Engineering Highly Reduced Molybdenum Polyoxometalates via the Incorporation of d and f Block Metal Ions.

ABSTRACT: The assembly of nanoscale polyoxometalate (POM) clusters has been dominated by the highly reduced icosahedral {Mo₁₃₂ } "browns" and the toroidal {Mo₁₅₄ } "blues" which are 45 % and 18 % reduced, respectively. We hypothesised that there is space for a greater diversity of structures in this immediate reduction zone. Here we show it is possible to make highly reduced mix-valence POMs by presenting new classes of polyoxomolybdates: [Mo^V ₅₂ Mo^VI ₁₂ H₂₆ O₂₀₀ ]^42- {Mo₆₄ } and [Mo^V ₄₀ Mo^VI ₃₀ H₃₀ O₂₁₅ ]^20- {Mo₇₀ }, 81 % and 57 % reduced, respectively. The {Mo₆₄ } cluster archetype has a super-cube structure and is composed of five different types of building blocks, each arranged in overlayed Archimedean or Platonic polyhedra. The {Mo₇₀ } cluster comprises five tripodal {Mo^V ₆ } and five tetrahedral {Mo^V ₂ Mo^VI ₂ } building blocks alternatively linked to form a loop with a pentagonal star topology. We also show how the reaction yielding the {Mo₆₄ } super-cube can be used in the enrichment of lanthanides which exploit the differences in selectivity in the self-assembly of the polyoxometalates.

SUBMITTER: Ribo EG 

PROVIDER: S-EPMC9401863 | biostudies-literature | 2022 May

REPOSITORIES: biostudies-literature