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

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.