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Issue 47, 2013
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Chain and layer networks of germanato-polyoxovanadates

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Abstract

Two new members of the {V15E6} (E = As, Sb, Ge, and Si) polyoxovanadate family, [{Mn(tren)(trenH2)}{Mn(tren)}4V15Ge6O48(H2O)0.5]·tren·2H2O (1, tren = tris(2-aminoethyl)amine) and [{Ni(tren)}4(trenH2)2V15Ge6O48(H2O)]·2H2O (2), have been prepared under solvothermal conditions. In 1, the {V15Ge6} cluster is expanded by five in situ formed crystallographically independent Mn2+ complexes via Mn–O(–V/Ge) bonds. Two independent Mn2+ complexes create a rare dinuclear [Mn2O2(tren)2]4+ moiety by bond formation with two terminal O atoms of the Ge2O7 groups of the adjacent {V15Ge6O48(H2O)0.5} clusters, thus connecting the {V15Ge6} cluster shells into a unique charge-neutral helical chain. In the structure of 2, the unusual and hitherto never observed {Ni(tren)(trenH2)Ni(tren)}6+ complex is formed in situ consisting of two tren molecules acting as tetradentate ligands to Ni2+ cations and one additional tren molecule connecting two Ni2+ cations bonded to neighboring cluster anions. The complexes act as linkers joining the {V15Ge6} moieties via Ni–O[double bond, length as m-dash]V bridges, forming a 2D structure. In the coordination polymers of 1 and 2, the spin structure of the {V15Ge6} cluster remains virtually unaffected by the coordinated MnII or NiII spin centers. For both compounds, the magnetic susceptibility can be decomposed into a sum of the contributions of both the {V15Ge6} cluster and the MnII or NiII cations, and a molecular field correction suffices to represent the weak antiferromagnetic coupling between them. Compound 1 is stable up to 350 °C as evidenced by in situ temperature-resolved X-ray powder diffraction studies.

Graphical abstract: Chain and layer networks of germanato-polyoxovanadates

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Supplementary files

Article information


Submitted
30 Jul 2013
Accepted
20 Sep 2013
First published
23 Sep 2013

CrystEngComm, 2013,15, 10238-10245
Article type
Paper

Chain and layer networks of germanato-polyoxovanadates

J. Wang, C. Näther, M. Speldrich, P. Kögerler and W. Bensch, CrystEngComm, 2013, 15, 10238
DOI: 10.1039/C3CE41512K

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