NIMBE, CEA, CNRS, Université Paris-Saclay, CEA Saclay , 91191 Gif-sur-Yvette , France.
ISIS , Université de Strasbourg , 8 allée Gaspard Monge , 67083 Strasbourg , France.
Inorg Chem. 2018 Jun 4;57(11):6283-6288. doi: 10.1021/acs.inorgchem.8b00147. Epub 2018 May 15.
cis-1,2-Cyclohexanedicarboxylic acid ( c-chdcH) 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, [UO( c-chdc)(DMF)] (1) and [UO( c-chdc)(HO)] (2), which crystallize as two-dimensional coordination polymers and do not include the additional cations present in solution. In contrast, the complex [NH][PPh][(UO)( c-chdc)(HO)]·3HO (3) crystallized in the presence of PPhBr, ammonium cations being generated in situ from acetonitrile hydrolysis. This complex of 8:9 uranium:ligand stoichiometry contains an octanuclear anionic cage of D 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.
顺式-1,2-环己烷二甲酸（c-chdcH）在存在不同可能抗衡离子的条件下，与硝酸铀酰在（溶剂）热条件下反应。得到了两个化学计量比为 1:1 的中性配合物，[UO( c-chdc)(DMF)]（1）和[UO( c-chdc)(HO)]（2），它们结晶为二维配位聚合物，不包括溶液中存在的额外阳离子。相比之下，在 PPhBr 存在下，[NH][PPh][(UO)( c-chdc)(HO)]·3HO（3）结晶，铵阳离子是由乙腈水解原位生成的。该配合物的铀：配体化学计量比为 8:9，包含一个具有 D 对称性的八核阴离子笼，铀原子呈伪立方排列。铵阳离子通过与指向内部的铀酰氧的四个氢键固定在笼内。这个笼状配合物具有发光性，尽管量子产率低至 0.06，表明作为包含物的光氧化剂的潜力有限。
