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Diphosphoryl-functionalized Polyoxometalates: Structurally and Electronically Tunable Hybrid Molecular Materials
Authors:Dr Sharad S Amin  Dr Kieran D Jones  Dr Alexander J Kibler  Dr Heather A Damian  Dr Jamie M Cameron  Dr Kevin S Butler  Dr Stephen P Argent  Max Winslow  Dr David Robinson  Dr Nicholas J Mitchell  Prof Hon Wai Lam  Dr Graham N Newton
Institution:1. The GlaxoSmithKline Carbon Neutral Laboratories for Sustainable Chemistry, University of Nottingham, Jubilee Campus, Triumph Road, Nottingham, NG7 2TU UK;2. The GlaxoSmithKline Carbon Neutral Laboratories for Sustainable Chemistry, University of Nottingham, Jubilee Campus, Triumph Road, Nottingham, NG7 2TU UK

School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD UK;3. Department of Chemistry and Forensics, School of Science and Technology, Nottingham Trent University, Nottingham, NG11 8NS UK;4. School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD UK

Abstract:Herein, we report the synthesis and characterization of a new class of hybrid Wells–Dawson polyoxometalate (POM) containing a diphosphoryl group (P2O6X) of the general formula P2W17O57(P2O6X)]6− (X=O, NH, or CR1R2). Modifying the bridging unit X was found to impact the redox potentials of the POM. The ease with which a range of α-functionalized diphosphonic acids (X=CR1R2) can be prepared provides possibilities to access diverse functionalized hybrid POMs. Compared to existing phosphonate hybrid Wells–Dawson POMs, diphosphoryl-substituted POMs offer a wider tunable redox window and enhanced hydrolytic stability. This study provides a basis for the rational design and synthesis of next-generation hybrid Wells–Dawson POMs.
Keywords:Clusters  Hybrid Materials  Organophosphorus  Polyoxometalates  Redox Properties
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