Assembly of\nthe Skirt-Like Giant Molybdenum Blue Cluster\n{Mo<sub>158</sub>} from Dimerization of {Mo<sub>79</sub>} Featuring\nan Octameric Skeleton

Cyclic compounds are appealing owing to their intrinsic\nporous\nstructures and facile accessibility as building blocks (BBs) for fabricating\nhigh-order assemblies. Nevertheless, the modular synthesis of such\nmolecular entities and their subsequent controlled assembly are still\nvery challenging. Herein, we report the synthesis of a gigantic molybdenum\nblue (MB) wheel {Mo<sub>158</sub>} (<b>1</b>), featuring a skirt-shaped\nstructure dimerized from {Mo<sub>79</sub>}. {Mo<sub>79</sub>} exhibits\nan unprecedented octameric architecture built from eight sets of {Mo<sub>8</sub>} BBs, and the controlled assembly of this smallest member\nin the MB library is achieved by proper wheel contraction induced\nby {Mo<sub>1</sub>} and edge-sharing {Mo<sub>2</sub>} BBs. Moreover,\n{Mo<sub>158</sub>} can function as a 4-connected giant synthon, connecting\nwith adjacent four clusters in a controlled manner via four Mo–O–Mo\nbridges, resulting in a high-order architecture with a 2D layer structure.\nIn addition to single-crystal X-ray diffraction, {Mo<sub>158</sub>} is fully characterized by a variety of spectroscopies, allowing\nfor the unambiguous determination of its structure and formula. This\nwork not only enriches the family of gigantic clusters but also demonstrates\ntheir potential for constructing more complex assemblies.