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

Pierre Thuéry 1, * Jack Harrowfield 2, *
* Corresponding author
1 LCMCE - Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF)
NIMBE UMR 3685 - Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M)
Abstract : 2-Carboxyphenylacetate (cpa 2 – ) and 1,2-phenylenediacetate (1,2-pda 2 – ) have been reacted with uranyl cations under solvo-hydrothermal conditions to generate six homo- or heterometallic complexes. Both [UO 2 (cpa)] ( 1 ) and [UO 2 (cpa)(phen)] ( 2 ), where phen is 1,10-phenanthroline, crystallize as monoperiodic coordination polymers. [Ni(bipy) 3 ][(UO 2 ) 2 (cpa) 3 ]×2.5H 2 O ( 3 ), is a diperiodic network with the hcb topology, in which the hexagonal cells distort to accommodate the counterions. [UO 2 (cpa) 2 Ni( R,S -Me 6 cyclam)] ( 4 ) crystallizes as a heterometallic diperiodic network, in which uranyl dicarboxylate chains are assembled by bridging Ni II cations. While [dmaepH 2 ][(UO 2 ) 2 (1,2-pda) 3 ]×3H 2 O ( 5 ), where dmaep is 1,4-bis(2ʹ-dimethylaminoethyl)piperazine, is a diperiodic hcb network, [QH] 2 [(UO 2 ) 2 (1,2-pda) 3 ]×3CH 3 CN ( 6 ), where Q is quinuclidine, is the first example of a triperiodic framework in the uranyl–phenylenediacetate family, its topological type being bto . The complex involving the related ligand 1,4-phenylenediacetate (1,4-pda 2 – ), [QH] 2 [(UO 2 ) 2 (1,4-pda) 3 ]×2CH 3 CN ( 7 ), is a daisy-chain-like monoperiodic polymer. These and previously reported results are discussed in terms of ligand flexibility and ability to form large chelate rings.
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Pierre Thuéry, Jack Harrowfield. Stepwise Introduction of Flexibility into Aromatic Dicarboxylates Forming Uranyl Ion Coordination Polymers: a Comparison of 2-Carboxyphenylacetate and 1,2-Phenylenediacetate. European Journal of Inorganic Chemistry, Wiley-VCH Verlag, 2021, 2021 (22), pp.2182-2192. ⟨10.1002/ejic.202100203⟩. ⟨cea-03203794⟩

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