Assembly of the Skirt-Like Giant Molybdenum Blue Cluster {Mo158} from Dimerization of {Mo79} Featuring an Octameric Skeleton

Abstract

Cyclic compounds are appealing owing to their intrinsic porous structures and facile accessibility as building blocks (BBs) for fabricating high-order assemblies. Nevertheless, the modular synthesis of such molecular entities and their subsequent controlled assembly are still very challenging. Herein, we report the synthesis of a gigantic molybdenum blue (MB) wheel {Mo₁₅₈} (1), featuring a skirt-shaped structure dimerized from {Mo₇₉}. {Mo₇₉} exhibits an unprecedented octameric architecture built from eight sets of {Mo₈} BBs, and the controlled assembly of this smallest member in the MB library is achieved by proper wheel contraction induced by {Mo₁} and edge-sharing {Mo₂} BBs. Moreover, {Mo₁₅₈} can function as a 4-connected giant synthon, connecting with adjacent four clusters in a controlled manner via four Mo–O–Mo bridges, resulting in a high-order architecture with a 2D layer structure. In addition to single-crystal X-ray diffraction, {Mo₁₅₈} is fully characterized by a variety of spectroscopies, allowing for the unambiguous determination of its structure and formula. This work not only enriches the family of gigantic clusters but also demonstrates their potential for constructing more complex assemblies.