Divalent cobalt coordination polymers containing both phenylenediacetate (phda) and bis(4-pyridylmethyl)piperazine (4-bpmp) ligands display differing dimensionalities and topologies. The para-substituted 1,4-phda ligand afforded {[Co(1,4-phda)(4-bpmp)(H 2 O) 2 ]$2H 2 O} n (1), a layered phase with standard (4,4) rhomboid grid topology. Use of the meta-substituted 1,3-phda ligand generated [Co(1,3-phda)(4-bpmp)] n (2), which has [Co(1,3-phda)] n layers pillared by pairs of 4-bpmp ligands into a three-dimensional (3D) coordination polymer with primitive cubic topology. Antiferromagnetically coupled {Co 2 (CO 2 ) 2 } dinuclear units (J ¼ À2.04(4) cm À1 ) are embedded within the structure of 2. The ortho-substituted derivative {[Co(1,2-phda)(4-bpmp) 1.5 (H 2 O)](H 2 4bpmp) 0.5 (ClO 4 )$12H 2 O} n (3) manifests an intriguing layered structure with 5-connected cobalt atom nodes and an Archimedean 3 3 4 4 5 3 cem topology with triangular and rectangular circuits.
Hydrothermal reaction of zinc nitrate, pyromellitic acid (H4pyro), and isomeric bis(pyridylmethyl)piperazines has afforded a pair of three-dimensional (3D) coordination polymers with intriguing 3D topologies. {[Zn2(Hpyro)2(H2O)2(H2-3-bpmp)]·H2O}
n
[1, 3-bpmp = bis(3-pyridylmethyl)piperazine] exhibits octahedral coordination at zinc and possesses a rare 4,5-connected binodal net with (4462)(4466) tcs topology. {[Zn2(Hpyro)2(H2-4-bpmp)]·4H2O}
n
[2, 4-bpmp = bis(4-pyridylmethyl)piperazine] has tetrahedral coordination at zinc and an unprecedented yet very simple 3,4-connected binodal (4.82)(4.82103) self-penetrated topology. Pyridyl nitrogen donor disposition and coordination geometry preference play a large role in structure-direction in this system. Complexes 1 and 2 undergo blue-violet light emission on excitation with ultraviolet light.
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