Issue 10, 2014

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

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

Supplementary files

Article information

Article type
Paper
Submitted
15 Dec 2013
Accepted
23 Dec 2013
First published
03 Jan 2014

Dalton Trans., 2014,43, 3931-3938

Author version available

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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