Abstract
AbstractWe 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.
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