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

Abstract

Constructing fullerene-like metal-organic nanocage integrating novel architectures and unique functions remains a formidable challenge. Herein, an unprecedented high-nuclearity fullerene-like heteropolyoxometalate cluster, {Na32[(V V O2)30(Mo VI O4)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 are 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.