Department of Chemistry, The George Washington University, 800 22nd Street, NW, Washington, DC, 20052, USA.
Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, WA, 99354, USA.
Chemistry. 2018 Sep 3;24(49):12747-12756. doi: 10.1002/chem.201801044. Epub 2018 Jul 2.
Hybrid materials bearing elements from the 5f block display a rich diversity of coordination geometries, connectivities, and assembly motifs. Exemplary in this regard have been uranyl coordination polymers, which feature a wide range of secondary building units resulting from hydrolysis and oligomerization of the [UO ] cation. An alternative approach to novel materials, however, suppresses hydrolysis and relies on non-covalent interactions (e.g. hydrogen or halogen bonding) to direct assembly of a more limited suite of species or building units. This may be achieved through the use of high-anion media to promote singular actinyl anions that are assembled with organic cations, or by way of functionalized chelating ligands that produce complexes suited for assembly through peripheral donor/acceptor sites. Presented in this Concept article is therefore an overview of our efforts in this arena. We highlight examples of each approach, share our thoughts regarding delineation of assembly criteria, and discuss the opportunities for exploring structure-property relationships in these systems.
含有 5f 族元素的杂化材料表现出丰富多样的配位几何形状、连接性和组装基序。在这方面，铀酰配位聚合物就是一个很好的例子，其特征是由于 [UO 2 ] 阳离子的水解和齐聚作用而产生的广泛的次级建筑单元。然而，一种替代新型材料的方法是抑制水解，并依赖于非共价相互作用（例如氢键或卤键）来指导更有限的一组物质或建筑单元的组装。这可以通过使用高阴离子介质来促进与有机阳离子组装的单一的锕酰阴离子来实现，或者通过使用功能化的螯合配体来产生适合通过外围供体/受体位点组装的配合物来实现。因此，本文概述了我们在这一领域的努力。我们强调了每种方法的实例，分享了我们对确定组装标准的看法，并讨论了在这些系统中探索结构-性能关系的机会。
