Aliphatic dicarboxylate copper coordination polymers with 3-pyridylmethylnicotinamide: Effect of chain length and steric bulk on dimensionality

作者：Salgado Maria D Torres; LaDuca Robert L^*

来源：Inorganica Chimica Acta, 2014, 423: 477-488.

DOI：10.1016/j.ica.2014.08.059

• Copper
• Dicarboxylate
• Crystal structure
• Coordination polymer
• Antiferromagnetism

Hydrothermal reaction of divalent copper salts, aliphatic dicarboxylic acids, and 3-pyridylmethylnicotinamide (3-pmna) has afforded a series of coordination polymer solids that were characterized via single-crystal X-ray crystallography. A significant dependence of the dimensionality and topology of these materials on the part of aliphatic chain length and substituent was revealed. Both [Cu-2(suc)(2)(3-pmna)](n) (1, suc = succinate) and its substituted congener {[Cu-2(dms)(2)(3-pmna)]center dot 4H(2)O}(n) (2, dms = 2,2-dimethyl-succinate) manifest {Cu-2(OCO)(4)} paddlewheel dimers, connected into chain motifs that are further linked by 3-pmna ligands into 2-D (4,4) grid networks. The enhanced steric bulk of the dms ligands in 2 impart larger interlamellar regions occupied by disordered water molecules. {[Cu-2(glu)(2)(3-pmna)]center dot H2O}(n) (3, glu = glutarate) has similar dimer-containing [Cu-2(glu)(2)](n) chain motifs, but retains a 1-D dimensionality due to bridging by syn-conformation 3-pmna ligands. [Cu(2-mglu)(3-pmna)] n (4, 2-mglu = 2-methylglutarate) features anti-syn {CuOCO}(n) chain patterns and a 3,5-connected (3.5(2))(3(2)5(3)6(4)7) 2-D topology. {[Cu-2(adp)(2)(3-pmna)(2)]center dot H2O}(n) (5, adp = adipate) exhibits 2-D [Cu-2(adp)(2)] n layers, linked by anti-conformation 3-pmna ligands into a very rare 3-D 3,5-connected hms net with (6(3))(6(9)8) topology. A minor 1-D chain product {[Cu-2(adp)(2)(3-pmna)]center dot 0.25H(2)O}(n) (6) was also isolated at higher temperature. Variable temperature magnetic susceptibility data for 5 indicates the presence of very weak antiferromagnetic coupling along its anti-syn bridged {CuOCO}(n) chains. Thermal properties of these new materials are also investigated.

• 出版日期2014-11-1