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S = 1/2 Trimers Driving the Magnetism in Two Li2Cu3(SeO3)4 Polymorphs
Shoushuang Li1, Mingming Hang1, Minfeng Lü1
1School of Materials Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang212100, Jiangsu, China.
Two new lithium copper selenite polymorphs, α and β, were synthesized. Despite different structures, both exhibit S=1/2 magnetic subunits, leading to magnetic ordering at low temperatures.
Area of Science:
- Solid-state chemistry
- Materials science
- Magnetism
Background:
- Lithium copper selenite compounds are of interest for their magnetic properties.
- Understanding structure-property relationships is crucial for designing new materials.
Purpose of the Study:
- To synthesize and characterize new polymorphs of Li2Cu3(SeO3)4.
- To investigate the magnetic properties and underlying interactions of these new phases.
Main Methods:
- Hydrothermal synthesis
- Single-crystal X-ray diffraction (XRD)
- Density Functional Theory (DFT+U) calculations
- Exact Diagonalization (ED) of the Heisenberg Hamiltonian
Main Results:
- Two new monoclinic polymorphs, α-Li2Cu3(SeO3)4 (P21/c) and β-Li2Cu3(SeO3)4 (P21/n), were identified.
- α-phase exhibits a 3D framework, while β-phase has 2D layers, yet both contain S=1/2 trimeric magnetic subunits.
- DFT+U and ED calculations revealed strong antiferromagnetic intratrimer couplings and weaker intertrimer exchanges, explaining magnetic ordering at TN ≈ 16 K (α) and TN ≈ 4 K (β).
Conclusions:
- The structural differences between α and β polymorphs do not prevent the formation of identical magnetic subunits.
- Intratrimer magnetic interactions are dominant, effectively creating S=1/2 macrospins that order at distinct low temperatures.
- This study provides insights into magnetic interactions in layered and framework copper-based materials.
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