A molecular placeholder strategy gives access to a family of transition-metal functionalized vanadium oxide clusters
Research output: Contribution to journal › Article › peer-review
Systematic access to metal-functionalized polyoxometalates has thus far
been limited to lacunary tungsten oxide and molybdenum oxide clusters.
The first controlled, stepwise bottom-up assembly route to
metal-functionalized molecular vanadium oxides is now presented. A
di-vacant vanadate cluster with two metal binding sites, (DMA)2[V12O32Cl]3−
(DMA=dimethylammonium) is formed spontaneously in solution and
characterized by single-crystal X-ray diffraction, ESI mass
spectrometry, 51V NMR spectroscopy, and elemental analyses.
In the cluster, the metal binding sites are selectively blocked by
hydrogen-bonded DMA placeholder cations. Reaction of the cluster with
transition metals TM (Fe3+, Co2+, Cu2+, Zn2+) gives access to mono-functionalized vanadate clusters (DMA)[{TM(L)}V12O32Cl]n−
(L=ligand). Metal binding is accomplished by significant distortions of
the vanadium oxide framework reminiscent of a pincer movement. Cluster
stability under technologically relevant conditions in the solid-state
and solution is demonstrated.
Original language | English |
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Pages (from-to) | 12269-12273 |
Journal | Chemistry - A European Journal |
Volume | 20 |
Issue number | 38 |
Early online date | 31 Jul 2014 |
DOIs | |
Publication status | Published - Sep 2014 |
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