Kalaj Mark, Carter Korey P, Savchenkov Anton V, Pyrch Mikaela M, Cahill Christopher L
Department of Chemistry, The George Washington University , 800 22nd Street, NW, Washington, D.C. 20052, United States.
Samara National Research University , Samara, 443086, Russian Federation.
Inorg Chem. 2017 Aug 7;56(15):9156-9168. doi: 10.1021/acs.inorgchem.7b01208. Epub 2017 Jul 25.
The syntheses and crystal structures of six new heterometallic compounds containing the UO cation, o-, m-, and p-iodobenzoic acid ligands, and Tl, Rb, and Cs cations which adopt the role of both charge balancing cation and secondary metal center are described, as are the luminescent properties for Tl containing compounds 1, 4, and 6. The structures of compounds 1-3 are isomorphous and contain uranyl monomers bound by o-iodobenzoic acid ligands with Tl, Rb, and Cs cations acting as secondary metal centers. Compounds 4 and 5 are also isomorphous and feature m-iodobenzoic acid ligands bound to the uranyl cation along with Tl and Rb cations. Compound 6 is unique in this series as it is assembled from a dimeric uranyl unit and features p-iodobenzoic acid ligands and Tl cations which function as charge balancing secondary metal centers. Single crystal X-ray diffraction analysis of these materials suggests that the secondary metal cations are incorporated based on the size of their ionic radius (Tl < Rb < Cs), which is directly related to the size of the "pocket" observed in 1-6. Further, Voronoi-Dirichlet tessellation and Hirshfeld surface analysis were used to probe the coordination environment of the secondary metal centers as part of ongoing efforts to develop metrics for determining the coordination number of secondary metal cations in similar systems.
描述了六种新型异金属化合物的合成及晶体结构，这些化合物含有UO阳离子、邻、间、对碘苯甲酸配体以及Tl、Rb和Cs阳离子，它们既充当电荷平衡阳离子又充当二级金属中心，还描述了含Tl化合物1、4和6的发光性质。化合物1 - 3的结构同构，包含由邻碘苯甲酸配体结合的铀酰单体，其中Tl、Rb和Cs阳离子作为二级金属中心。化合物4和5也同构，其特征是间碘苯甲酸配体与铀酰阳离子以及Tl和Rb阳离子结合。化合物6在该系列中是独特的，因为它由二聚铀酰单元组装而成，具有对碘苯甲酸配体和充当电荷平衡二级金属中心的Tl阳离子。对这些材料的单晶X射线衍射分析表明，二级金属阳离子是根据其离子半径大小（Tl < Rb < Cs）掺入的，这与在1 - 6中观察到的“口袋”大小直接相关。此外，作为开发确定类似体系中二级金属阳离子配位数指标的持续努力的一部分，使用了Voronoi - Dirichlet镶嵌和Hirshfeld表面分析来探究二级金属中心的配位环境。
