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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 {Mo120Ce6} to afford two half-closed gigantic molybdenum blue clusters {Mo180} (1) and {Mo130Ce6} (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 {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. [ABSTRACT FROM AUTHOR]

We report an approach to synthesize molecular tungsten-oxide-based pentagonal building blocks, in a new {W21O72} unit, and show how this leads to a family of gigantic molecular architectures including [H12W48O164]28− {W48}, [H20W56O190]24− {W56}, and [H12W92O311]58− {W92}. The {W48} and {W56} clusters are both dimeric species incorporating two {W21} units and the {W56} species is the first example of a molecular metal oxide cluster containing a chiral “double-stranded” motif which is stable in solution as confirmed by mass spectrometry. The {W92} anion having four {W21} units is one of the largest transition metal substituted isopolyoxotungstates known. [ABSTRACT FROM AUTHOR]

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 {Mo120Ce6} to afford two half-closed gigantic molybdenum blue clusters {Mo180} (1) and {Mo130Ce6} (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 {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. [ABSTRACT FROM AUTHOR]