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Ti{sub 2}Nb{sub 6}O{sub 12}, a novel niobium oxide cluster compound with Chevrel phase intercluster connectivity type

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/ja990759e· OSTI ID:20000039

The formation of metal-metal bonds is a characteristic feature of compounds containing early transition metals in low oxidation states. In these metal-rich compounds, discrete or condensed octahedral metal clusters are commonly encountered. The niobium oxide cluster compound Ti{sub 2}Nb{sub 6}O{sub 12} was synthesized from NbO, NbO{sub 2}, and TiO{sub 2} in the presence of NaF melt at 950 C. It crystallizes in an original structure type based on octahedral cluster units (Nb{sub 6}O{sub 12}{sup i})O{sub 6}{sup a}. The clusters connect to each other through outer-inner linkages to form a three-dimensional framework containing cubeoctahedral cavities. The cluster connectivity pattern in Ti{sub 2}Nb{sub 6}O{sub 12} and intercluster metal-metal distances are similar to those found in the Chevrel phases. The Ti{sup 4+} ions have a distorted octahedral environment formed by the oxide ligands belonging to the clusters. Band structure calculations indicate that the lowest unoccupied band in Ti{sub 2}NB{sub 6}O{sub 12} resembles the conduction band in the superconducting Chevrel phases.

Research Organization:
Wake Forest Univ., Winston-Salem, NC (US)
OSTI ID:
20000039
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 29 Vol. 121; ISSN JACSAT; ISSN 0002-7863
Country of Publication:
United States
Language:
English

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