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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
Author(s) -
Thuéry Pierre,
Harrowfield Jack
Publication year - 2021
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202100203
Subject(s) - uranyl , chemistry , crystallography , counterion , ligand (biochemistry) , hydrothermal synthesis , piperazine , crystal engineering , polymer , coordination polymer , stereochemistry , crystal structure , inorganic chemistry , hydrothermal circulation , ion , supramolecular chemistry , organic chemistry , biochemistry , receptor , seismology , geology
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(2′‐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.