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 (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.

Making one VIV substitution for Mo on classical [MoV2O4]2+ group: the first heterobimetallic Mo–V subunit in polyoxomolybdate–bisphosphonate family

“…38 The V–O bond lengths in this anion range from 0.194 to 0.204 nm, meaning that vanadyl (VO) is not present. 39 The [Mo VI 2 O 6 ] structural unit is composed of two Mo octahedra in a face-sharing mode which are stabilized by two phosphonato groups and the hydroxyl of HL 4− ligands via P–O–Mo and C–O–Mo covalent bonding. The PO 3 group adopts the 3.120 coordination mode and the OH group bound to the C atom is found to be deprotonated, which was probably from the higher pH value of the solution.…”

Selective electrochemical CO2 conversion with a hybrid polyoxometalate

“…23–25 By tailoring the nature of the organic moiety in particular, the resulting hybrid species can demonstrate synergistic properties which can be finely tuned. 26–30…”

“…This is important as the phosphonate bridging unit in organic–inorganic hybrid POMs is known to be sensitive to hydrolytic cleavage. 26,29,44…”