Self-assembly of high-nuclear core-shell polyoxovanadates with Lindqvsit templates

Only rarely have polyoxometalates been recorded to form core-shell clusters, which presumably relates to the scarcity of appropriate building blocks. Herein, two high-nuclear core-shell polyoxophosphovanadates [M6O19]2-subset of[Na8VV6VIV12O18(PhPO3)24]2+ (M = W 1, Mo 2) are synthesized utilizing Lindqvist polyoxometalates as templates. Both clusters exhibit a nested three-shell architecture characterized by an octahedron@cube@octahedron configuration. The outer shell [VV6VIV12O18(PhPO3)24]6- consists of two simple {VO5} and {PhPO3} building blocks connected alternately and exhibits the same octahedral geometry as the inner core [M6O19]2- due to anionic template effects. To the best of our knowledge, compounds 1 and 2 represent the first core-shell polyoxovanadates templated by Lindqvist polyoxometalates. Furthermore, compound 1 demonstrates efficacy and stability as a catalyst for the oxidation of sulfide. This work provides a new perspective on the construction of novel core-shell polyoxometalates.