A molecular placeholder strategy to access a family of transition-metal-functionalized vanadium oxide clusters. Kastner, K., Margraf, J., Clark, T., & Streb, C. Chemistry - A European Journal, 2014.
abstract   bibtex   
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.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, 51VNMR 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.
@article{
 title = {A molecular placeholder strategy to access a family of transition-metal-functionalized vanadium oxide clusters},
 type = {article},
 year = {2014},
 identifiers = {[object Object]},
 keywords = {functionalization,metal oxide clusters,polyoxometalates,polyoxovanadates,self-assembly},
 volume = {20},
 id = {a06b873e-67e5-3022-b6f0-56e410197cee},
 created = {2017-06-11T12:49:23.879Z},
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 abstract = {© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.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, 51VNMR 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.},
 bibtype = {article},
 author = {Kastner, K. and Margraf, J.T. and Clark, T. and Streb, C.},
 journal = {Chemistry - A European Journal},
 number = {38}
}

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