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

Li, N; Luo, H-K; Wright, DS; Hanf, S; Matthews, P

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


Authors

N Li

H-K Luo

DS Wright

S Hanf



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.

Acceptance Date Dec 12, 2016
Publication Date Dec 12, 2016
Publicly Available Date Mar 28, 2024
Journal Dalton Transactions
Print ISSN 1477-9226
Publisher Royal Society of Chemistry
Pages 578-585
DOI https://doi.org/10.1039/c6dt04288k
Publisher URL https://doi.org/10.1039/c6dt04288k

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