Cobalt phenylenediacetate coordination polymers containing long-spanning dipyridyl ligands: rectangular grid, primitive cubic, and 5-connected Archimedean layered net topologies

Abstract

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.

Crystal structure of poly[aqua(μ2-2,5-bis(4-pyridyl)-1,3,4-oxadiazole-κ2 N,N)(μ2-1,3-phenylenediacetato-κ3 O,O′:O′′)cobalt(II)], C22H18CoN4O6

“…It is well known that exible multicarboxylate acids, such as o-phenylenediacetic acid (H 2 phda) [6][7][8][9], are widely used to link metals to produce MOFs. On the other hand, exobidentate rodlike N,N′-donor ligands can have signi cant in uence on the assembly systems of multicarboxylate ligands and metal centers.…”

Luminescent cadmium phenylenedipropionate coordination polymers with long-spanning dipyridine ligands

“…A recently published family of divalent cobalt coordination polymers with phda and long-spanning bis(4-pyridylmethyl)piperazine (bpmp, Scheme 1) ligands reveals an important topological dependence imparted by the carboxylate pendant arm disposition [15]. {[Co(1,4-phda)(4-bpmp)(H 2 O) 2 ]Á2H 2 O} n exhibits a very common 4-connected 2-D grid topology, while its ortho-acetate analog {[Co(1,2-phda)(4-bpmp) 1.5 (H 2 O)](H 2 4-bpmp) 0.5 (ClO 4 )Á12H 2 O} n possesses a unique 5-connected layered framework with an Archimedean topology based on rectangular and triangular circuits.…”

“…Expansion of the scope of coordination polymer topologies has been made possible by the use of more conformationally flexible phenylenediacetate (phda) ligands [12][13][14][15][16]. A recently published family of divalent cobalt coordination polymers with phda and long-spanning bis(4-pyridylmethyl)piperazine (bpmp, Scheme 1) ligands reveals an important topological dependence imparted by the carboxylate pendant arm disposition [15].…”

Structure and properties of cobalt ortho-phenylenediacetate coordination polymers with rigid dipyridyl ligands

“…The increased conformational flexibility of the pendant acetate arms of the isomeric phda ligands can result in variable carboxylate binding modes, providing access to various coordination polymer topologies. Utilizing the long-spanning bis(4-pyridylmethyl)piperazine (4-bpmp) as a neutral co-ligand, a series of cobalt phda coordination polymers were recently prepared in our laboratory [24]. {[Co(pphda)(4-bpmp)(H 2 O) 2 ]Á2H 2 O} n (pphda = para-phenylenediacetate) has a standard (4,4) rhomboid grid topology, while [Co(mphda)(4-bpmp)] n (mphda = meta-phenylenediacetate) possesses dinuclear {Co 2 (OCO) 2 } units linked into a 6-connected primitive cubic topology.…”

“…In comparison to benzenedicarboxylates, phenylenediacetate ligands (phda) have seen more infrequent use to date in this chemistry [19][20][21][22][23][24]. The increased conformational flexibility of the pendant acetate arms of the isomeric phda ligands can result in variable carboxylate binding modes, providing access to various coordination polymer topologies.…”