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., Argent, S. P., Winslow, M., Robinson, D., Mitchell, N. J., Lam, H. W., & 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