Effect of metal coordination environment on topology of coordination polymers containing 2,5-thiophenedicarboxylate and long-spanning dipyridine ligands

2014 
Abstract Hydrothermal reaction of a metal nitrate, 2,5-thiophenedicarboxylic acid (H 2 tpdc), and bis(4-pyridylmethyl)piperazine (4-bpmp) afforded a series of crystalline coordination polymers with different dimensionality and topology depending on the metal coordination geometry. These materials were characterized by single-crystal X-ray diffraction. [Cu(tpdc)(4-bpmp)(H 2 O)] n ( 1 ), with square pyramidal coordination, shows parallel stacked (4,4) grid motifs. {[Co(tpdc)(4-bpmp) 1.5 (H 2 O) 2 ]·4H 2 O} n ( 2 ) exhibits graphitic (6,3) honeycomb layer motifs and octahedral coordination at the metal. {[Cd(tpdc)(4-bpmp)(H 2 O)]·H 2 O} n ( 3 ) shows pentagonal bipyramidal geometry and manifests (4,4) grid layers as in 1 , but with 2D + 2D → 3D parallel entanglement. [Zn(tpdc)(4-bpmp)(H 2 O)] n ( 4 ), which has distorted “5 + 1” octahedral coordination at zinc, displays an acentric 6 6 3-D diamondoid topology. Luminescent properties of 3 and 4 are presented, along with thermal analyses.
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