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Issue 18, 2014
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Variations in topology and magnetic properties of hepta- and octacyanometallates of molybdenum with manganese(ii)

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Abstract

Treatment of [Mn(dpop)(H2O)2]Cl2 (dpop = 2,13-dimethyl-3,6,9,12,18-pentaazabicyclo-[12.3.1]octadeca-1(18),2,12,14,16-pentaene) with K4[Mo(CN)7]·2H2O under varied synthetic conditions afforded four different compounds: {[Mn(dpop)]4[(dpop)Mn(H2O)]2[MoIII(CN)7]3·27H2O}n (1), {[(dpop)Mn(H2O)][MoIII(CN)7][Mn(dpop)]3[MoIV(CN)8]·29H2O}n (2), {[(dpop)Mn(H2O)]2[MoIV(CN)8]2[Mn(dpop)]4[MoIII(CN)7]·12H2O}n (3), and [(dpop)Mn(H2O)]2[MoIV(CN)8]·9H2O (4). Compound 1 contains only [MoIII(CN)7]4− anions and exhibits a corrugated two-dimensional layered architecture. The structure of 2 with a 1 : 1 ratio of MoIII : MoIV is best described as a ladder-like chain composed of [MoIII(CN)7]4−-based pentanuclear [MoIIIMnII4] fragments which are further linked by in situ produced [MoIV(CN)8]4− anions. In the case of 3, [Mn8Mo8] rings containing bent [MoIIIMnII2] fragments are extended into a two-dimensional layer with the ratio of [Mo(CN)7]4− : [Mo(CN)8]4− being 1 : 2. Compound 4 exhibits a bent trinuclear structure in which two CN groups of [Mo(CN)8]4− function as μ2-bridges to [Mn(dpop)(H2O)]2+ fragments. Magnetic studies suggest significant antiferromagnetic coupling interactions occur between Mo(III) and Mn(II) ions while, not surprisingly, interactions between the Mn(II) ions through diamagnetic [MoIV(CN)8]4− anions are negligible. Compound 1 exhibits ferrimagnetic ordering below 3.0 K whereas 2 shows the signature of single molecule magnet behavior with slow relaxation of the magnetization and an effective energy barrier (Ueff) of 8.1 K.

Graphical abstract: Variations in topology and magnetic properties of hepta- and octacyanometallates of molybdenum with manganese(ii)

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The article was received on 11 Dec 2013, accepted on 18 Feb 2014 and first published on 20 Mar 2014


Article type: Paper
DOI: 10.1039/C3DT53485E
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Dalton Trans., 2014,43, 6802-6810

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    Variations in topology and magnetic properties of hepta- and octacyanometallates of molybdenum with manganese(II)

    Q. Wang, Y. Zhang, H. Southerland, A. V. Prosvirin, H. Zhao and K. R. Dunbar, Dalton Trans., 2014, 43, 6802
    DOI: 10.1039/C3DT53485E

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