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Issue 41, 2011
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Manganese(II)-carboxylate-pseudohalide systems derived from 1,4-bis(4-carboxylatopyridinium-1-methylene)benzene: structures and magnetism

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Abstract

The reactions of manganese(II) acetate or perchlorate, sodium azide or sodium cyanate, and the zwitterionic dicarboxylate ligand 1,4-bis(4-carboxylatopyridinium-1-methylene)benzene (L) under different conditions yielded three different Mn(II) coordination polymers with mixed carboxylate and azide (or cyanate) bridges: {[Mn (L1)0.5(N3)(OAc)]·3H2O}n (1), {[Mn4(L1)(N3)8(H2O)4(CH3OH)2]·[L1]}n (2), and {[Mn3(L1)(NCO)6(H2O)4]·[L1]·[H2O]2}n (3). The compounds exhibit diverse structures and magnetic properties. In 1, the 1D uniform anionic [Mn(N3)(COO)2]n chains with the (μ-EO-N3)(μ-COO)2 triple bridges (EO = end-on) are interlinked by the dipyridinium L ligands into highly undulated 2D layers. Magnetic studies on 1 reveal that the mixed triple bridges induce antiferromagnetic coupling between Mn(II) ions. Compounds 2 and 3 consist of 1D neutral polymeric chains and co-crystallized zwitterions, and the chains are formed by the L ligands interlinking linear polynuclear units. The polynuclear unit in 2 is tetranuclear with (μ-EO-N3)2 as central bridges and (μ-EO-N3)2(μ-COO) as peripheral bridges, while that in 3 is trinuclear with (μ-NCO)2(μ-COO) bridges. Magnetic studies demonstrate that the magnetic coupling through the mixed azide/isocyanate and carboxylate bridges in 2 and 3 is antiferromagnetic. An expression of magnetic susceptibility based on a 2-J model for linear tetranuclear systems of classical spins has been deduced and applied to 2.

Graphical abstract: Manganese(ii)-carboxylate-pseudohalide systems derived from 1,4-bis(4-carboxylatopyridinium-1-methylene)benzene: structures and magnetism

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Publication details

The article was received on 25 May 2011, accepted on 08 Aug 2011 and first published on 14 Sep 2011


Article type: Paper
DOI: 10.1039/C1DT10977D
Citation: Dalton Trans., 2011,40, 10966-10974
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    Manganese(II)-carboxylate-pseudohalide systems derived from 1,4-bis(4-carboxylatopyridinium-1-methylene)benzene: structures and magnetism

    Y. Wang, Q. Sun, Q. Yue, A. Cheng, Y. Song and E. Gao, Dalton Trans., 2011, 40, 10966
    DOI: 10.1039/C1DT10977D

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