NDLI: Relating highly distorted Jahn–Teller MnO<sub>6</sub> to colouration in manganese violet pigments

Content Provider	Royal Society of Chemistry (RSC)
Author	Wright, Adrian J. Begum, Yasmin
Copyright Year	2012
Abstract	‘Manganese violet’ pigments have been known for over 150 years, but are receiving renewed interest due to their non-toxicity and earth-abundant components. For the first time we report here a detailed study into the structural aspects that define the sought-after pigment properties of these materials. This work identified two polymorphs, designated as α- and β-NH4MnP2O7 that provide the strong colouration and compared them to a commercially available sample. Rietveld analysis of neutron powder diffraction data indicated that the α-polymorph crystallised in space group P21/c (a = 7.4252(3) Å, b = 9.6990(4) Å, c = 8.6552(4) Å and β = 105.627(3)°) and exhibited a highly distorted MnO6 coordination sphere. The apparent [2 + 2 + 2] distortion gives rise to the optical properties and appears to be driven, in part, by a “plasticity effect” in the Mn coordination induced by the pyrophosphate ligand. A second polymorph β-NH4MnP2O7 was found to crystallise in space group P (a = 8.4034(6) Å, b = 6.1498(4) Å, c = 6.1071(4) Å, α = 104.618(5)°, β = 100.748(5)° and γ = 96.802(6)°) and possessed similarly distorted MnO6 octahedra, but was found to differ from α-NH4MnP2O7 in the relative dimensions of the intersecting framework tunnels that contained the ammonium cations. UV-visible spectroscopy was used to characterise optical behaviour and a combination of TGA-MS and in situ high temperature X-ray powder diffraction were used to determine thermal decomposition pathways.
Starting Page	21110
Ending Page	21116
Page Count	7
File Format	HTM / HTML PDF
ISSN	09599428
Volume Number	22
Issue Number	39
Journal	Journal of Materials Chemistry
DOI	10.1039/c2jm33731b
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Rietveld Manganese violet Pigment Granulocyte Gerrit Rietveld Neutron diffraction Powder diffraction Space group Pyrophosphate Ligand Shapeshifting Octahedron Relative Dimensions Ammonium Ultraviolet\u2013visible spectroscopy
Content Type	Text
Resource Type	Article
Subject	Chemistry Materials Chemistry

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