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

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

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.

Citation

Amin, S. S., Jones, K. D., Kibler, A. J., Damian, H. A., Cameron, J. M., Butler, K. S., …Newton, G. N. (2023). Diphosphoryl‐functionalized Polyoxometalates: Structurally and Electronically Tunable Hybrid Molecular Materials. Angewandte Chemie International Edition, 62(23), Article e202302446. https://doi.org/10.1002/anie.202302446

• Journal Article Type: Article
• Acceptance Date: Mar 27, 2023
• Online Publication Date: Mar 29, 2023
• Publication Date: Jun 5, 2023
• Deposit Date: Jun 13, 2023
• Publicly Available Date: Jun 13, 2023
• Journal: Angewandte Chemie International Edition
• Print ISSN: 1433-7851
• Electronic ISSN: 1521-3773
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• Volume: 62
• Issue: 23
• Article Number: e202302446
• DOI: https://doi.org/10.1002/anie.202302446
• Keywords: Clusters; Hybrid Materials; Organophosphorus; Polyoxometalates; Redox Properties
• Public URL: https://nottingham-repository.worktribe.com/output/19778700
• Publisher URL: https://onlinelibrary.wiley.com/doi/10.1002/anie.202302446
• Additional Information: Received: 2023-02-16; Published: 2023-04-26