Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 53, Issue 7, Pages 1934-1938Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201307721
Keywords
band gap; cobalt; polyoxometalates; structure elucidation; titanium
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Funding
- China Scholarship Council
- EU (ERC-Advanced Investigator Award)
- EPSRC
- NSFC [21273163]
- Emmanuel College (Cambridge)
- EPSRC [EP/F00253X/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/F00253X/1] Funding Source: researchfish
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Metal-doped polyoxotitanium cages are a developing class of inorganic compounds which can be regarded as nano- and sub-nano sized molecular relatives of metal-doped titania nanoparticles. These species can serve as models for the ways in which dopant metal ions can be incorporated into metal-doped titania (TiO2), a technologically important class of photocatalytic materials with broad applications in devices and pollution control. In this study a series of cobalt(II)-containing cages in the size range ca. 0.7-1.3nm have been synthesized and structurally characterized, allowing a coherent study of the factors affecting the band gaps in well-defined metal-doped model systems. Band structure calculations are consistent with experimental UV/Vis measurements of the TixOy absorption edges in these species and reveal that molecular dipole moment can have a profound effect on the band gap. The observation of a dipole-induced band-gap decrease mechanism provides a potentially general design strategy for the formation of low band-gap inorganic cages.
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