A unique heteropolyoxotantalate (hetero-POTa) cluster [POTaO] (PTa) was first developed using pyrophosphate as a key to open the ultrastable skeleton of the classical Lindqvist-type [TaO] precursor. The PTa cluster can serve as a general and flexible secondary building unit to create a family of brand-new multidimensional POTa architectures. This work not only promotes the limited structural diversity of hetero-POTa but also provides a practical strategy for new extended POTa architectures.
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