Mn3+ in trigonal bipyramidal coordination: A new blue chromophore

Andrew E. Smith, Hiroshi Mizoguchi, Kris Delaney, Nicola A. Spaldin, Arthur W. Sleight, M. A. Subramanian

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102 Citations (Scopus)

Abstract

(Graph Presented) We show that trivalent manganese, Mn3+, imparts an intense blue color to oxides when it is introduced at dilution in trigonal bipyramidal coordination. Our optical measurements and first-principles density functional theory calculations indicate that the blue color results from an intense absorption in the red/green region. This absorption is due in turn to a symmetry-allowed optical transition between the valence-band maximum, composed of Mn 3dx2-y2,xy states strongly hybridized with O 2p x,y states, and the narrow Mn 3dz2-based conduction-band minimum. We begin by demonstrating and explaining the effect using a well-defined prototype system: the hexagonal YMnO3-YInO3 solid solution. We then show that the behavior is a general feature of diluted Mn3+ in this coordination environment.

Original languageEnglish
Pages (from-to)17084-17086
Number of pages3
JournalJournal of the American Chemical Society
Volume131
Issue number47
DOIs
Publication statusPublished - 2 Dec 2009
Externally publishedYes

Cite this

Smith, A. E., Mizoguchi, H., Delaney, K., Spaldin, N. A., Sleight, A. W., & Subramanian, M. A. (2009). Mn3+ in trigonal bipyramidal coordination: A new blue chromophore. Journal of the American Chemical Society, 131(47), 17084-17086. https://doi.org/10.1021/ja9080666