具有优异拓扑结构和稳定性的混合guest @ host复合材料（Porph @ MOF或guest @ Porph-MOF）的模块化设计进行了说明。这篇综述总结了卟啉-MOF复合材料中配位的卟啉配体和功能性客体分子的协同增效作用，以增强在各种氧化还原应用中的催化性能。这篇综述揭示了在（金属）卟啉-MOFs中新的可调谐异质金属开放活性位点的工程设计，这些位点是用于增强化学和生物介质催化过程的现成平台。
更新日期：2020-01-23
中文翻译：
金属卟啉金属有机框架：在环境和生物介质中催化应用的受控合成。
近年来，作为多孔配位聚合物（PCP）的一个新的子家族，使用卟啉大环化合物作为配体和/或柱状连接基，开发了具有仿生特征的卟啉-MOF（Porph-MOF）。然而，对于卟啉配体及其衍生物的配位的控制对于通过自组装方法工程设计新的可调式Porph-MOF框架仍然是一个挑战。在以下方面存在主要挑战：（i）合成过程中Porph-MOF的大开口孔的坍塌；（ii）通过轴向配位使不饱和金属位点（UMCs）失活；（iii）两种配位的趋势部分（在外围的中碳和β-碳位点）和N4-吡啶核与金属阳离子配合。在这方面，这篇综述涵盖了Porph-MOFs相对于其对应的共价有机框架（Porph-COFs）的设计进展。强调了定制设计的卟啉/金属卟啉配体的潜在用途。Porph-MOF的合成策略还通过具有优异拓扑结构和稳定性的混合guest @ host复合材料（Porph @ MOF或guest @ Porph-MOF）的模块化设计进行了说明。这篇综述总结了卟啉-MOF复合材料中配位的卟啉配体和功能性客体分子的协同增效作用，以增强在各种氧化还原应用中的催化性能。这篇综述揭示了在（金属）卟啉-MOFs中新的可调谐异质金属开放活性位点的工程设计，这些位点是用于增强化学和生物介质催化过程的现成平台。
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