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

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.