4.7 Article

Solid-Phase Quasi-Intramolecular Redox Reaction of [Ag(NH3)2]MnO4: An Easy Way to Prepare Pure AgMnO2

Journal

INORGANIC CHEMISTRY
Volume 60, Issue 6, Pages 3749-3760

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.0c03498

Keywords

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Funding

  1. European Structural and Investments Funds [GINOP-2.3.3-15-2016-0009]
  2. European Union [VEKOP-2.3.2-16-2017-00013, GINOP-2.2.1-15-2017-00084]
  3. State of Hungary
  4. European Regional Development Fund
  5. Hungarian National Research Fund (OTKA) [SNN 118012]
  6. Ministry of Education, Science and Technological Development of the Republic of Serbia [451-03-68/2020-14/200125]
  7. Janos Bolyai Research Scholarship
  8. New National Excellence program of the Ministry for Innovation and Technology [UNKP-20-5-PE-7]
  9. NRDI [K 124212, TNN_16 123631]
  10. BME Nanotechnology and Materials Science TKP2020 IE grant of NKFIH Hungary [BME IE-NAT TKP2020]
  11. [GINOP-2.3.2-15-2016-00053]

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Two monoclinic polymorphs of [Ag(NH3)(2)]MnO4 containing a unique coordination mode of permanganate ions were prepared, with the high-temperature polymorph used as a precursor to synthesize pure AgMnO2. During thermal decomposition, the hydrogen bonds between permanganate ions and ammonia atoms induced a solid-phase quasi-intramolecular redox reaction, leading to the formation of finely dispersed elementary silver, amorphous MnOx compounds, and gases such as H2O, N-2, and NO. Subsequent annealing of the primary decomposition product resulted in the formation of amorphous silver manganese oxides, which transformed into AgMnO2 at higher temperatures.
Two monoclinic polymorphs of [Ag(NH3)(2)]MnO4 containing a unique coordination mode of permanganate ions were prepared, and the high-temperature polymorph was used as a precursor to synthesize pure AgMnO2. The hydrogen bonds between the permanganate ions and the hydrogen atoms of ammonia were detected by IR spectroscopy and single-crystal X-ray diffraction. Under thermal decomposition, these hydrogen bonds induced a solid-phase quasi-intramolecular redox reaction between the [Ag(NH3)(2)](+) cation and MnO4- anion even before losing the ammonia ligand or permanganate oxygen atom. The polymorphs decomposed into finely dispersed elementary silver, amorphous MnOx compounds, and H2O, N-2 and NO gases. Annealing the primary decomposition product at 573 K, the metallic silver reacted with the manganese oxides and resulted in the formation of amorphous silver manganese oxides, which started to crystallize only at 773 K and completely transformed into AgMnO2 at 873 K.

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