Abstract
Understanding the process of the self-assembly of gigantic polyoxometalates and their subsequent molecular growth, by the addition of capping moieties onto the oxo-frameworks, is critical for the development of the designed assembly of complex high-nuclearity cluster species, yet such processes remain far from being understood. Herein we describe the molecular growth from {Mo(150) } and {Mo(120) Ce(6) } to afford two half-closed gigantic molybdenum blue clusters {Mo(180) } (1) and {Mo(130) Ce(6) } (2), respectively. Compound 1 features a hat-shaped structure with the parent wheel-shaped {Mo(150) } being capped by a {Mo(30) } unit on one side. Similarly, 2 exhibits an elliptical lanthanide-doped wheel {Mo(120) Ce(6) } that is sealed by a {Mo(10) } unit on one side. Moreover, the observation of the parent uncapped {Mo(150) } and {Mo(120) Ce(6) } clusters as minor products during the synthesis of 1 and 2 strongly suggests that the molecular growth process can be initialized from {Mo(150) } and {Mo(120) Ce(6) } in solution, respectively.