From Serendipity to Rational Design: Tuning the Blue Trigonal Bipyramidal Mn3+ Chromophore to Violet and Purple through Application of Chemical Pressure
| Autor: | Simon Lorger, Munirpallam A. Subramanian, Arthur W. Sleight, Jun Li, Judith K. Stalick |
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| Rok vydání: | 2016 |
| Předmět: |
business.industry
chemistry.chemical_element 02 engineering and technology Yttrium Crystal structure Chromophore 010402 general chemistry 021001 nanoscience & nanotechnology 01 natural sciences Magnetic susceptibility 0104 chemical sciences Inorganic Chemistry Crystallography Trigonal bipyramidal molecular geometry Optics chemistry Crystal field theory Physical and Theoretical Chemistry 0210 nano-technology business Hue Solid solution |
| Zdroj: | Inorganic Chemistry. 55:9798-9804 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/acs.inorgchem.6b01639 |
| Popis: | We recently reported that an allowed d–d transition of trigonal bipyramidal (TBP) Mn3+ is responsible for the bright blue color in the YIn1–xMnxO3 solid solution. The crystal field splitting between a′(dz2) and e′(dx2–y2, dxy) energy levels is very sensitive to the apical Mn–O distance. We therefore applied chemical pressure to compress the apical Mn–O distance in YIn1–xMnxO3, 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 Ti4+/Zn2+ and Al3+ onto the TBP In/Mn site, which yielded novel violet/purple phases. The general formula is YIn1–x–2y–zMnxTiyZnyAlzO3 (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 shor... |
| Databáze: | OpenAIRE |
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