Self-assembly of a high-nuclearity fullerene-like heteropolyoxometalate cage

Abstract

Constructing fullerene-like metal–organic cage integrating novel architectures and unique functions remains a formidable challenge. Herein, an unprecedented high-nuclearity fullerene-like heteropolyoxometalate cage, {Na₃₂[(V^VO₂)₃₀(Mo^VIO₄)₁₂(PhPO₃)₄₈(CH₃COO)₁₂](CO₃)₂}·5MeCN (Mo₂₄V₃₀P₄₈, MeCN = acetonitrile), was successfully synthesized via a one-pot method. This anionic cluster can be described as a pseudo-cubic cage assembled from 12 {Mo₂V₂P₄} quadrilaterals and 6 {VO₆} octahedra. Sodium ions are employed as templates to fill the cage. The entire structure displays a distinct four-shell {Mo₂₄}@{V₃₀P₄₈}@{Na₂₄}@{Na₈} arrangement. Since all the {Mo₂} units and Na⁺ ions are located on the {V₃₀P₄₈} cage, this structure can also be simplified as a fullerene-like heterometallic cage composed of 12 {Mo₂V₂P₄} hexagons, 8 {NaV₃P₃} hexagons, and 24 {NaV₂P₃} pentagons. Additionally, Mo₂₄V₃₀P₄₈ exhibits high solution stability, as confirmed by ESI-MS, PXRD and SEM, which makes it a highly efficient and stable catalyst for phenolic oxidation reactions.