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Stabilization of a Tetrahedral (Mn5+O4) Chromophore in Ternary Barium Oxides as a Strategy toward Development of New Turquoise/Green-Colored Pigments

Laha, Sourav and Tamilarasan, Subramani and Natarajan, Srinivasan and Gopalakrishnan, Jagannatha (2016) Stabilization of a Tetrahedral (Mn5+O4) Chromophore in Ternary Barium Oxides as a Strategy toward Development of New Turquoise/Green-Colored Pigments. In: INORGANIC CHEMISTRY, 55 (7). pp. 3508-3514.

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Official URL: http://dx.doi.org/10.1021/acs.inorgchem.5b02957

Abstract

An experimental investigation of the stabilization of the turquoise-colored chrornophore (Mn5+O4) in various oxide hosts, viz., A(3)(VO4)(2) (A = Ba, Sr, Ca), YVO4, and Ba2MO4 (M = Ti, Si), has been carried out. The results reveal that substitution of Mn5+O4 occurs in Ba-3(VO4)(2) forming the entire solid solution series Ba-3(V1-x MnxO4)(2) (0 < x <= 1.0), while with the corresponding strontium derivative, only up to about 10% of Mn5+O4 substitution is possible. Ca-3(VO4)(2) and YVO4 do not stabilize Mn5+O4 at all. With Ba2MO4 (M = Ti, Si), we could prepare only partially substituted materials, Ba2M1-xMn5+O4+x/2 for x up to 0.15, that are turquoise-colored. We rationalize the results that a large stabilization of the O 2p-valence band states occurs in the presence of the electropositive barium that renders the Mn5+ oxidation state accessible in oxoanion compounds containing PO43-, VO43-, etc. By way of proof-of-concept, we synthesized new turquoise-colored Mn5+O4 materials, Ba-5(BO3)(MnO4)(2)Cl and Ba-5(BO3)(PO4)(MnO4)Cl, based on the apatite-Ba-5(PO4)(3)Cl-structure.

Item Type: Journal Article
Additional Information: Copy right for this article belongs to the AMER CHEMICAL SOC, 1155 16TH ST, NW, WASHINGTON, DC 20036 USA
Department/Centre: Division of Chemical Sciences > Solid State & Structural Chemistry Unit
Depositing User: Id for Latest eprints
Date Deposited: 11 May 2016 05:55
Last Modified: 11 May 2016 05:55
URI: http://eprints.iisc.ac.in/id/eprint/53772

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