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Electron transfer phase transition and oxidization process in NaCo0.44Mn0.56[Fe(CN)6]0.90 (0.00 ≤ x ≤ 1.60)
Hiroki Iwaizumi1, Takayuki Shibata2, Yutaka Moritomo1,3,4
1Graduate School of Pure & Applied Science, University of Tsukuba, Tennodai 1-1-1, Tsukuba, Ibaraki 305-7571, Japan. moritomo.yutaka.gf@u.tsukba.ac.jp.
Chemical Communications (Cambridge, England)
|November 17, 2021
Summary
This study reveals an electron transfer phase transition in NaCo0.44Mn0.56[Fe(CN)6]0.90 across a broad sodium concentration range. This transition alters the oxidation states of cobalt, manganese, and iron.
Area of Science:
- Materials Science
- Solid State Chemistry
- Coordination Chemistry
Background:
- Understanding phase transitions in complex inorganic compounds is crucial for developing new functional materials.
- Sodium-containing coordination compounds exhibit diverse electronic and magnetic properties influenced by sodium concentration.
Purpose of the Study:
- To investigate the phase diagram and electron transfer (ET) phase transition of NaCo0.44Mn0.56[Fe(CN)6]0.90.
- To determine the range of sodium concentration (x) over which the ET phase transition occurs.
- To analyze the changes in oxidation states of Co, Mn, and Fe during the phase transition.
Main Methods:
- Synthesis and characterization of NaCo0.44Mn0.56[Fe(CN)6]0.90 for 0.00 ≤ x ≤ 1.60.
- Analysis of the phase diagram and identification of the electron transfer phase transition region.
- Application of an extended electron transfer model to describe the concentration of Fe species.
Main Results:
- An electron transfer (ET) phase transition was observed in the wide concentration range of 0.19 ≤ x ≤ 1.38.
- The extended ET model successfully reproduced the variations in [Fe2+(CN)6]4- and [Fe3+(CN)6]3- concentrations at the transition.
- The ET phase transition reversed the oxidation order of Co, Mn, and Fe from Co-Mn-Fe (low T) to Fe-Mn-Co (high T).
Conclusions:
- The compound NaCo0.44Mn0.56[Fe(CN)6]0.90 exhibits a significant electron transfer phase transition driven by sodium concentration.
- The observed transition provides insights into the complex interplay between structure, oxidation states, and electronic properties in Prussian blue analogues.
- This research contributes to the understanding of tunable electronic properties in coordination materials through controlled doping and stoichiometry.
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