title: Orbital Engineering: Photoactivation of an Organofunctionalized Polyoxotungstate.
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[P2W17O57(PO5H5C7)2]⋅6 C4H9NO, 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.
authors: Graduate School of Pure and Applied Sciences, University of Tsukuba, Tennodai 1-1-1, Tsukuba, 305-8571, Japan.
authors: Jamie M
authors: 0000-0003-0138-933X
authors: JM
authors: Cameron
authors: Graduate School of Pure and Applied Sciences, University of Tsukuba, Tennodai 1-1-1, Tsukuba, 305-8571, Japan.
authors: Satomi
authors: S
authors: Fujimoto
authors: School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK.
authors: Katharina
authors: K
authors: Kastner
authors: Graduate School of Pure and Applied Sciences, University of Tsukuba, Tennodai 1-1-1, Tsukuba, 305-8571, Japan.
authors: Rong-Jia
authors: 0000-0001-7898-567X
authors: RJ
authors: Wei
authors: School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK.
authors: David
authors: 0000-0003-2760-7163
authors: D
authors: Robinson
authors: Faculty of Engineering, University of Nottingham, University Park, Nottingham, NG7 2RD, UK.
authors: Victor
authors: 0000-0001-7045-5244
authors: V
authors: Sans
authors: School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK.
authors: Graham N
authors: 0000-0003-2246-4466
authors: GN
authors: Newton
authors: Graduate School of Pure and Applied Sciences, University of Tsukuba, Tennodai 1-1-1, Tsukuba, 305-8571, Japan.
authors: H Hiroki
authors: 0000-0002-4682-4705
authors: HH
authors: Oshio
keywords: catalysis; electrochemistry; photochemistry; polyoxometalates; visible light