Diphosphoryl-functionalized Polyoxometalates: Structurally and Electronically Tunable Hybrid Molecular Materials

Sharad S Amin; Kieran D Jones; Alexander J Kibler; Heather A Damian; Jamie M Cameron; Kevin S Butler; Stephen P Argent; Max Winslow; David Robinson; Nicholas J Mitchell; Hon Wai Lam; Graham N Newton

doi:10.1002/anie.202302446

Diphosphoryl-functionalized Polyoxometalates: Structurally and Electronically Tunable Hybrid Molecular Materials

Angew Chem Int Ed Engl. 2023 Jun 5;62(23):e202302446. doi: 10.1002/anie.202302446. Epub 2023 Apr 26.

Authors

Sharad S Amin^{1

2}, Kieran D Jones^{1

2}, Alexander J Kibler^{1

2}, Heather A Damian^{1

2}, Jamie M Cameron^{1

2}, Kevin S Butler^{1

2}, Stephen P Argent^{1

2}, Max Winslow³, David Robinson³, Nicholas J Mitchell², Hon Wai Lam^{1

2}, Graham N Newton^{1

2}

Affiliations

¹ The GlaxoSmithKline Carbon Neutral Laboratories for Sustainable Chemistry, University of Nottingham, Jubilee Campus, Triumph Road, Nottingham, NG7 2TU, UK.
² 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.

Abstract

Herein, we report the synthesis and characterization of a new class of hybrid Wells-Dawson polyoxometalate (POM) containing a diphosphoryl group (P₂ O₆ X) of the general formula [P₂ W₁₇ O₅₇ (P₂ O₆ X)]^6- (X=O, NH, or CR¹ R² ). 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=CR¹ R² ) 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.

Abstract

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