Orbital Engineering: Photoactivation of an Organofunctionalized Polyoxotungstate

Jamie M Cameron; Satomi Fujimoto; Katharina Kastner; Rong-Jia Wei; David Robinson; Victor Sans; Graham N Newton; H Hiroki Oshio

doi:10.1002/chem.201605021

Orbital Engineering: Photoactivation of an Organofunctionalized Polyoxotungstate

Chemistry. 2017 Jan 1;23(1):47-50. doi: 10.1002/chem.201605021. Epub 2016 Nov 30.

Authors

Jamie M Cameron¹, Satomi Fujimoto¹, Katharina Kastner², Rong-Jia Wei¹, David Robinson², Victor Sans³, Graham N Newton², H Hiroki Oshio¹

Affiliations

¹ Graduate School of Pure and Applied Sciences, University of Tsukuba, Tennodai 1-1-1, Tsukuba, 305-8571, Japan.
² School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK.
³ Faculty of Engineering, University of Nottingham, University Park, Nottingham, NG7 2RD, UK.

PMID: 27801953
DOI: 10.1002/chem.201605021

Abstract

Tungsten-based polyoxometalates (POMs) have been 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. Herein, an organic-inorganic hybrid polyoxometalate, K₆ [P₂ W₁₇ O₅₇ (PO₅ H₅ C₇ )₂ ]⋅6 C₄ H₉ NO, was found to exhibit enhanced redox behaviour and photochemistry compared to its purely inorganic counterparts. Hybridization with electron-withdrawing moieties was shown to tune 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.

Keywords: catalysis; electrochemistry; photochemistry; polyoxometalates; visible light.

Publication types

Research Support, Non-U.S. Gov't