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Orbital engineering: photoactivation of an organofunctionalized polyoxotungstate

Newton, Graham; Oshio, Hiroki; Cameron, Jamie; Fujimoto, Satomi; Kastner, Katharina; Wei, Rong Jia; Robinson, David; Sans, Victor

Authors

Hiroki Oshio

Jamie Cameron

Satomi Fujimoto

Katharina Kastner

Rong Jia Wei

David Robinson

Victor Sans



Abstract

Tungsten-based polyoxometalates (POMs) are employed as UV-driven photo-catalysts for a range of organic transformations. Their photoactivity is dependent on electronic transitions between frontier orbitals, and thus manipulation of orbital energy levels provides a promising means of extending their utility into the visible regime. Here, an organic-inorganic hybrid polyoxometalate, K₆[P₂2W₁₇O₅₇(PO₅H₅C₇)₂]·6C₄H₉NO, was found to exhibit enhanced redox behavior and photochemistry compared to its purely inorganic counterparts. Hybridization with electron withdrawing moieties was shown to modify the frontier orbital energy levels and reduce the HOMO-LUMO gap, leading to direct visible-light photoactivation of the hybrid, and establishing a simple, cheap and effective approach to the generation of visible-light-activated hybrid nanomaterials

Citation

Newton, G., Oshio, H., Cameron, J., Fujimoto, S., Kastner, K., Wei, R. J., …Sans, V. (2017). Orbital engineering: photoactivation of an organofunctionalized polyoxotungstate. Chemistry - A European Journal, 23(1), 47-50. https://doi.org/10.1002/chem.201605021

Journal Article Type Article
Acceptance Date Oct 31, 2016
Online Publication Date Nov 30, 2016
Publication Date Jan 1, 2017
Deposit Date Nov 14, 2016
Publicly Available Date Mar 28, 2024
Journal Chemistry - a European Journal
Print ISSN 0947-6539
Electronic ISSN 1521-3765
Publisher Wiley
Peer Reviewed Peer Reviewed
Volume 23
Issue 1
Pages 47-50
DOI https://doi.org/10.1002/chem.201605021
Keywords Polyoxometalates; Photochemistry; Visible-light; Catalysis; Electrochemistry
Public URL https://nottingham-repository.worktribe.com/output/830852
Publisher URL http://onlinelibrary.wiley.com/doi/10.1002/chem.201605021/abstract
Additional Information This is the peer reviewed version of the following article: Newton, G. N., Oshio, H., Cameron, J., Fujimoto, S., Kastner, K., Wei, R.-J., Robinson, D. and Sans, V. (2016), Orbital Engineering: Photoactivation of an Organofunctionalized Polyoxotungstate. Chem. Eur. J., which has been published in final form at http://dx.doi.org/10.1002/chem.201605021. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.