Crystal Structures, Optical Behavior, and Magnetic Properties in Hydrated Lanthanide Iron Sulfates

Chloe Jones; Silu Huang; Tyler L. Spano; Eric A. Gabilondo; Mohammed Al-Fahdi; Kara Trim; Mary Douglas; Rongying Jin; Andrew Miskowiec; P. Shiv Halasyamani; Ming Hu; Jie Ling

doi:10.1021/acs.inorgchem.5c04526

Crystal Structures, Optical Behavior, and Magnetic Properties in Hydrated Lanthanide Iron Sulfates

Chloe Jones
, Silu Huang
, Tyler L. Spano
, Eric A. Gabilondo
, Mohammed Al-Fahdi
, Kara Trim
, Mary Douglas
, Rongying Jin
, Andrew Miskowiec
, P. Shiv Halasyamani
, Ming Hu
, Jie Ling

Materials & Chemistry Group

Research output: Contribution to journal › Article › peer-review

Abstract

Single crystals of LnFe(SO₄)₃(H₂O)₂ (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm; compounds 1–11) and LnFe(SO₄)₃(H₂O) (Ln = Tm, Yb, Lu; compounds 12–14) were synthesized under hydrothermal conditions. Single-crystal X-ray diffraction (SCXRD) analysis revealed that the dihydrated compounds (1–11) crystallize in centrosymmetric (CS) structures, with the lanthanide ions adopting eight-coordinate geometries. In contrast, the monohydrated compounds (12–14) exhibit noncentrosymmetric (NCS) structures, where the lanthanide ions are seven-coordinated. Vibrating sample magnetometry (VSM) confirmed that compounds 2, 4, and 7–11 are paramagnetic below 400 K, with compound 8 displaying the highest magnetic susceptibility. Compounds 1, 5, 6, 13, and 14 show a sharp increase in magnetic susceptibility at Néel temperatures (T_N) of approximately 72, 76, 70, 58, and 56 K, respectively, indicating antiferromagnetic ordering. High-temperature magnetic susceptibility measurements further support the presence of antiferromagnetic transitions in these compounds. Second harmonic generation (SHG) measurements showed that the noncentrosymmetric Yb (compound 13) and Lu (compound 14) compounds exhibit SHG intensities of 0.3× and 1.6× that of potassium dihydrogen phosphate (KDP), respectively.

Original language	English
Pages (from-to)	2173-2183
Number of pages	11
Journal	Inorganic Chemistry
Volume	65
Issue number	4
DOIs	https://doi.org/10.1021/acs.inorgchem.5c04526
State	Published - Feb 2 2026

Funding

J.L. acknowledges financial support from the NSF EPSCoR Research Fellow Program (Award No. 2429504) and the Alabama Graduate Research Scholars Program (GRSP), funded through the Alabama Commission on Higher Education and administered by Alabama EPSCoR. R.J. acknowledges support from the U.S. Department of Energy, Office of Science, under Grant No. DE-SC0024501. E.A.G. thanks the Welch Foundation (Grant E-1457) for its support. M.H. thanks Theia, an AI-focused HPC cluster at the University of South Carolina supported by the NSF (Award No. 2320292).

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10.1021/acs.inorgchem.5c04526

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@article{027632deeaf543059667a4613d0a205e,

title = "Crystal Structures, Optical Behavior, and Magnetic Properties in Hydrated Lanthanide Iron Sulfates",

abstract = "Single crystals of LnFe(SO4)3(H2O)2 (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm; compounds 1–11) and LnFe(SO4)3(H2O) (Ln = Tm, Yb, Lu; compounds 12–14) were synthesized under hydrothermal conditions. Single-crystal X-ray diffraction (SCXRD) analysis revealed that the dihydrated compounds (1–11) crystallize in centrosymmetric (CS) structures, with the lanthanide ions adopting eight-coordinate geometries. In contrast, the monohydrated compounds (12–14) exhibit noncentrosymmetric (NCS) structures, where the lanthanide ions are seven-coordinated. Vibrating sample magnetometry (VSM) confirmed that compounds 2, 4, and 7–11 are paramagnetic below 400 K, with compound 8 displaying the highest magnetic susceptibility. Compounds 1, 5, 6, 13, and 14 show a sharp increase in magnetic susceptibility at N{\'e}el temperatures (TN) of approximately 72, 76, 70, 58, and 56 K, respectively, indicating antiferromagnetic ordering. High-temperature magnetic susceptibility measurements further support the presence of antiferromagnetic transitions in these compounds. Second harmonic generation (SHG) measurements showed that the noncentrosymmetric Yb (compound 13) and Lu (compound 14) compounds exhibit SHG intensities of 0.3× and 1.6× that of potassium dihydrogen phosphate (KDP), respectively.",

author = "Chloe Jones and Silu Huang and Spano, \{Tyler L.\} and Gabilondo, \{Eric A.\} and Mohammed Al-Fahdi and Kara Trim and Mary Douglas and Rongying Jin and Andrew Miskowiec and Halasyamani, \{P. Shiv\} and Ming Hu and Jie Ling",

note = "Publisher Copyright: {\textcopyright} 2026 The Authors. Published by American Chemical Society",

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doi = "10.1021/acs.inorgchem.5c04526",

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TY - JOUR

T1 - Crystal Structures, Optical Behavior, and Magnetic Properties in Hydrated Lanthanide Iron Sulfates

AU - Jones, Chloe

AU - Huang, Silu

AU - Spano, Tyler L.

AU - Gabilondo, Eric A.

AU - Al-Fahdi, Mohammed

AU - Trim, Kara

AU - Douglas, Mary

AU - Jin, Rongying

AU - Miskowiec, Andrew

AU - Halasyamani, P. Shiv

AU - Hu, Ming

AU - Ling, Jie

PY - 2026/2/2

Y1 - 2026/2/2

N2 - Single crystals of LnFe(SO4)3(H2O)2 (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm; compounds 1–11) and LnFe(SO4)3(H2O) (Ln = Tm, Yb, Lu; compounds 12–14) were synthesized under hydrothermal conditions. Single-crystal X-ray diffraction (SCXRD) analysis revealed that the dihydrated compounds (1–11) crystallize in centrosymmetric (CS) structures, with the lanthanide ions adopting eight-coordinate geometries. In contrast, the monohydrated compounds (12–14) exhibit noncentrosymmetric (NCS) structures, where the lanthanide ions are seven-coordinated. Vibrating sample magnetometry (VSM) confirmed that compounds 2, 4, and 7–11 are paramagnetic below 400 K, with compound 8 displaying the highest magnetic susceptibility. Compounds 1, 5, 6, 13, and 14 show a sharp increase in magnetic susceptibility at Néel temperatures (TN) of approximately 72, 76, 70, 58, and 56 K, respectively, indicating antiferromagnetic ordering. High-temperature magnetic susceptibility measurements further support the presence of antiferromagnetic transitions in these compounds. Second harmonic generation (SHG) measurements showed that the noncentrosymmetric Yb (compound 13) and Lu (compound 14) compounds exhibit SHG intensities of 0.3× and 1.6× that of potassium dihydrogen phosphate (KDP), respectively.

AB - Single crystals of LnFe(SO4)3(H2O)2 (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm; compounds 1–11) and LnFe(SO4)3(H2O) (Ln = Tm, Yb, Lu; compounds 12–14) were synthesized under hydrothermal conditions. Single-crystal X-ray diffraction (SCXRD) analysis revealed that the dihydrated compounds (1–11) crystallize in centrosymmetric (CS) structures, with the lanthanide ions adopting eight-coordinate geometries. In contrast, the monohydrated compounds (12–14) exhibit noncentrosymmetric (NCS) structures, where the lanthanide ions are seven-coordinated. Vibrating sample magnetometry (VSM) confirmed that compounds 2, 4, and 7–11 are paramagnetic below 400 K, with compound 8 displaying the highest magnetic susceptibility. Compounds 1, 5, 6, 13, and 14 show a sharp increase in magnetic susceptibility at Néel temperatures (TN) of approximately 72, 76, 70, 58, and 56 K, respectively, indicating antiferromagnetic ordering. High-temperature magnetic susceptibility measurements further support the presence of antiferromagnetic transitions in these compounds. Second harmonic generation (SHG) measurements showed that the noncentrosymmetric Yb (compound 13) and Lu (compound 14) compounds exhibit SHG intensities of 0.3× and 1.6× that of potassium dihydrogen phosphate (KDP), respectively.

UR - https://www.scopus.com/pages/publications/105029314822

U2 - 10.1021/acs.inorgchem.5c04526

DO - 10.1021/acs.inorgchem.5c04526

M3 - Article

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AN - SCOPUS:105029314822

SN - 0020-1669

VL - 65

SP - 2173

EP - 2183

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 4

ER -

Crystal Structures, Optical Behavior, and Magnetic Properties in Hydrated Lanthanide Iron Sulfates

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