Pigments and Near-Infrared Phosphors Based on Mn5.

The optical properties of Mn⁵⁺ ions, which are responsible for the intense green-turquoise-blue coloration of Mn⁵⁺-based pigments and the near-infrared emission of phosphors, are the focus of this article. Mn⁵⁺ ions enter crystalline matrices in four-fold coordinated positions and can maintain their 5+ valence state when crystalline hosts meet the conditions described in this work. Mn⁵⁺ ions have [Ar]3d² electronic configuration and always experience a strong crystal field due to a high electric charge; therefore, their lower electronic states have the ³A₂ < ¹E < ¹A₁ < ³T₂ < ³T₁ progression in energy. We present the properties of several Mn⁵⁺-based pigments and discuss the electronic transitions responsible for their coloration. Specifically, we show that the color is determined by the spin-allowed ³A₂ → ³T₁(³F) absorption, which extends across the orange-red-deep red spectral region and is strongly influenced by crystal field strength. The narrow-band emission Mn⁵⁺-activated near-infrared phosphors arise from the spin-forbidden ¹E → ³A₂ transition, whose energy is independent of the crystal field strength and determined by the nephelauxetic effect. We demonstrate the linear relationship between ¹E state energy and the nephelauxetic parameter β₁ using Racah parameter literature data for Mn⁵⁺ phosphors. Lastly, we address the recent applications of these Mn⁵⁺ phosphors in luminescence thermometry.