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

Kemp's triacid (cis,cis-1,3,5-trimethylcyclohexane-1,3,5-tricarboxylic acid, H₃kta) was 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, [PPh₃Me][UO₂(kta)]·0.5H₂O (1), [PPh₄][UO₂(kta)] (2), [C(NH₂)₃][UO₂(kta)] (3), [Cd(bipy)₃][UO₂(kta)]₂ (4), and [Zn(phen)₃][UO₂(kta)]₂·2H₂O (5) (bipy = 2,2'-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 neighboring layers are observed depending on the counterion, with complexes 4 and 5, in particular, displaying cavities containing the bulky cations. [Co(en)₃]₂[(UO₂)₂(kta)(Hkta)₂]₂·2NMP·10H₂O (6) (en = 1,2-ethanediamine; NMP = N-methyl-2-pyrrolidone) 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. [(UO₂)₃Pb(kta)₂(Hkta)(H₂O)]₂·1.5THF (7) (THF = tetrahydrofuran) and [(UO₂)₂Pb₂(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.