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.

Hydrothermal synthesis has afforded a family of divalent metal adipate (adp) coordination polymers incorporating the kinked dipodal organodiimine 4,4'-dipyridylamine (dpa). As revealed by single-crystal X-ray diffraction, the structures of these materials are critically dependent on the metal coordination geometry, the carboxylate binding modes, and the conformations of the flexible adipate moieties. In all cases, hydrogen-bonding interactions imparted by the dpa tethers also play a structure-directing role. All materials were further characterized via infrared spectroscopy and elemental and thermogravimetric analysis. [Co(adp)(dpa)] (1) displays doubly interpenetrated three-dimensional (3-D) networks with a decorated alpha-Po-type (pcu) topology. In contrast, [Ni(adp)(dpa)(H2O)] (2) possesses a triply interpenetrated binodal cooperite-type (pts) framework, the highest level of interpenetration yet reported for this structure type. [Zn(adp)(dpa)].H2O (3) presents mutually inclined polycatenated 2-D graphitic layers consisting of neutral dimeric [Zn2(mu2-adp)2] kernels conjoined by dipodal dpa ligands. Compound 1 exhibited weak antiferromagnetic coupling between its carboxylate-bridged Co atoms, following Curie-Weiss behavior with Theta=-3.3 K. Compound 3 manifested blue light emission under ultraviolet excitation, as well as a reversible structural reorganization upon dehydration/rehydration.

Two cadmium glutarate coordination polymers incorporating the hydrogen-bonding capable tethering organodiimines 4,4′-dipyridylamine (dpa) or bis(4-pyridylmethyl)piperazine (bpmp) have been prepared and structurally characterized. [Cd(glutarate)(dpa)] n (1) manifests a doubly interpenetrated decorated R-Po (pcu, 4 12 6 3 topology) lattice, with octahedral coordination at cadmium. Compound 1 undergoes blue-violet luminescence upon UV irradiation. Use of the longer tethering organodiimine resulted in the formation of {[Cd(glutarate)(bpmp)(H 2 O)] • 6H 2 O} n (2), which displays non-interpenetrated (4,4)-rhomboid grid coordination polymer layers. In contrast to 1, the cadmium ions in 2 adopt a pentagonal bipyramidal coordination geometry, with aqua ligands allowing construction of a hexagonal boron nitride (bnn, 4 4 6 6 topology) supramolecular framework through interlayer hydrogen bonding. Unprecedented one-dimensional water molecule tapes with 2T5(2)7(2) classification occupy large ellipsoid channels coursing through the structure of 2, stabilizing the coordination polymer framework through hydrogen bonding. Upon partial dehydration the structure of 2 degrades irreversibly.

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