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

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....

Full description

Saved in:
Bibliographic Details
Published in:Angewandte Chemie 2023-06, Vol.135 (23), p.n/a
Main Authors: 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.
Format: Article
Language:English
Subjects:
Chemical synthesis
Chemistry
Clusters
Hybrid Materials
Organophosphorus
Phosphonates
Polyoxometalates
Polyoxometallates
Redox Properties
Wells
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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. The synthesis and characterization of a new class of hybrid diphosphoryl Wells–Dawson polyoxometalate (POM) is described. The covalent tethering of diphosphoryl compounds to the inorganic cluster gives redox‐active materials with enhanced hydrolytic stability compared to the corresponding phosphonate analogues. These readily modifiable precursors provide a platform for structural and electronic modulation of the POM, enabling the rational design and synthesis of next‐generation hybrid Wells–Dawson POMs.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.202302446