Zwitterionic and Anionic Polycarboxylates as Coligands in Uranyl Ion Complexes, and Their Influence on Periodicity and Topology.

The three zwitterionic di- and tricarboxylate ligands 1,1'-[(2,3,5,6-tetramethylbenzene-1,4-diyl)bis(methylene)]bis(pyridin-1-ium-4-carboxylate) (L1), 1,1'-[(2,3,5,6-tetramethylbenzene-1,4-diyl)bis(methylene)]bis(pyridin-1-ium-3-carboxylate) (L1), and 1,1',1″-[(2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene)]tris(pyridin-1-ium-4-carboxylate) (L2) have been used as ligands to synthesize a series of 15 uranyl ion complexes involving various anionic coligands, in most cases polycarboxylates. [(UO)(L1)(cbtc)(HO)]·10HO (, cbtc = ,,1,2,3,4-cyclobutanetetracarboxylate) is a discrete, dinuclear ring-shaped complex with a central cbtc pillar. While [UO(L1)(NO)] (), [UO(L1)(OAc)] (), and [UO(L1)(HCOO)] () are simple chains, [(UO)(L1)(1,3-pda)] (, 1,3-pda = 1,3-phenylenediacetate) is a daisy chain and [UO(L1)(pdda)]·10HO (, pdda = 1,2-phenylenedioxydiacetate) is a double-stranded, ribbon-like chain. Both [UO(L1)(pht)]·5HO (, pht = phthalate) and [(UO)(L1)(pht)(OH)] () crystallize as diperiodic networks with the topology, the latter involving hydroxo-bridged trinuclear nodes. [(UO)(L1)(/-1,3-chdc)] (, /-1,3-chdc = /-1,3-cyclohexanedicarboxylate) and [UO(L1)(-1,4-chdc)]·1.5HO (, -1,4-chdc = -1,4-cyclohexanedicarboxylate) are also diperiodic, with the VO and topologies, respectively. Both [(UO)(L1)(/-1,4-chdc)] () and [(UO)(L1)(1,2-pda)] (, 1,2-pda = 1,2-phenylenediacetate) crystallize as diperiodic networks with topology, and they display threefold parallel interpenetration. [HL2][(UO)(L2)(adc)]Br (, adc = 1,3-adamantanedicarboxylate) contains a very corrugated network with two different kinds of cells, and the uncoordinated HL2 molecule associates with the coordinated L2 to form a capsule containing the bromide anion. [(UO)(L1)(kpim)] (, kpim = 4-ketopimelate) is a three-periodic framework with L1 molecules pillaring diperiodic subunits, whereas (UO)(L2)(-1,4-chdc)Br·6HO (), the only cationic complex in the series, is a triperiodic framework with topology and -1,4-chdc anions pillaring diperiodic subunits. Solid-state emission spectra and photoluminescence quantum yields are reported for all complexes.