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Cavity Formation in Uranyl Ion Complexes with Kemp's Tricarboxylate: Grooved Diperiodic Nets and Polynuclear Cages

Pierre Thuéry 1 Jack Harrowfield 2
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 : Kemp’s triacid (cis,cis-1,3,5-trimethylcyclohexane-1,3,5-tricarboxylic acid, H$_3$kta) has been reacted with uranyl nitrate under solvo-hydrothermal conditions in the presence of diverse counterions or additional metal cations to give eight zero- or diperiodic complexes. All the coordination polymers in the series, [PPh$_3$Me][UO$_2$(kta)]$\cdot$0.5H$_2$O (1), [PPh$_4$][UO$_2$(kta)] (2), [C(NH$_2$)$_3$][UO$_2$(kta)] (3), [Cd(bipy)$_3$][UO$_2$(kta)]$_2$ (4), and [Zn(phen)$_3$][UO$_2$(kta)]$_2$$\cdot$2H$_2$O (5) (bipy = 2,2ʹ-bipyridine, phen = 1,10-phenanthroline) crystallize as networks with the hcb topology, the ligand being in the chair conformation with the three carboxylate groups equatorial, except in 3 in which the axial/diequatorial boat conformation is present. Various degrees of corrugation and different arrangements of neighbouring layers are observed depending on the counterion, with complexes 4 and 5 in particular displaying cavities containing the bulky cations. [Co(en)$_3$]$_2$[(UO$_2$)$_2$(kta)(Hkta)$_2$]$_2$$\cdot$2NMP$\cdot$10H$_2$O (6) (en = 1,2-ethanediamine) contains a metallatricyclic, tetranuclear anionic species, displaying two clefts in which the cations are held by extensive hydrogen bonding, and with the ligands in both triaxial chair and axial/diequatorial boat conformations. [(UO$_2$)$_3$Pb(kta)$_2$(Hkta)(H$_2$O)]$_2$$\cdot$1.5THF (7) and [(UO$_2$)$_2$Pb$_2$(kta)$_2$(Hkta)(NMP)]$_2$ (8) are two heterometallic cage compounds containing only the convergent, triaxial chair form of the ligand, which have the same topology in spite of the different U/Pb ratio. These complexes are compared to previous ones also involving Kemp’s triacid anions, and the roles of ligand conformation and of counterions in the formation of cavities, either in cage-like species or as grooves in diperiodic networks, is discussed.
Keywords : Kemp's triacid
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Submitted on : Monday, January 25, 2021 - 10:49:35 AM
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Pierre Thuéry, Jack Harrowfield. Cavity Formation in Uranyl Ion Complexes with Kemp's Tricarboxylate: Grooved Diperiodic Nets and Polynuclear Cages. Inorganic Chemistry, American Chemical Society, 2021, 60, pp.1683-1697. ⟨10.1021/acs.inorgchem.0c03205⟩. ⟨cea-03112974⟩

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