Metal–metal bonds in polyoxometalate chemistry

Abstract

Half a century ago, F. Albert Cotton emphasized the relevance of metal-metal bonding in the constitution of cluster materials. Based on his description, nanoscale polyoxometalates (POMs) normally would not be...

Polyoxoplatinates as covalently dynamic electron sponges and molecular electronics materials

“…We also looked at polyoxoplatinates that exhibit metal-metal bonds, a feature that is not too common for classical and fully-oxydised POMs. 38 Until date, late transition metal-based POMs, have been highlighted as important models for understanding the catalytic activity of noble metal catalysis, 93 and as potential precursors for the generation of metal clusters. 21,94 As a result most efforts until now were invested in cuboidal polyoxopalladates.…”

“…covalent dynamics) and their application electron storage materials, sustainability technologies and "POMtronics". 38 In this line, [Pt III 12O8(SO4)12] 4− is also an instance of a metal-metal bonded POM. Structurally, [Pt III 12O8(SO4)12] 4− is a "saturated" (i.e., plenary) POM characterized by high thermal stability, 32,33 and high symmetry that renders this POM as a "Keplerate" architecture.…”

“…covalent dynamics) and their application in electron storage materials, sustainable technologies and “POMtronics”. 38 Along these lines, [Pt III 12 O 8 (SO 4 ) 12 ] 4− is also an example of a metal–metal bonded POM. Structurally, [Pt III 12 O 8 (SO 4 ) 12 ] 4− is a “saturated” ( i.e.…”

“…32,33 Although in the original work Wickleder referred to [Pt III 12O8(SO4)12] 4− as cluster ion, owing to the high oxo-ligand saturation [Pt III 12O8(SO4)12] 4− is widely recognized as a POM, 3,[34][35][36][37] or more precisely as a form of a metal-metal bonded POM. 38 The polyanion [Pt12O8(SO4)12] 4was originally isolated as deep red single crystals of the ammonium salt formed by reacting Pt(NO3)2 and concentrated sulfuric acid in a sealed glass ampoule at 350 °C for three days followed by slow cooling. 32 The latter conditions are highly oxidising and suitable for formation of POMs or extended metal oxides, 39,40 but rather uncommon for the formation of metal or alloy type cluster materials with carbonyl or thiol protecting ligands.…”

Composition-driven archetype dynamics in polyoxovanadates

“…Polyoxometalates (POMs) are forms of molecular metal oxides conventionally built of early transition metals (V, Mo, W, Nb and Ta) in high oxidation states. 1,2 In terms of bonding, the construction of POMs exclusively relies on metal–oxygen bonds, 3 which may differ in terms of inertness. 4 The metal and oxygen atoms often assemble into a small number of skeletal frameworks resulting in representative structural archetypes.…”