Confined Electron-Transfer Reactions within a Molecular Metal Oxide 'Trojan Horse'

摘要

Heteropolyoxometalates (HPOMs) are molecular metal oxide clusters characterized by a vast structural diversity,'11 rich electrochemistry,'21 and versatile catalytic activities.'31 HPOMs frequently are derived from archetypal metal oxide cages of the general composition (MO3),(M = Mo,W) that incorporate structurally vital tetrahedral anions (e.g.,[SO4]2",[PO4]3~,[SiO4]4 ).Yet since the first structural elucidation of the archetypal Keggin HPOM [(MO3)12PO4]3~ in 1933,and after many thousands of publications on developments in the HPOM area,'4^61 the role of the central template in these exceptionally stable molecules has primarily remained a structural one.