| Autor: |
Froeschke, Samuel, Bestha, Kranthi Kumar, Fucke, Rico, Schiemenz, Sandra, Popov, Alexey, Naumann, Marco, Knupfer, Martin, Giebeler, Lars, Wolf, Daniel, Kizhake Malayil, Ranjith Kumar, Sivan, Saramgi Chencheriparambil, Grafe, Hans-Joachim, Gräßler, Nico, Corredor, Laura T., Wolter, Anja U. B., Büchner, Bernd, Schmidt, Peer, Hampel, Silke |
| Zdroj: |
Chemistry of Materials; May 2024, Vol. 36 Issue: 9 p4240-4253, 14p |
| Abstrakt: |
In this work, we apply the concept of solid solutions to the two 2D transition metal trihalides CrCl3and MoCl3. While CrCl3belongs to the magnetically active CrX3family, the magnetism in MoCl3is intrinsically suppressed by the formation of aligned Mo–Mo dimers, which also distort the regular honeycomb lattice that is typical for the 2D transition metal trihalides. We report suitable synthesis conditions for the gapless solid solution and crystal growth by chemical vapor transport. The CrCl3–MoCl3solid solution was initially synthesized at 650 °C for 100 h under addition of MoCl5as mineralizer, and bulk crystals were subsequently grown by vapor transport in a temperature gradient from 600 °C → 550 °C for 60 h. The obtained solid solution exhibits multiple composition-dependent phase transitions at room temperature, as confirmed by powder X-ray diffraction measurements. The possible presence of Mo–Mo dimers in the solid solution was further investigated by infrared, Raman, electron energy loss, and nuclear quadrupole resonance spectroscopies. The combined results indicate that the Mo–Mo dimers are present over a wide range of compositions. Their orientation changes from parallel alignment for compositions from 70% ≤ c(Mo3+) ≤ 100% to random orientation for samples with c(Mo3+) < 70% content, which significantly affects the course of lattice parameters. Finally, the magnetic properties of the powder samples show a correlation between the Mo3+content and the transition temperature into the low-temperature phase. |
| Databáze: |
Supplemental Index |
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