Exploring the Molecular Growth of Two Gigantic Half‐Closed Polyoxometalate Clusters {Mo 180 } and {Mo 130 Ce 6 }

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. Here we describe that the molecular growth from {Mo150} and {Mo120Ce6} to afford two half-closed gigantic molybdenum blue clusters {Mo180} (1) and {Mo130Ce6} (2), respectively. 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 {Mo120Ce6} that is sealed by a {Mo10} unit on one side. Moreover, the observation of the parent uncapped {Mo150} and {Mo120Ce6} clusters as minor products during the synthesis of 1 and 2 strongly suggests that the molecular growth process can be initialized from {Mo150} and {Mo120Ce6} in solution, respectively.