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 Butler, Stephen P. Argent, Max Winslow, David Robinson, Nicholas J. Mitchell, Hon Wai Lam, Graham N. Newton
Abstract
Abstract Herein, we report the synthesis and characterization of a new class of hybrid Wells–Dawson polyoxometalate (POM) containing a diphosphoryl group (P 2 O 6 X) of the general formula [P 2 W 17 O 57 (P 2 O 6 X)] 6− (X=O, NH, or CR 1 R 2 ). 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=CR 1 R 2 ) 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.