Two- and three-dimensional lanthanide-organic frameworks constructed using 1-hydro-6-oxopyridine-3-carboxylate and oxalate ligands.
6-Hydroxypyridine-3-carboxylic acid (6-HOPy-3-CO(2)H) reacts with Ln(2)O(3) (Ln = Nd, Sm, Eu, Gd) and oxalic acid (H(2)OX) under hydrothermal conditions to generate four novel lanthanide-organic coordination polymeric networks [Ln(2)(1H-6-Opy-3-CO(2))(2)(OX)(2)(H(2)O)(3)] x 2.5 H(2)O (Ln = Nd, 1; Sm, 2; 1H-6-Opy-3-CO(2)(-) = 1-hydro-6-oxopyridine-3-carboxylate) and [Ln(1H-6-Opy-3-CO(2))(OX)(H(2)O)(2)] x H(2)O (Ln = Eu, 3; Gd, 4). The new co-ligand 1H-6-Opy-3-CO(2)(-) anion was generated by the autoisomerization of the single deprotonated 6-HOPy-3-CO(2)(-) anion (from the enol form into the ketone one). 1 and 2 are isomorphous, they possess a three-dimensional architecture constructed from Ln(3+) ions bridged by oxalate anions and two types of 1H-6-Opy-3-CO(2)(-) bridges, showing a three-nodal (4,5)-connected topology (3.4(2).5(2).6(3).7.8)(2)(3.5(3).6(2))(2)(3(2).6.7(2).8) or a simplified uninodal 6-connected topology (3(3).4(6).5(5).6), both topologies are completely new; while only one type of 1H-6-Opy-3-CO(2)(-) bridge is used to construct the two-dimensional layer networks of 3 and 4 besides oxalate bridges, both complexes 3 and 4 are isostructural, exhibiting the honeycomb topology 6(3). The lanthanide contraction effect is believed to play a key role in directing the formation of a particular structure. A magnetic study of 1-3 indicated that the coupling interaction between Ln(3+) ions is weak.
Liu
Cai-Ming
CM
Beijing National Laboratory for Molecular Sciences, Center for Molecular Science, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, PR China. cmliu@iccas.ac.cn
Xiong
Ming
M
Zhang
De-Qing
DQ
Du
Miao
M
Zhu
Dao-Ben
DB
D018360:Crystallography, X-Ray; D028581:Lanthanoid Series Elements / Q000737:chemistry*; D008024:Ligands; D008280:Magnetics; D008958:Models, Molecular; D009525:Niacin / Q000031:analogs & derivatives* / Q000737:chemistry; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010070:Oxalates / Q000737:chemistry*; D011728:Pyridones / Q000737:chemistry*
D028581:Lanthanoid Series Elements; D008024:Ligands; D009942:Organometallic Compounds; D010070:Oxalates; D011728:Pyridones; D009525:Niacin