Inorganic Chemistry
ARTICLE
’ CONCLUSIONS
We prepared three unprecedented MnIII-containing WDST
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complexes, [Na2(H2O)2MnIII2(As2W15O56)2]16ꢀ (2), [MnIII-
(H2O)MnIII2(As2W15O56)2]15ꢀ (4), and [MnIII2(H2O)2MnIII
-
2
(As2W15O56)2]12ꢀ (6). Their parent MnII analogues, [Na2(H2O)2-
MnII (As2W15O56)2]18ꢀ (1) and [Na(H2O)2MnII(H2O)MnII -
2
2
(As2W15O56)2]17ꢀ (3), are also novel. These five new complexes
were fully characterized by FTIR, ATG, UVꢀvis, elemental
analysis, magnetic susceptibility, electrochemistry, and single-
crystal X-ray crystallography, where possible. Comparable studies
carried out on both MnII complexes and their well-known parent
[MnII (H2O)2MnII (As2W15O56)2]16ꢀ (5) clearly demonstrate
2
2
the influence of the oxidation states of the Mn centers (+II or +III)
on their structural, magnetic, and electrochemical properties. We
isolated, using cyclic voltammetry, the redox couple MnIII/II. We
also observed that it was easier to reach the higher oxidation states
of manganese (+IV and +V) starting with the MnII-containing
WDST complexes than with their MnIII counterparts. Possibilities
of preparing mixed-metal WDST complexes with MnIII and other
d or f metal ions such as FeIII, CrIII, or GdIII promise very inter-
esting magnetic properties.
’ ASSOCIATED CONTENT
S
Supporting Information. Three X-ray crystallographic
b
files in CIF format of [Na2(H2O)2MnIII2(As2W15O56)2]16ꢀ
,
[MnIII(H2O)MnIII2(As2W15O56)2]15ꢀ, and [Na(H2O)2MnII-
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(H2O)MnII (As2W15O56)2]17ꢀ; two alternative methods for
2
the synthesis of compound 4; X-ray photoelectron spectroscopy
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6 compounds in solution from pH 1 to pH 6; complementary
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ꢀ
Gꢀomez-Garcia, C. J. Chem. Rev. 1998, 98, 273–296. (h) M€uller, A.;
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’ AUTHOR INFORMATION
(11) (a) Tourney, C. M.; Tournꢀe, G. F.; Zonnevijlle, F. J. Chem. Soc.,
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Corresponding Author
*E-mail: israel.mbomekalle@chimie.uvsq.fr.
’ ACKNOWLEDGMENT
This work was supported by the Centre National de la Recherche
Scientifique (UMR 8180 and 8182), the University of Versailles,
and the University of Paris-Sud XI.
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