Flexible Aliphatic Diammonioacetates as Zwitterionic Ligands in UO₂²⁺ Complexes: Diverse Topologies and...

N,N,N',N'-Tetramethylethane-1,2-diammonioacetate (L1) and N,N,N',N'-tetramethylpropane-1,3-diammonioacetate (L2) are two flexible zwitterionic dicarboxylates which have been used as ligands for the uranyl ion, 12 complexes having been obtained from their coupling to diverse anions, mostly anionic polycarboxylates, or oxo, hydroxo and chlorido donors. The protonated zwitterion is a simple counterion in [H₂L1][UO₂(2,6-pydc)₂] (1), where 2,6-pydc^2- is 2,6-pyridinedicarboxylate, but it is deprotonated and coordinated in all the other complexes. [(UO₂)₂(L2)(2,4-pydcH)₄] (2), where 2,4-pydc^2- is 2,4-pyridinedicarboxylate, is a discrete, binuclear complex due to the terminal nature of the partially deprotonated anionic ligands. [(UO₂)₂(L1)(ipht)₂]·4H₂O (3) and [(UO₂)₂(L1)(pda)₂] (4), where ipht^2- and pda^2- are isophthalate and 1,4-phenylenediacetate, are monoperiodic coordination polymers in which central L1 bridges connect two lateral strands. Oxalate anions (ox^2-) generated in situ give [(UO₂)₂(L1)(ox)₂] (5) a diperiodic network with the hcb topology. [(UO₂)₂(L2)(ipht)₂]·H₂O (6) differs from 3 in being a diperiodic network with the V₂O₅ topological type. [(UO₂)₂(L1)(2,5-pydc)₂]·4H₂O (7), where 2,5-pydc^2- is 2,5-pyridinedicarboxylate, is a hcb network with a square-wave profile, while [(UO₂)₂(L1)(dnhpa)₂] (8), where dnhpa^2- is 3,5-dinitro-2-hydroxyphenoxyacetate, formed in situ from 1,2-phenylenedioxydiacetic acid, has the same topology but a strongly corrugated shape leading to interdigitation of layers. (2R,3R,4S,5S)-Tetrahydrofurantetracarboxylic acid (thftcH₄) is only partially deprotonated in [(UO₂)₃(L1)(thftcH)₂(H₂O)] (9), which crystallizes as a diperiodic polymer with the fes topology. [(UO₂)₂Cl₂(L1)₃][(UO₂Cl₃)₂(L1)] (10) is an ionic compound in which discrete, binuclear anions cross the cells of the cationic hcb network. 2,5-Thiophenediacetate (tdc^2-) is peculiar in promoting self-sorting of the ligands in the ionic complex [(UO₂)₅(L1)₇(tdc)(H₂O)][(UO₂)₂(tdc)₃]₄·CH₃CN·12H₂O (11), which is the first example of heterointerpenetration in uranyl chemistry, involving a triperiodic, cationic framework and diperiodic, anionic hcb networks. Finally, [(UO₂)₇(O)₃(OH)_4.3Cl_2.7(L2)₂]Cl·7H₂O (12) crystallizes as a 2-fold interpenetrated, triperiodic framework in which chlorouranate undulating monoperiodic subunits are bridged by the L2 ligands. Complexes 1, 2, 3, and 7 are emissive with photoluminescence quantum yields in the range of 8-24%, and their solid-state emission spectra show the usual dependence on number and nature of donor atoms.