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Weber, Dominik; Huber, Manop; Gorelik, Tatiana E.; Abakumov, Artem M.; Becker, Nils; Niehaus, Oliver; Schwickert, Christian; Culver, Sean P.; Boysen, Hans; Senyshyn, Anatoliy; Poettgen, Rainer; Dronskowski, Richard; Ressler, Thorsten; Kolb, Ute and Lerch, Martin (2017): Molybdenum Oxide Nitrides of the Mo-2(O,N,square)(5) Type: On the Way to Mo2O5. In: Inorganic Chemistry, Vol. 56, No. 15: pp. 8782-8792

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Abstract

Blue-colored molybdenum oxide nitrides of the Mo-2(O,N,square)(5) type were synthesized by direct nitridation of commercially available molybdenum trioxide with a mixture of gaseous ammonia and oxygen. Chemical composition, crystal structure, and stability of the obtained and hitherto unknown compounds are studied extensively. The average oxidation state of +5 for molybdenum is proven by Mo K near-edge X-ray absorption spectroscopy;the magnetic behavior is in agreement with compounds exhibiting (MoO6)-O-v units. The new materials are stable up to similar to 773 K in an inert gas atmosphere. At higher temperatures, decomposition is observed. X-ray and neutron powder diffraction, electron diffraction, and high-resolution transmission electron microscopy reveal the structure to be related to VNb9O24.9-type phases, however, with severe disorder hampering full structure determination. Still, the results demonstrate the possibility of a future synthesis of the potential binary oxide Mo2O5. On the basis of these findings, a tentative suggestion on the crystal structure of the potential compound Mo2O5, backed by electronic-structure and phonon calculations from first principles, is given.

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