[V15Ge6O42S6(H2O)](12-), a Thiogermanatopolyoxovanadate Cluster Featuring the Spin Topology of the Molecular Magnet [V15As6O42(H2O)](6-)

作者：Wang Jing; Nather Christian; Koegerler Paul; Bensch Wolfgang^*

来源：European Journal of Inorganic Chemistry, 2012, (8): 1237-1242.

DOI：10.1002/ejic.201101187

• Cluster compounds
• Solvothermal synthesis
• Solid-state structures
• Polyoxovanadate
• Magnetic properties

The new compound [Co(tren)(trenH(2))](2)[{Co(tren)}(2)-V15Ge6O42S6(H2O)]center dot 9H(2)O [1, tren = tris(2-aminoethyl)amine] has been obtained under solvothermal conditions and features the unique thiogermanatovanadatopolyoxoanion [(V15Ge6O42S6)-Ge-IV-O-IV(H2O)](12-) as the main structural motif. Compound 1 crystallizes in the monoclinic space group P2(1/c) with a = 15.4711(2), b = 26.4031(4), c = 26.7213(4) angstrom, V = 10874.2(3) angstrom(3), and Z = 4. The [V15Ge6O42S6(H2O)](12)- cluster anion displays the spin topology reported for the molecular magnets [(V15As6O42)-As-IV-O-III(H2O)](6-) and [(V15Sb6O42)-Sb-IV-O-III](6-) and therefore represents a new member of the {V15E6} family, which has allowed us to study the magnetic exchange interactions between the vanadyl (d(1)) groups of the geometrically frustrated central V-3 triangle, which is sandwiched between strongly antiferromagnetically coupled V-6 hexagons. The cluster shell is expanded by two {Co(tren)}(2+)-based complexes through Co-S bonds, which reduce the high negative charge of the anion. The Co2+ ions in the [Co(tren)(trenH(2))](4+) countercations are coordinated to one tetradentate tren and a monodentate, doubly protonated tren ligand.

• 出版日期2012-3