Uranyl Ion Complexes with Chiral Malic and Citramalic, and Prochiral Citric and Tricarballylic Acids: Influence of Coligands and Additional Metal Cations

Pierre Thuéry 1, * Jack Harrowfield 2, *
* Auteur correspondant
1 LCMCE - Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF)
NIMBE UMR 3685 - Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M)
Abstract : Seven homo-or heterometallic uranyl ion complexes with R,S-malic (H$_3$ml), R-citramalic (H$_3$cml), citric (H$_4$cit) and tricarballylic (H$_3$tca) acids were obtained under (solvo-)hydrothermal conditions and characterized by their crystal structure and, for five of them, their uranyl emission spectrum. All the malate, citramalate and citrate complexes contain the frequently observed 2:2 dimeric uranyl subunit in which the alkoxide group is bridging, these subunits being generally assembled into one-dimensional (1D) polymeric chains by bridging carboxylate groups. [(UO$_2$)$_4$(ml)$_2$(C$_2$O$_4$)(NMP)$_4$] (1) and [(UO$_2$)$_2$Cu$_2$(ml)$_2$(C$_2$O$_4$)(phen)$_2$] (2), which contain oxalate anions formed in situ, crystallize as two-dimensional (2D) networks, the increase in dimensionality being provided by uranyl or copper oxalate bridges. [(UO$_2$)$_2$Ni(cml)$_2$(cyclam)] (3) is also a 2D species, while [(UO$_2$)$_2$Cd(cml)$_2$(bipy)(H$_2$)$_2$] (4) crystallizes as a three-dimensional (3D) framework (even if Cd$^{II}$ cations are disregarded). [(UO$_2$)$_2$Zn(Hcit)$_2$(bipy)$_2$(H$_2$O)] (5) is a 1D polymer with decorating Zn(bipy)$_2$(H$_2$O)$^{2+}$ groups, while [(UO$_2$)$_2$Cd(Hcit)$_2$(bipy)$_2$] (6) is a 2D network. [(UO$_2$)$_2$Pb(tca)$_2$(H$_2$O)$_4$] (7), in which the three carboxylate groups are chelating and two of them further bridging, is a 3D framework. The uranyl emission spectra of complexes 3–6 are in agreement with a previously described trend, the largest blue-shift being found for the eight-coordinate complex 7.
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European Journal of Inorganic Chemistry, Wiley-VCH Verlag, 2017, 〈http://onlinelibrary.wiley.com/doi/10.1002/ejic.201701406/full〉
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Pierre Thuéry, Jack Harrowfield. Uranyl Ion Complexes with Chiral Malic and Citramalic, and Prochiral Citric and Tricarballylic Acids: Influence of Coligands and Additional Metal Cations. European Journal of Inorganic Chemistry, Wiley-VCH Verlag, 2017, 〈http://onlinelibrary.wiley.com/doi/10.1002/ejic.201701406/full〉. 〈cea-01671219〉

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