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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 27, Number 11
BKCSDE 27(11)
November 20, 2006 

Lanthanide-Oxalate Coordination Polymers Formed by Reductive Coupling of Carbon Dioxide to Oxalate: [Ln2(3,5-pdc)2(C2O4)(H2O)4]·2H2O (Ln = Eu, Sm, Ho, Dy; pdc = Pyridinedicarbox
Hyun Sue Huh, Soon W. Lee*
Lanthanide, Oxalate formation, Hydrothermal reaction, X-ray diffraction
Hydrothermal reactions of Ln(NO3)3·5H2O (Ln = Eu (1), Sm (2), Ho (3), Dy (4)) with 3,5-pyridinedicarboxylic acid (3,5-pdcH2) in the presence of 4,4'-bipyridine led to the formation of the 3-D Ln(III)-coordination polymers with a formula unit of [Ln2(3,5-pdc)2(C2O4)(H2O)4]·2H2O. These polymers contain a bridging oxalate ligand (C2O42-). On the basis of GC-MS study of the mother liquor remaining after the reaction, we proposed that the C2O42- formation proceeds in three steps: (1) Ln(III)-mediated decarboxylation of 3,5-pdcH2 to give CO2, (2) the reduction of CO2 to CO2·- by the Ln(II) species, and (3) the reductive coupling of the two CO2·- radicals to the oxalate (C2O42-) ion. All polymers were structurally characterized by X-ray diffraction.
1839 - 1843
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