Monoclinic LaGa1−xMnxGe2O7: a new blue chromophore based on Mn3+in the trigonal bipyramidal coordination with longer apical bond lengths

Divya, S.; Rao, P. Prabhakar; Sameera, S.; James, Vineetha; Raj, Athira K. V.

doi:10.1039/c5ra01714a

Cited by 13 publications

(1 citation statement)

References 20 publications

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“…Bluish-purple or violet colors can also be produced by introducing Mn 3+ into the TBP sites of YbFe 2 O 4 -related structures . Our work has motivated others to search for the TBP Mn 3+ chromophore in different structures. , …”

Section: Introductionmentioning

confidence: 86%

From Serendipity to Rational Design: Tuning the Blue Trigonal Bipyramidal Mn³⁺ Chromophore to Violet and Purple through Application of Chemical Pressure

Lorger

Stalick

et al. 2016

Inorg. Chem.

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We recently reported that an allowed d-d transition of trigonal bipyramidal (TBP) Mn is responsible for the bright blue color in the YInMnO solid solution. The crystal field splitting between a'(d) and e'(d, d) energy levels is very sensitive to the apical Mn-O distance. We therefore applied chemical pressure to compress the apical Mn-O distance in YInMnO, move the allowed d-d transition to higher energy, and thereby tune the color from blue to violet/purple. This was accomplished by substituting smaller cations such as Ti/Zn and Al onto the TBP In/Mn site, which yielded novel violet/purple phases. The general formula is YInMnTiZnAlO (x = 0.005-0.2, y = 0.1-0.4, and z ≤ 0.1), where the color darkens with the increasing amount of Mn. Higher y or small additions of Al provide a more reddish hue to the resulting purple colors. Substituting other rare earth cations for Y has little impact on color. Crystal structure analysis by neutron powder diffraction confirms a shorter apical Mn-O distance compared with that in the blue YInMnO. Magnetic susceptibility measurements verify the 3+ oxidation state for Mn. Diffuse reflection spectra were obtained over the wavelength region 200-2500 nm. All samples show excellent near-infrared reflectance comparable to that of commercial TiO, making them ideal for cool pigment applications such as energy efficient roofs of buildings and cars where reducing solar heat to save energy is desired. In a comparison with commercial purple pigments, such as Co(PO), our pigments are much more thermally stable and chemically inert, and are neither toxic nor carcinogenic.

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Section: Introductionmentioning

confidence: 86%

From Serendipity to Rational Design: Tuning the Blue Trigonal Bipyramidal Mn³⁺ Chromophore to Violet and Purple through Application of Chemical Pressure

Lorger

Stalick

et al. 2016

Inorg. Chem.

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ChemInform Abstract: Monoclinic LaGa_1‐xMn_xGe₂O₇: A New Blue Chromophore Based on Mn³⁺ in the Trigonal Bipyramidal Coordination with Longer Apical Bond Lengths.

et al. 2015

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Lengths. -Blue pigments of LaGa 1-xMnxGe2O7 are prepared by firing La2O3, Ga2O3, Mn2O3, and GeO2 in stoichiometric amounts using H3BO3 as a flux (Pt crucible, 1100 C, 6 h). Substitution of Mn 3+ in LaGaGe2O7 changes the color from white (x = 0) to blue (x = 0.1-0.4) which is discussed in terms of the presence of a diminished symmetry-allowed transition at 1.7 eV and an increased symmetry-forbidden transition at 2.1 eV arising from prolonged Mn-O apical bonds. Temperature dependent magnetic susceptibility measurements reveal the presence of Mn 3+ along with Mn 4+ which also agrees with lattice parameter variations. -(SARASWATHY, D.; RAO*, P. P.; SAMEERA, S.; JAMES, V.; RAJ, A. K. V.; RSC Adv. 5 (2015) 35, 27278-27281, http://dx.

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Exploring the Colour of 3d Transition‐Metal Ions in Trigonal Bipyramidal Coordination: Identification of Purple‐Blue (CoO₅) and Beige‐Red (NiO₅) Chromophores in LiMgBO₃Host

et al. 2015

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Monoclinic LaGa_1−xMn_xGe₂O₇: a new blue chromophore based on Mn³⁺in the trigonal bipyramidal coordination with longer apical bond lengths

Abstract: Blue pigments of LaGa1‐xMnxGe2O7 are prepared by firing La2O3, Ga2O3, Mn2O3, and GeO2 in stoichiometric amounts using H3BO3 as a flux (Pt crucible, 1100 °C, 6 h).

Cited by 13 publications

References 20 publications

From Serendipity to Rational Design: Tuning the Blue Trigonal Bipyramidal Mn³⁺ Chromophore to Violet and Purple through Application of Chemical Pressure

From Serendipity to Rational Design: Tuning the Blue Trigonal Bipyramidal Mn³⁺ Chromophore to Violet and Purple through Application of Chemical Pressure

ChemInform Abstract: Monoclinic LaGa_1‐xMn_xGe₂O₇: A New Blue Chromophore Based on Mn³⁺ in the Trigonal Bipyramidal Coordination with Longer Apical Bond Lengths.

Exploring the Colour of 3d Transition‐Metal Ions in Trigonal Bipyramidal Coordination: Identification of Purple‐Blue (CoO₅) and Beige‐Red (NiO₅) Chromophores in LiMgBO₃Host

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Monoclinic LaGa1−xMnxGe2O7: a new blue chromophore based on Mn3+in the trigonal bipyramidal coordination with longer apical bond lengths

Abstract: Blue pigments of LaGa1‐xMnxGe2O7 are prepared by firing La2O3, Ga2O3, Mn2O3, and GeO2 in stoichiometric amounts using H3BO3 as a flux (Pt crucible, 1100 °C, 6 h).

Cited by 13 publications

References 20 publications

From Serendipity to Rational Design: Tuning the Blue Trigonal Bipyramidal Mn3+ Chromophore to Violet and Purple through Application of Chemical Pressure

From Serendipity to Rational Design: Tuning the Blue Trigonal Bipyramidal Mn3+ Chromophore to Violet and Purple through Application of Chemical Pressure

ChemInform Abstract: Monoclinic LaGa1‐xMnxGe2O7: A New Blue Chromophore Based on Mn3+ in the Trigonal Bipyramidal Coordination with Longer Apical Bond Lengths.

Exploring the Colour of 3d Transition‐Metal Ions in Trigonal Bipy­ramidal Coordination: Identification of Purple‐Blue (CoO5) and Beige‐Red (NiO5) Chromophores in LiMgBO3Host

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Monoclinic LaGa_1−xMn_xGe₂O₇: a new blue chromophore based on Mn³⁺in the trigonal bipyramidal coordination with longer apical bond lengths

From Serendipity to Rational Design: Tuning the Blue Trigonal Bipyramidal Mn³⁺ Chromophore to Violet and Purple through Application of Chemical Pressure

From Serendipity to Rational Design: Tuning the Blue Trigonal Bipyramidal Mn³⁺ Chromophore to Violet and Purple through Application of Chemical Pressure

ChemInform Abstract: Monoclinic LaGa_1‐xMn_xGe₂O₇: A New Blue Chromophore Based on Mn³⁺ in the Trigonal Bipyramidal Coordination with Longer Apical Bond Lengths.

Exploring the Colour of 3d Transition‐Metal Ions in Trigonal Bipyramidal Coordination: Identification of Purple‐Blue (CoO₅) and Beige‐Red (NiO₅) Chromophores in LiMgBO₃Host