A Molecular Placeholder Strategy To Access a Family of Transition‐Metal‐Functionalized Vanadium Oxide Clusters |
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| Authors: | Katharina Kastner Johannes T Margraf Prof?Dr Timothy Clark Prof?Dr Carsten Streb |
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| Institution: | 1. Institute of Inorganic Chemistry I, Ulm University, Albert‐Einstein‐Allee 11, 89081 Ulm (Germany), Fax: (+49)?731‐50‐23031 http://www.strebgroup.net;2. Previous address: Department of Chemistry and Pharmacy, Institute of Inorganic Chemistry II, Friedrich‐Alexander‐University Erlangen‐Nuremberg, Egerlandstrasse 1, 91058 Erlangen (Germany);3. Department of Chemistry and Pharmacy, Computer‐Chemistry‐Center, Friedrich‐Alexander‐University Erlangen‐Nuremberg, N?gelsbachstrasse 25, 91052 Erlangen (Germany) |
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| 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)2V12O32Cl]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. |
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| Keywords: | functionalization metal oxide clusters polyoxometalates polyoxovanadates self‐assembly |
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