Counterion-Controlled Formation of an Octanuclear Uranyl Cage with cis-1,2-Cyclohexanedicarboxylate Ligands,Inorganic Chemistry

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Counterion-Controlled Formation of an Octanuclear Uranyl Cage with cis-1,2-Cyclohexanedicarboxylate Ligands
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2018-05-15 00:00:00 , DOI: 10.1021/acs.inorgchem.8b00147
Pierre Thuéry ₁ , Youssef Atoini ₂ , Jack Harrowfield ₂

Affiliation

cis-1,2-Cyclohexanedicarboxylic acid (c-chdcH₂) was reacted with uranyl nitrate under (solvo-)hydrothermal conditions in the presence of different possible counterions. Two neutral complexes of 1:1 stoichiometry were obtained, [UO₂(c-chdc)(DMF)] (1) and [UO₂(c-chdc)(H₂O)] (2), which crystallize as two-dimensional coordination polymers and do not include the additional cations present in solution. In contrast, the complex [NH₄][PPh₄][(UO₂)₈(c-chdc)₉(H₂O)₆]·3H₂O (3) crystallized in the presence of PPh₄Br, ammonium cations being generated in situ from acetonitrile hydrolysis. This complex of 8:9 uranium:ligand stoichiometry contains an octanuclear anionic cage of D₃ symmetry with a pseudo-cubic arrangement of uranium atoms. The ammonium cation is held within the cage through four hydrogen bonds with uranyl oxo groups directed inward. This cage complex is luminescent, although with a low quantum yield of 0.06, indicating limited potential as a photo-oxidant of included species.

中文翻译：

带有顺式-1,2-环己烷二羧酸酯配体的八核铀酰笼的反离子控制形成

在（溶剂-）水热条件下，在不同的可能抗衡离子存在下，使顺式-1,2-环己烷二甲酸（c - chdcH ₂）与硝酸铀酰反应。获得了两个化学计量比为1：1的中性络合物[UO ₂（c -chdc）（DMF）]（1）和[UO ₂（c -chdc）（H ₂ O）]（2），它们结晶为两个-配位聚合物，不包含溶液中存在的其他阳离子。相反，复合物[NH ₄ ] [PPh ₄ ] [（UO ₂）₈（c -chdc）₉在PPh ₄ Br存在下结晶的（H ₂ O）₆ ]·3H ₂ O（3），由乙腈水解就地生成铵阳离子。这种8：9铀：配体化学计量比的配合物包含D ₃对称的八核阴离子笼，铀原子为伪立方排列。铵阳离子通过四个氢键保持在笼中，其中有向内的铀酰氧代基团。该笼络合物是发光的，尽管具有0.06的低量子产率，表明作为所包含物质的光氧化剂的潜力有限。

更新日期：2018-05-15

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