Stepwise Introduction of Flexibility into Aromatic Dicarboxylates Forming Uranyl Ion Coordination Polymers: a Comparison of 2?Carboxyphenylacetate and 1,2?Phenylenediacetate

2-Carboxyphenylacetate (cpa2?) and 1,2-phenylenediacetate (1,2-pda2?) have been reacted with uranyl cations under solvo-hydrothermal conditions to generate six homo- or heterometallic complexes. Both [UO2(cpa)] (1) [UO2(cpa)(phen)] (2), where phen is 1,10-phenanthroline, crystallize as monoperiodic coordination polymers. [Ni(bipy)3][(UO2)2(cpa)3]?2.5H2O (3), a diperiodic network the hcb topology, in which hexagonal cells distort accommodate counterions. [UO2(cpa)2Ni(R,S-Me6cyclam)] (4) crystallizes dicarboxylate chains are assembled by bridging NiII cations. While [dmaepH2][(UO2)2(1,2-pda)3]?3H2O (5), dmaep 1,4-bis(2?-dimethylaminoethyl)piperazine, network, [QH]2[(UO2)2(1,2-pda)3]?3CH3CN (6), Q quinuclidine, first example of triperiodic framework uranyl–phenylenediacetate family, its topological type being bto. The complex involving related ligand 1,4-phenylenediacetate (1,4-pda2–), [QH]2[(UO2)2(1,4-pda)3]?2CH3CN (7), daisy-chain-like polymer. These previously reported results discussed terms flexibility ability form large chelate rings.