Crown Ethers and Their Alkali Metal Ion Complexes as Assembler Groups in Uranyl–Organic Coordination Polymers with cis -1,3-, cis -1,2-, and trans -1,2-Cyclohexanedicarboxylates

Abstract : Alkali metal cations (Na$^+$, K$^+$) and crown ether molecules (12C4, 15C5, 18C6) were used as additional reactants during the hydrothermal synthesis of uranyl ion complexes with cis/trans-1,3-, cis-1,2- and trans-1,2-cyclohexanedicarboxylic acids ($c/t$-1,3-chdcH$_2$, c-1,2-chdcH$_2$, and t-1,2-chdcH$_2$, respectively, the latter as racemic or pure (1R,2R) enantiomer). Oxalate anions generated in situ are present in all the six complexes isolated and crystallographically characterized, [(UO$_2$)$_2$(c-1,3-chdc)$_2$(C$_2$O$_4$)][UO$_2$(H$_2$O)$_5$]·(12C4)·2H$_2$O (1), [(UO$_2$)$_4$Na$_2$(c-1,2-chdc)$_2$(C$_2$O$_4$)$_3$(15C5)$_2$] (2), [(UO$_2$)$_4$K$_2$(c-1,2-chdc)$_2$(C$_2$O$_4$)$_3$(18C6)$_{1.5}$(H$_2$O)$_{1.5}$] (3), [(UO$_2$)$_{12}$K$_5$(R-t-1,2-chdc)$_4$(C$_2$O$_4$)$_{10}$(18C6)$_5$(OH)(H$_2$O)$_3$]·4H$_2$O (4), [(UO$_2$)$_{12}$K$_5$(rac-t-1,2-chdc)$_4$(C$_2$O$_4$)${10}$(18C6)$_5$(OH)(H$_2$O)$_3$]·4H$_2$O (5), and [(UO$_2$)$_8$K$_4$(rac-t-1,2-chdc)$_4$(C$_2$O$_4$)$_6$(18C6)$_3$(H$_2$O)$_2$] (6). In complex 1, the [UO$_2$(H$_2$O)$_5$]$_2$+ counterions link the ladderlike uranyl-containing one-dimensional polymers and the uncomplexed crown ether molecules through hydrogen bonds. In all the other complexes, two-dimensional uranyl/chdc/oxalate subunits are formed, with topologies depending on the stoichiometry, in which the 1,2-chdc$^{2–}$ ligands are bound to three uranium atoms, one of them chelated by the two carboxylate groups, and the oxalate ligands are bis-chelating. In complex 2, the Na(15C5)$^+$ cations are bound to one layer through double Na-carboxylate or Na-oxo cis-bonding and they are thus mere decorating groups. In contrast, the quasi-planar K(18C6)$^+$ groups in 3–6, partially affected by disorder, are generally trans-coordinated to two uranyl oxo groups pertaining to different layers, thus uniting the latter into a three-dimensional framework.
Type de document :
Article dans une revue
Crystal Growth and Design, American Chemical Society, In press, 18 (5), pp.3167-3177. 〈https://doi.org/10.1021/acs.cgd.8b00266〉. 〈10.1021/acs.cgd.8b00266〉
Liste complète des métadonnées

Littérature citée [60 références]  Voir  Masquer  Télécharger

https://hal-cea.archives-ouvertes.fr/cea-01759418
Contributeur : Serge Palacin <>
Soumis le : vendredi 6 avril 2018 - 08:28:57
Dernière modification le : mercredi 9 mai 2018 - 07:35:35

Fichier

CrownEther_Thuery2018_V0 (1).p...
Fichiers produits par l'(les) auteur(s)

Identifiants

Citation

Pierre Thuéry, Youssef Atoini, Jack Harrowfield. Crown Ethers and Their Alkali Metal Ion Complexes as Assembler Groups in Uranyl–Organic Coordination Polymers with cis -1,3-, cis -1,2-, and trans -1,2-Cyclohexanedicarboxylates. Crystal Growth and Design, American Chemical Society, In press, 18 (5), pp.3167-3177. 〈https://doi.org/10.1021/acs.cgd.8b00266〉. 〈10.1021/acs.cgd.8b00266〉. 〈cea-01759418〉

Partager

Métriques

Consultations de la notice

197

Téléchargements de fichiers

40