title: Template-dependent photochemical reactivity of molecular metal oxides.
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.
authors.affiliation: Institute of Inorganic Chemistry, Ulm University, Albert-Einstein-Allee 11, 89081 Ulm (Germany) web: http://www.strebgroup.net.
authors.forename: Johannes
authors.initials: J
authors.lastname: Tucher
authors.affiliation: Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials, Friedrich-Alexander-University Erlangen-Nuernberg, Egerlandstr. 3, 91058 Erlangen (Germany).
authors.forename: Katrin
authors.initials: K
authors.lastname: Peuntinger
authors.affiliation: Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials, Friedrich-Alexander-University Erlangen-Nuernberg, Egerlandstr. 3, 91058 Erlangen (Germany).|Department of Chemistry and Pharmacy, Computer Chemistry Center, Friedrich-Alexander-University Erlangen-Nuernberg, Nägelsbachstr. 25, 91052 Erlangen (Germany).
authors.forename: Johannes T
authors.initials: JT
authors.lastname: Margraf
authors.affiliation: Department of Chemistry and Pharmacy, Computer Chemistry Center, Friedrich-Alexander-University Erlangen-Nuernberg, Nägelsbachstr. 25, 91052 Erlangen (Germany).
authors.forename: Timothy
authors.initials: T
authors.lastname: Clark
authors.affiliation: Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials, Friedrich-Alexander-University Erlangen-Nuernberg, Egerlandstr. 3, 91058 Erlangen (Germany). dirk.guldi@fau.de.
authors.forename: Dirk M
authors.initials: DM
authors.lastname: Guldi
authors.affiliation: Institute of Inorganic Chemistry, Ulm University, Albert-Einstein-Allee 11, 89081 Ulm (Germany) web: http://www.strebgroup.net. carsten.streb@uni-ulm.de.
authors.forename: Carsten
authors.initials: C
authors.lastname: Streb
keywords: density functional calculations; metal oxide; polyoxometalate; self-assembly; template