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Issue 2, 2017
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The influence of halides in polyoxotitanate cages; dipole moment, splitting and expansion of d-orbitals and electron–electron repulsion

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Abstract

Metal-doped polyoxotitanate (M-POT) cages have been shown to be efficient single-source precursors to metal-doped titania [TiO2(M)] (state-of-the-art photocatalytic materials) as well as molecular models for the behaviour of dopant metal ions in bulk titania. Here we report the influence halide ions have on the optical and electronic properties of a series of halide-only, and cobalt halide-‘doped’ POT cages. In this combined experimental and computational study we show that halide ions can have several effects on the band gaps of halide-containing POT cages, influencing the dipole moment (hole–electron separation) and the structure of the valance band edge. Overall, the band gap behaviour stems from the effects of increasing orbital energy moving from F to I down Group 17, as well as crystal-field splitting of the d-orbitals, the potential effects of the Nephelauxetic influence of the halides and electron–electron repulsion.

Graphical abstract: The influence of halides in polyoxotitanate cages; dipole moment, splitting and expansion of d-orbitals and electron–electron repulsion

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Publication details

The article was received on 10 Nov 2016, accepted on 12 Dec 2016 and first published on 12 Dec 2016


Article type: Paper
DOI: 10.1039/C6DT04288K
Citation: Dalton Trans., 2017,46, 578-585
  • Open access: Creative Commons BY license
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    The influence of halides in polyoxotitanate cages; dipole moment, splitting and expansion of d-orbitals and electron–electron repulsion

    S. Hanf, P. D. Matthews, N. Li, H. Luo and D. S. Wright, Dalton Trans., 2017, 46, 578
    DOI: 10.1039/C6DT04288K

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