Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 142, Issue 16, Pages 7295-7300Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.0c01486
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Funding
- Israel Science Foundation (ISF) [170/17]
- National Natural Science Foundation of China-ISF Joint Grant Program [3102/19]
- PBC-Israel
- Spanish Ministerio de Ciencia e Innovacion [CTQ2017-87269-P]
- Generalitat de Catalunya [2014SGR199]
- ICREA Foundation
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Among molecular building blocks, metal oxide cluster anions and their countercations provide multiple options for the self-assembly of functional materials. Currently, however, rational design concepts are limited to electrostatic interactions with metal or organic countercations or to the attachment and subsequent reactions of functionalized organic ligands. We now demonstrate that bridging mu-oxo linkages can be used to string together a bifunctional Keggin anion building block, [PNb2Mo10O40](5-) (1), the diniobium(V) analogue of [PV2Mo10O40](5-) (2). Induction of mu-oxo ligation between the Nb-V=O moieties of 1 in acetonitrile via step-growth polymerization gives linear polymers with entirely inorganic backbones, some comprising over 140 000 repeating units, each with a 3- charge, exceeding that of previously reported organic or inorganic polyelectrolytes. As the chain grows, its flexible mu-oxo-linked backbone, with associated countercations, coils into a compact 270 nm diameter spherical secondary structure as a result of electrostatic interactions not unlike those within ionic lattices. More generally, the findings point to new options for the rational design of multidimensional structures based on mu-oxo linkages between Nb-V=Ofunctionalized building blocks.
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