POMzites: A Family of Zeolitic Polyoxometalate Frameworks from a Minimal Building Block Library.
POMzites: A Family of Zeolitic Polyoxometalate Frameworks from a Minimal Building Block Library.
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DOI：
10.1021/jacs.7b01807
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发表时间：
2017-04-26
影响因子：
15
通讯作者：
Cronin L
中科院分区：
文献类型：
--
作者：
Boyd T;Mitchell SG;Gabb D;Long DL;Song YF;Cronin L
通过对30余种含环杂多阴离子[P8 W 48 O 184]40-（简称{P8 W 48}）的配位聚合物的分类和分析，说明了环杂多阴离子[P8 W 48 O 184]40-（简称{P8 W 48}）是构建多孔骨架材料的理想结构单元的原因。该分析表明，第一行过渡金属（TM）与{P8 W 48}的环外配位通常产生在一维、二维或三维中延伸通过{W-O-TM-O-W}桥的骨架。然而，尽管这些化合物具有丰富的结构多样性，但对TM与{P8 W 48}环的配位知之甚少，因此在很大程度上是不可预测的，并且直到现在还没有出现任何可以允许合理设计的结构分类。在此，我们不仅提出了一种新的方法来理解和分类这类新的材料，我们还提出了三个基于{P8 W 48}的框架，补充了先前描述的那些框架。这些新的化合物帮助我们假设了这些材料的新分类。这是可能的，因为发现{P8 W 48}环的TM协调位点，一旦完全映射，就导致明确定义的连通性类别。总之，分析提供了对每个框架内的构件连接性的性质的洞察，以促进相关结构之间的比较，并从根本上统一这个化合物家族。因此，我们暂时将这些化合物命名为“POMzite”，以反映每个家族成员的POM基组成和沸石性质，尽管关键的是，POMzite在其制备的模块化方式上不同于沸石。由于预期会合成更多的POMzite，本文介绍的分类系统和术语将允许在已建立的材料的背景下对新化合物进行分类和理解。更好地理解TM与{P8 W 48}环的配位可以允许新框架的靶向合成，而不是依赖于当前方法中明显的偶然性。
We describe why the cyclic heteropolyanion [P8W48O184]40– (abbreviated as {P8W48}) is an ideal building block for the construction of intrinsically porous framework materials by classifying and analyzing >30 coordination polymers incorporating this polyoxometalate (POM) ligand. This analysis shows that the exocyclic coordination of first-row transition metals (TMs) to {P8W48} typically yields frameworks which extend through {W–O–TM–O–W} bridges in one, two, or three dimensions. However, despite the rich structural diversity of such compounds, the coordination of TMs to the {P8W48} ring is poorly understood, and therefore largely unpredictable, and had not until now been present with any structural classification that could allow rational design. Herein, not only do we present a new approach to understand and classify this new class of materials, we also present three {P8W48}-based frameworks which complement those frameworks which have previously been described. These new compounds help us postulate a new taxonomy of these materials. This is possible because the TM coordination sites of the {P8W48} ring are found, once fully mapped, to lead to well-defined classes of connectivity. Together, analysis provides insight into the nature of the building block connectivity within each framework, to facilitate comparisons between related structures, and to fundamentally unite this family of compounds. Hence we have tentatively named these compounds as “POMzites” to reflect the POM-based composition and zeolitic nature of each family member, although crucially, POMzites differ from zeolites in the modular manner of their preparation. As the synthesis of further POMzites is anticipated, the classification system and terminology introduced here will allow new compounds to be categorized and understood in the context of the established materials. A better understanding of TM coordination to the {P8W48} ring may allow the targeted synthesis of new frameworks rather than the reliance on serendipity apparent in current methods.