Engineering Highly Reduced Molybdenum Polyoxometalates via the Incorporation of <i>d</i> and <i>f</i> Block Metal Ions

The assembly of nanoscale polyoxometalate (POM) clusters has been dominated by the highly reduced icosahedral {Mo132} “browns” and toroidal {Mo154} “blues” which are 45 % 18 reduced, respectively. We hypothesised that there is space for a greater diversity structures in this immediate reduction zone. Here we show it possible to make mix-valence POMs presenting new classes polyoxomolybdates: [MoV52MoVI12H26O200]42− {Mo64} [MoV40MoVI30H30O215]20− {Mo70}, 81 57 cluster archetype super-cube structure composed five different types building blocks, each arranged overlayed Archimedean or Platonic polyhedra. {Mo70} comprises tripodal {MoV6} tetrahedral {MoV2MoVI2} blocks alternatively linked form loop with pentagonal star topology. also how reaction yielding can be used enrichment lanthanides exploit differences selectivity self-assembly polyoxometalates.