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Issue 5, 2013
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Structural diversity directed by switchable coordination of substitute groups in a ternary CuII-triazole-sulfoisophthalate self-assembly system: synthesis, crystal structures and magnetic behavior

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Abstract

Four magnetic samples with different building blocks and dimensionalities, {[Cu4(atr)23-OH)2(sip)2]·4H2O}n (1), {[Cu4(atr)2(H2O)8(μ-OH)2(sip)2]·1.3CH3OH·0.7H2O}n (2), {[Cu3(atr)4(H2O)2(sip)2]·4H2O}n (3) and {[Cu3(atr)4(H2O)23-OH)(sip)(Hsip)]·2CH3OH·2.75H2O}n (4) (atr = 4-amino-1,2,4-triazole and sip3− = 5-sulfoisophthalate), were obtained and characterized structurally and magnetically. Complex 1 exhibits a three-dimensional (3D) robust framework with butterfly-like CuII4 clusters periodically extended by tetratopic sip3− connectors. Complex 2 possesses a 2D layer with alternating CuII3 + CuII1 chains crosslinked by pairs of ditopic sip3− linkers. By contrast, the latter two entities feature 1D broad ribbons with linear (for 3) and triangular CuII3 cores (for 4) propagated by bidirectional sip3− connectors. Structural analysis reveals that the diverse building blocks and dimensionalities of 1–4 are significantly dominated by the tunable coordination of exocyclic amino- and/or sulfonate-group of the mixed ligands. Magnetically, antiferromagnetic interactions with variable strength transmitted by –NN– moiety of atr and hydroxyl mediators result in overall S = 0 (for 1) and 1/2 (for 3 and 4) spin ground states. These interesting results indicate that coordinative side group in the ternary metal ion-azolate-carboxylate system can be utilized to generate aesthetically pleasing building units and variably polytopic connectors, leading to differently extended superstructures and magnetic behavior.

Graphical abstract: Structural diversity directed by switchable coordination of substitute groups in a ternary CuII-triazole-sulfoisophthalate self-assembly system: synthesis, crystal structures and magnetic behavior

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Publication details

The article was received on 24 Aug 2012, accepted on 25 Oct 2012 and first published on 25 Oct 2012


Article type: Paper
DOI: 10.1039/C2DT31935G
Citation: Dalton Trans., 2013,42, 1581-1590
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    Structural diversity directed by switchable coordination of substitute groups in a ternary CuII-triazole-sulfoisophthalate self-assembly system: synthesis, crystal structures and magnetic behavior

    E. Yang, Z. Liu, C. Zhang, Y. Yang and X. Zhao, Dalton Trans., 2013, 42, 1581
    DOI: 10.1039/C2DT31935G

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