Template-dependent photochemical reactivity of molecular metal oxides

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

doi:10.1002/chem.201501129

Template-dependent photochemical reactivity of molecular metal oxides

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

School of Pharmacy & Biomedical Sciences

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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)2V12O33]− (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.

Original language	English
Pages (from-to)	8716-8719
Journal	Chemistry - A European Journal
Volume	21
Issue number	24
Early online date	23 Apr 2015
DOIs	https://doi.org/10.1002/chem.201501129
Publication status	Published - 8 Jun 2015

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http://doi.wiley.com/10.1002/chem.201501129

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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)2V12O33]− (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.",

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AU - Tucher, Johannes

AU - Peuntinger, Katrin

AU - Margraf, Johannes T.

AU - Clark, Timothy

AU - Guldi, Dirk M.

AU - Streb, Carsten

PY - 2015/6/8

Y1 - 2015/6/8

N2 - 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)2V12O33]− (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.

AB - 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)2V12O33]− (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.

U2 - 10.1002/chem.201501129

DO - 10.1002/chem.201501129

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JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

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ER -

Template-dependent photochemical reactivity of molecular metal oxides

Abstract

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