TY - JOUR
T1 - A molecular placeholder strategy gives access to a family of transition-metal functionalized vanadium oxide clusters
AU - Kastner, Katharina
AU - Margraf, Johannes T.
AU - Clark, Tim
AU - Streb, Carsten
N1 - No agreement is in place with the funder of this work to make a post-print available
PY - 2014/9
Y1 - 2014/9
N2 - 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.
AB - 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.
KW - Polyoxometalate
KW - MOF
U2 - 10.1002/chem.201403592
DO - 10.1002/chem.201403592
M3 - Article
SN - 0947-6539
VL - 20
SP - 12269
EP - 12273
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 38
ER -