Divalent Metal Succinate/4,4‘-Dipyridylamine Extended Solids:  From Helical Chains to Diverse Three-Dimensional Networks Featuring Double, Quadruple, or Self-Interpenetration

Abstract

Hydrothermal synthesis has afforded a family of five divalent metal succinate (suc) coordination polymers incorporating the kinked dipodal organodiimine 4,4′-dipyridylamine (dpa), which were structurally characterized by single-crystal X-ray diffraction and thermogravimetric analysis. [Co(suc)(dpa) 2 ] (1) manifests chiral helical one-dimensional (1-D) chains formed from the linkage of neighboring Co atoms through bischelating bisbridging succinate moieties, with pendant dpa ligands. {[Ni(dpa) 2 -(suc) 0.5 ]Cl} (2) possesses a rare self-interpenetrated 5-connected cationic framework with a unique 6 10 topology, constructed from the junction of quadruply interpenetrated adamantoid [Ni(dpa) 2 ] 2n+ networks via bischelating µ 2 -succinate ligands. {[Cu(suc)-(dpa)]‚0.5H 2 O} (3) exhibits a doubly interpenetrated CdSO 4 net (6 5 8 topology) containing both 1-D double braided cationic helical [Cu(dpa)] 2+ ribbons and orthogonally situated zigzag [Cu(suc)] chains. The quadruply interpenetrated three-dimensional (3-D) network structure (4 2 6 3 8 topology, SrAl 2 -type) of {[Zn(suc) 0.5/2 (dpa)]‚H 2 O} ( 4) is built from [Zn(suc) 0.5/2 ] chains interlocked with dpa tethers. {[Cd(suc)(dpa)]‚H 2 O} (5) displays doubly interpenetrated 6-connected R-Po networks based on {Cd 2 O 2 } dimers within [Cd(suc)] two-dimensional (2-D) layers, in turn pillared by dpa ligands. The coordination geometry about the metal atoms and the succinate binding modes and conformations in these compounds vary widely, playing a significant role in promoting the diversity of the observed structural motifs. Supramolecular hydrogen-bonding interactions through the dpa amine subunit are evident in all cases.

A Substituent Change Exerts a Large Dimensionality and Water Tetramer Morphology Difference in Luminescent Cadmium Succinate Coordination Polymers Containing 3‐Pyridylnicotinamide

“…[28] A decrease in dimensionality was observed, moving from the unsubstituted dicarboxylate in the 2D (4,4)-grid material [Zn 4 (H 2 O)(ip) 4 (py) 6 ] n to the sterically bulky 5-tert-butylisophthalate ligand (tbip) in the 1D single-stranded chain phase [Zn(tbip)(py) 2 ] n . A similar trend was seen in the related dpa-containing phases {[Cd(suc)(dpa)]·H 2 O} n [17] and [Cd(dmsuc)(dpa)] n (dmsuc = 2,2-dimethylsuccinate). [29] The former displays a twofold interpenetrated {Cd 2 O 2 } dimer-based 6-connected pcu framework, whereas the latter manifests an acentric system of twofold parallel interpenetrated (4,4) grid layers.…”

“…[16][17][18][19][20] The incorporation of dipyridyl coligands such as the rigidrod tether 4,4Ј-bipyridine (bpy) or its kinked amine derivative 4,4Ј-dipyridylamine (dpa) has broadened the scope of possible topologies in this genre of crystalline materials. For example, [Cd(Hpht) 2 (bpy)] n (pht = phthalate) has a self-penetrated 6-connected 3D network with 5 10 6 4 7 topology, [9] while {[Cd(phth)(dpa)(H 2 O)]·4H 2 O} n displays a unique chiral self-penetrated 4-connected 7 4 8 2 yyz topology.…”

Two new 1D coordination polymers: syntheses, structures and properties

“…However, flexible carboxylate and N-donor scaf-folded coordination polymers have received less attention. Even so, the prediction and synthesis of the solid-state architectures still remain a long-term challenge for the chemists [5][6][7][8][9][10].…”

Structure and magnetic properties of a copper malonate/dipyridylamine layered coordination polymer with both syn–anti and anti–anti copper carboxylate chains

“…Taking advantage of these characteristics, we have recently prepared several new phases containing both aliphatic dicarboxylates and dpa [17,18]. {[Ni(dpa) 2 (succinate) 0.5 ]Cl} [17] manifests a unique ''regular'' 6 10 topology 5-connected self-penetrated 3-D framework, while [Ni(adipate)(dpa)(H 2 O)] organizes into the first threefold interpenetrated PtS lattice [18].…”

“…Taking advantage of these characteristics, we have recently prepared several new phases containing both aliphatic dicarboxylates and dpa [17,18]. {[Ni(dpa) 2 (succinate) 0.5 ]Cl} [17] manifests a unique ''regular'' 6 10 topology 5-connected self-penetrated 3-D framework, while [Ni(adipate)(dpa)(H 2 O)] organizes into the first threefold interpenetrated PtS lattice [18]. In this communication we report the synthesis, structural characterization, and magnetic properties of the 2-D ''herringbone'' layered phase {[Cu 2 (mal) 2 (dpa)(H 2 O) 2 ] AE H 2 O} n (1), which represents a rare example of a coordination polymer containing both syn-anti and anti-anti copper carboxylate 1-D chains.…”