Polyoxometalates (POMs) are complex inorganic, anionic structures made of metal cations surrounded by oxo anions. These metals include tungsten (VI), vanadium (V), molybdenum (VI), and many more. POMs exist in a range of structures and sizes, resulting in discrete clusters. POMs are relatively easy to prepare and modify, leading to their application in a variety of areas, including medications, catalytic effects, substitution reactions, and much more. Traditionally, POMs contain W=O terminal bonds, such as in [PW12O40] 3-. We have prepared a polyoxonitridometalate, [PW12O39N]4-,containing a single WN triple bond. This functionalization could result in new linkages between new POMs, allowing for new materials to be created. Polyoxonitridometalates could also serve as structural and electronic models for the more complex extended solid-state metal oxonitrides, with the benefit of being able to control the substitution location for the nitrogen. The figure below shows the relationship between oxides, nitrides, oxonitrides, and polyoxonitridometalates. Oxygen and nitrogen are next to each other on the periodic table, and O2- and N3-are isoelectronic. With similar size, it would appear to be an easy exchange between the two yet this is not what was observed. The WN triple bond was generated from the preparation of WNCl3 and coordinated to [PW11O39]7- in a glove box due to the sensitivity of WNCl3 to hydrolysis with water in the air. Following formation and isolation of [PW12O39N]4-, it was characterized by FT-IR spectroscopy, 31P NMR spectroscopy, and X-ray crystallography. Determining the position of the WN moiety in the anionic cluster proved challenging, and other crystallographic techniques may need to be employed to differentiate the terminal oxygens from the terminal nitrogen.

Preparation and characterization of a polyoxonitridometalate

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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