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Updated: Jun 24, 2025
Hyperspectral Imaging as a Tool to Study Optical Anisotropy in Lanthanide-Based Molecular Single Crystals
Published on: April 14, 2020
Hourglass-Shaped Homo- and Heteronuclear Nonanuclear Lanthanide Clusters: Structures, Magnetism, Photoluminescence,
Priya Pandey1, Deepanshu Chauhan1, Mrinalini G Walawalkar1
1Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.
Abstract:
Synthesis of nonameric cationic clusters [Dy9(acac)16(μ3-OH)8(μ4-OH)2]OH·6H2O (1), [Dy8Tb (acac)16(μ3-OH)8(μ4-OH)2]OH·2H2O (2), and [Gd9(acac)16(μ3-OH)8(μ4-OH)2]OH·6H2O (3) (acac = acetylacetonate) is reported. The emission spectrum of 1 shows Dy(III) ion characteristic bands assignable to the 4F9/2 → 6H (J = 15/2 to 9/2) transitions. Emission due to both Dy(III) and Tb(III) ions is observed for 2 in the visible range, with Tb(III) specific bands appearing due to the 5D4 → 7F (J = 6, 4, and 3) transitions. Cluster 3 exhibits a significant magnetocaloric effect (MCE), with -ΔSm values increasing with decrease in temperature and increase in field, reaching -ΔSmmax = 20.98 J kg-1 K-1 at 2 K and 9 T. Isotropic magnetic coupling constants (Js) in 3 derived from density functional theory (DFT) calculations reveal that the exchange interactions are antiferromagnetic and weak. Compound 3 possesses S = 7/2 ground state arising from the central Gd(III) ion along with several nested excited states due to competing antiferromagnetic interactions that yield reasonably large MCE values. Utilizing computed exchange coupling interactions, we have performed ab initio CASSCF/RASSI-SO/POL_ANISO calculations on antiferromagnetic 1 and 2 to estimate the exchange interactions using the Lines model. For 2, Dy(III)···Tb(III) exchange interactions were extracted for the first time and were found to be weakly antiferromagnetically coupled.
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