Exploring the Molecular Growth of Two Gigantic Half-Closed Polyoxometalate Clusters {Mo180 } and {Mo130 Ce6 }.

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 {Mo150 } and {Mo120 Ce6 } to afford two half-closed gigantic molybdenum blue clusters {Mo180 } (1) and {Mo130 Ce6 } (2), respectively. Compound 1 features a hat-shaped structure with the parent wheel-shaped {Mo150 } being capped by a {Mo30 } unit on one side. Similarly, 2 exhibits an elliptical lanthanide-doped wheel {Mo120 Ce6 } that is sealed by a {Mo10 } unit on one side. Moreover, the observation of the parent uncapped {Mo150 } and {Mo120 Ce6 } clusters as minor products during the synthesis of 1 and 2 strongly suggests that the molecular growth process can be initialized from {Mo150 } and {Mo120 Ce6 } in solution, respectively.