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Tucher J, Peuntinger K, Margraf JT, et al. Template-dependent photochemical reactivity of molecular metal oxides. Chemistry. 2015;21(24):8716-9doi: 10.1002/chem.201501129.
Tucher, J., Peuntinger, K., Margraf, J. T., Clark, T., Guldi, D. M., & Streb, C. (2015). Template-dependent photochemical reactivity of molecular metal oxides. Chemistry (Weinheim an der Bergstrasse, Germany), 21(24), 8716-9. https://doi.org/10.1002/chem.201501129
Tucher, Johannes, et al. "Template-dependent photochemical reactivity of molecular metal oxides." Chemistry (Weinheim an der Bergstrasse, Germany) vol. 21,24 (2015): 8716-9. doi: https://doi.org/10.1002/chem.201501129
Tucher J, Peuntinger K, Margraf JT, Clark T, Guldi DM, Streb C. Template-dependent photochemical reactivity of molecular metal oxides. Chemistry. 2015 Jun 08;21(24):8716-9. doi: 10.1002/chem.201501129. Epub 2015 Apr 23. PMID: 25907798.
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Chemistry. 2015 Jun 08;21(24):8716-9. doi: 10.1002/chem.201501129. Epub 2015 Apr 23.

Template-dependent photochemical reactivity of molecular metal oxides.

Chemistry (Weinheim an der Bergstrasse, Germany)

Johannes Tucher, Katrin Peuntinger, Johannes T Margraf, Timothy Clark, Dirk M Guldi, Carsten Streb

Affiliations

  1. Institute of Inorganic Chemistry, Ulm University, Albert-Einstein-Allee 11, 89081 Ulm (Germany) web: http://www.strebgroup.net.
  2. Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials, Friedrich-Alexander-University Erlangen-Nuernberg, Egerlandstr. 3, 91058 Erlangen (Germany).
  3. Department of Chemistry and Pharmacy, Computer Chemistry Center, Friedrich-Alexander-University Erlangen-Nuernberg, Nägelsbachstr. 25, 91052 Erlangen (Germany).
  4. Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials, Friedrich-Alexander-University Erlangen-Nuernberg, Egerlandstr. 3, 91058 Erlangen (Germany). [email protected].
  5. Institute of Inorganic Chemistry, Ulm University, Albert-Einstein-Allee 11, 89081 Ulm (Germany) web: http://www.strebgroup.net. [email protected].

PMID: 25907798 DOI: 10.1002/chem.201501129

Abstract

A combined experimental and theoretical study shows that the photooxidative activity of two isostructural metal oxide clusters depends on their internal templates. To this end, two halide-templated bismuth vanadium oxide clusters [X(Bi(dmso)3 )2 V12 O33 ](-) (X=Cl(-) , Br(-) ) are reported and fully characterized. The two clusters show similar absorption features and illustrate that bismuth incorporation results in increased visible-light absorption. Significantly higher photooxidative activity is observed for the bromide-templated cluster compared with the chloride-templated one. Detailed photophysical assays and complementary DFT calculations suggest that the more efficient triplet excited state formation in the Br(-) -containing cluster is the decisive step in the photocatalysis and is due to the heavy-atom effect of the bromide. This concept can therefore open new pathways towards the optimization of photocatalytic activity in metal oxide clusters.

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords: density functional calculations; metal oxide; polyoxometalate; self-assembly; template

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