Orbital Engineering: Photoactivation of an Organofunctionalized Polyoxotungstate

详细信息    查看全文

• 作者：Dr. Jamie M. Cameron ; Satomi Fujimoto ; Dr. Katharina Kastner ; Dr. Rong-Jia Wei ; Dr. David Robinson ; Dr. Victor Sans ; Dr. Graham N. Newton and Prof. Dr. H. Hiroki Oshio
• 刊名：Chemistry - A European Journal
• 出版年：2017
• 出版时间：January 1, 2017
• 年：2017
• 卷：23
• 期：1
• 页码：47-50
• 全文大小：1374K
• ISSN：1521-3765

文摘

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.