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CrystEngComm

Design and understanding of solid-state and crystalline materials




Paper

CrystEngComm, 2009, 11, 777 - 783, DOI: 10.1039/b815916e


Dicarboxylate anion-dependent assembly of Ni(II) coordination polymers with 4,4-dipyridyl sulfide

Lu-Fang Ma, Li-Ya Wang, Jiang-Liang Hu, Yao-Yu Wang, Stuart R. Batten and Jian-Ge Wang


Four new coordination polymers, [Ni(isop)(bps)(H2O)]2n·5H2O (1), [Ni(O2N–BDC)(bps)(H2O)]2n (2), [Ni(OH–BDC)(bps)2(H2O)]n (3) and {[Ni2(H2O)(tbip)2(bps)2]}n (4) (bps = 4,4-dipyridyl sulfide, H2isop= isophthalic acid, O2N–BDC = 5-nitroisophthalic acid, OH–BDC = 5-hydroxyisophthalic acid, H2tbip = 5-tert-butyl isophthalic acid), have been isolated from parallel hydrothermal reactions of Ni(OAc)2·4H2O and bps with isop, O2N–BDC, OH–BDC and H2tbip, respectively.Compound 1 is an unusual 2D double layered supramolecular motif generated by hydrogen bonding interactions of two single 2D (4,4) networks. Compound 2 has a highly puckered 2D (4,4) sheet and further stack via OO intermolecular contacts to form a 3D supramolecular structure.Compound 3 features a 2D rectangular grid layer with terminal bps ligands projecting into the interlayer space, leading to a highly interdigitated packing motif and further expansion to generate a 3-D network through interlayer C–H stacking interactions. Compound 4 contains [Ni2(H2O)]4+ dimers bridged by pairs of ligands into a single 3D diamond network with alternately left-handed and right-handed helical channels. As compared to isop, the coexistence of electron-donating (–OH, –C(CH3)3) or electron-withdrawing (–NO2) groups in the dicarboxylate derivatives has a significant effect on the molecular self-assembly. Variable-temperature magnetic susceptibility measurements reveals the existence of weak ferromagnetic interactions between the nickel centers in 4.

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