Hybrid polyoxometalates as post-functionalization platforms: from fundamentals to emerging applications.,Chemical Society Reviews

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Hybrid polyoxometalates as post-functionalization platforms: from fundamentals to emerging applications.
Chemical Society Reviews ( IF 40.4 ) Pub Date : 2019-12-03 , DOI: 10.1039/c8cs00854j
Alexander V Anyushin ₁ , Aleksandar Kondinski ₁ , Tatjana N Parac-Vogt ₁

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Polyoxometalates (POMs) represent an important group of metal-oxo nanoclusters, typically comprised of early transition metals in high oxidation states (mainly V, Mo and W). Many plenary POMs exhibit good pH, solvent, thermal and redox stability, which makes them attractive components for the design of covalently integrated hybrid organic-inorganic molecules, herein referred to as hybrid-POMs. Until now, thousands of organic hybrid-POMs have been reported; however, only a small fraction can be further functionalized using other organic molecules or metal cations. This emerging class of 'post-functionalizable' hybrid-POMs constitute a valuable modular platform that permits coupling of POM properties with different organic and metal cation functionalities, thereby expanding the key physicochemical properties that are relevant for application in (photo)catalysis, bioinorganic chemistry and materials science. The post-functionalizable hybrid-POM platforms offer an opportunity to covalently link multi-electron redox responsive POM cores with virtually any (bio)organic molecule or metal cation, generating a wide range of materials with tailored properties. Over the past few years, these materials have been showcased in the preparation of framework materials, functional surfaces, surfactants, homogeneous and heterogeneous catalysts and light harvesting materials, among others. This review article provides an overview on the state of the art in POM post-functionalization and highlights the key design and structural features that permit the discovery of new hybrid-POM platforms. In doing so, we aim to make the subject more comprehensible, both for chemists and for scientists with different materials science backgrounds interested in the applications of hybrid (POM) materials. The review article goes beyond the realms of polyoxometalate chemistry and encompasses emerging research domains such as reticular materials, surfactants, surface functionalization, light harvesting materials, non-linear optics, charge storing materials, and homogeneous acid-base catalysis among others.

中文翻译：

杂多金属氧酸盐作为后功能化平台：从基础到新兴应用。

多金属氧酸盐（POM）代表了重要的一组金属-氧纳米簇，通常由处于高氧化态（主要是V，Mo和W）的早期过渡金属组成。许多全POM表现出良好的pH值，溶剂，热和氧化还原稳定性，这使其成为设计共价整合的杂化有机-无机分子（此处称为杂化POM）的诱人成分。到目前为止，已经报道了成千上万的有机混合POM。然而，使用其他有机分子或金属阳离子只能将一小部分进一步官能化。这类新兴的“后功能化”混合POM构成了有价值的模块化平台，可将POM属性与不同的有机和金属阳离子功能耦合在一起，从而扩展了与（光）催化，生物无机化学和材料科学相关的关键物理化学性质。后功能化的混合POM平台提供了将多电子氧化还原反应性POM核与几乎任何（生物）有机分子或金属阳离子共价连接的机会，从而产生了具有定制性质的多种材料。在过去的几年中，这些材料在骨架材料，功能性表面，表面活性剂，均相和非均相催化剂以及光收集材料等的制备中得到了展示。这篇评论文章概述了POM后功能化的最新技术，并重点介绍了允许发现新的混合POM平台的关键设计和结构特征。在这样做，我们的目标是让化学家和对混合（POM）材料的应用感兴趣的具有不同材料科学背景的科学家都可以更容易理解该主题。这篇综述文章超越了多金属氧酸盐化学领域，涵盖了新兴的研究领域，例如网状材料，表面活性剂，表面功能化，光收集材料，非线性光学，电荷存储材料以及均相酸碱催化等。

更新日期：2020-02-13

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