Mechanistic insights into polyoxometalate self-assembly in organic solvent: conversion of a cyclic polyoxovanadate-ethoxide to its Lindqvist congener

Abstract

We report the synthesis of a cyclic hexavanadate polyoxovanadate-alkoxide cluster, [VO(OC₂H₅)₂]₆, and its conversion, under solvothermal conditions, to an oxygen-deficient Lindqvist assembly, [V₆O₆(OC₂H₅)₁₂]ⁿ (n = 1−, 0). This study presents insights into the mechanism of organo-functionalized polyoxovandate-alkoxide formation, namely identifying essential intermediates and the source of the central μ₆-O²⁻ ligand.