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Issue 10, 2014
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Novel thioarsenates {[Mn(2,2′-bipy)2(SCN)][Mn(2,2′-bipy)](AsVS4)}2 and {[Mn(2,2′-bipy)2(SCN)]2[AsIII2(S2)2S2]}: introducing an anionic second ligand to modify MnII complex cations of 2,2′-bipyridine

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Abstract

Two novel manganese thioarsenates, {[Mn(2,2′-bipy)2(SCN)][Mn(2,2′-bipy)](AsVS4)}2 (1, 2,2′-bipy = 2,2′-bipyridine) and {[Mn(2,2′-bipy)2(SCN)]2[AsIII2(S2)2S2]} (2), containing thiocyanate-modified Mn-2,2′-bipy complex cations were synthesized. They feature two terminal [Mn(2,2′-bipy)2(SCN)]+ complex cations bridged by a polyanion {[Mn(2,2′-bipy)]2(AsVS4)2}2− for 1 and a cyclic thioarsenate anion (AsIII2S6)2− for 2. In 2, the [AsIII2(S2)2S2]2− anion can be described as two (AsIIIS3)3− trigonal-pyramids interlinked through S–S bonds. The method to obtain new metal complex cations shown here, introducing an anionic second ligand to modify the number of coordination sites and the charges of the metal complex cations simultaneously, is different from the traditional methods, varying either the TM center or the organic ligand or employing mixed neutral organic ligands, and may open up a new route for preparing novel chalcogenidometalates. Compounds 1 and 2 exhibit wide optical gaps of 2.20 and 2.67 eV, respectively, and photoluminescence with the emission maxima occurring around 440 nm. Magnetic measurements show the presence of antiferromagnetic interactions between MnII centers in the two compounds.

Graphical abstract: Novel thioarsenates {[Mn(2,2′-bipy)2(SCN)][Mn(2,2′-bipy)](AsVS4)}2 and {[Mn(2,2′-bipy)2(SCN)]2[AsIII2(S2)2S2]}: introducing an anionic second ligand to modify MnII complex cations of 2,2′-bipyridine

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Publication details

The article was received on 15 Dec 2013, accepted on 23 Dec 2013 and first published on 03 Jan 2014


Article type: Paper
DOI: 10.1039/C3DT53515K
Citation: Dalton Trans., 2014,43, 3931-3938
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    Novel thioarsenates {[Mn(2,2′-bipy)2(SCN)][Mn(2,2′-bipy)](AsVS4)}2 and {[Mn(2,2′-bipy)2(SCN)]2[AsIII2(S2)2S2]}: introducing an anionic second ligand to modify MnII complex cations of 2,2′-bipyridine

    G. Liu, G. Guo, M. Wang and J. Huang, Dalton Trans., 2014, 43, 3931
    DOI: 10.1039/C3DT53515K

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