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) ( p L1), 1,1'-[(2,3,5,6-tetramethylbenzene-1,4-diyl)bis(methylene)]bis(pyridin-1-ium-3-carboxylate) ( m 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 2 ) 2 ( p L1) 2 (cbtc)(H 2 O) 2 ]·10H 2 O ( 1 , cbtc 4- = cis , trans , cis- 1,2,3,4-cyclobutanetetracarboxylate) is a discrete, dinuclear ring-shaped complex with a central cbtc 4- pillar. While [UO 2 ( p L1)(NO 3 ) 2 ] ( 2 ), [UO 2 ( p L1)(OAc) 2 ] ( 3 ), and [UO 2 ( p L1)(HCOO) 2 ] ( 4 ) are simple chains, [(UO 2 ) 2 ( m L1)(1,3-pda) 2 ] ( 5 , 1,3-pda 2- = 1,3-phenylenediacetate) is a daisy chain and [UO 2 ( p L1)(pdda)] 3 ·10H 2 O ( 6 , pdda 2- = 1,2-phenylenedioxydiacetate) is a double-stranded, ribbon-like chain. Both [UO 2 ( p L1)(pht)]·5H 2 O ( 7 , pht 2- = phthalate) and [(UO 2 ) 3 ( m L1)(pht) 2 (OH) 2 ] ( 8 ) crystallize as diperiodic networks with the sql topology, the latter involving hydroxo-bridged trinuclear nodes. [(UO 2 ) 2 ( p L1)( c / t -1,3-chdc) 2 ] ( 9 , c / t -1,3-chdc 2- = cis / trans -1,3-cyclohexanedicarboxylate) and [UO 2 ( p L1)( t -1,4-chdc)]·1.5H 2 O ( 10 , t -1,4-chdc 2- = trans -1,4-cyclohexanedicarboxylate) are also diperiodic, with the V 2 O 5 and sql topologies, respectively. Both [(UO 2 ) 2 ( m L1)( c / t -1,4-chdc) 2 ] ( 11 ) and [(UO 2 ) 2 ( p L1)(1,2-pda) 2 ] ( 12 , 1,2-pda 2- = 1,2-phenylenediacetate) crystallize as diperiodic networks with hcb topology, and they display threefold parallel interpenetration. [HL2][(UO 2 ) 3 (L2)(adc) 3 ]Br ( 13 , adc 2- = 1,3-adamantanedicarboxylate) contains a very corrugated hcb 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 2 ) 2 ( p L1)(kpim) 2 ] ( 14 , kpim 2- = 4-ketopimelate) is a three-periodic framework with p L1 molecules pillaring fes diperiodic subunits, whereas [(UO 2 ) 2 (L2) 2 ( t -1,4-chdc)](NO 3 ) 1.7 Br 0.3 ·6H 2 O ( 15 ), the only cationic complex in the series, is a triperiodic framework with dmc topology and t -1,4-chdc 2- anions pillaring fes diperiodic subunits. Solid-state emission spectra and photoluminescence quantum yields are reported for all complexes.