A molecular placeholder strategy gives access to a family of transition-metal functionalized vanadium oxide clusters

Katharina Kastner, Johannes T. Margraf, Tim Clark, Carsten Streb

Research output: Contribution to journalArticlepeer-review

Abstract

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 languageEnglish
Pages (from-to)12269-12273
JournalChemistry - A European Journal
Volume20
Issue number38
Early online date31 Jul 2014
DOIs
Publication statusPublished - Sep 2014

Keywords

  • Polyoxometalate
  • MOF

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