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Structural and Magnetic Transitions Caused by Dimer Formation in the CrCl3–MoCl3 Solid Solution

  • In this work, we apply the concept of solid solutions to the two 2D transition metal trihalides CrCl3 and MoCl3. While CrCl3 belongs to the magnetically active CrX3 family, the magnetism in MoCl3 is 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–MoCl3 solid solution was initially synthesized at 650 °C for 100 h under addition of MoCl5 as 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 resonanceIn this work, we apply the concept of solid solutions to the two 2D transition metal trihalides CrCl3 and MoCl3. While CrCl3 belongs to the magnetically active CrX3 family, the magnetism in MoCl3 is 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–MoCl3 solid solution was initially synthesized at 650 °C for 100 h under addition of MoCl5 as 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.show moreshow less

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Author: Samuel FroeschkeORCiD, Kranthi Kumar Bestha, Rico Fucke, Sandra Schiemenz, Alexey PopovORCiD, Marco Naumann, Martin Knupfer, Lars GiebelerORCiD, Daniel WolfORCiD, Ranjith Kumar Kizhake Malayil, Saramgi Chencheriparambil Sivan, Hans-Joachim GrafeORCiD, Nico GräßlerORCiD, Laura T. Corredor, Anja U. B. Wolter, Bernd BüchnerORCiD, Peer SchmidtORCiD, Silke HampelORCiD
DOI:https://doi.org/10.1021/acs.chemmater.3c03109
ISSN:0897-4756
ISSN:1520-5002
Title of the source (English):Chemistry of Materials
Document Type:Scientific journal article peer-reviewed
Language:English
Year of publication:2024
Volume/Year:36
Issue number:9
First Page:4240
Last Page:4253
Faculty/Chair:Fakultät 2 Umwelt und Naturwissenschaften / FG Anorganische Chemie
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