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Layered RbLnGeS4 (ln = Ce, Pr, Nd, Sm, Gd) : Crystal structures, Rb-site disorder–order transition, and structure–property correlations. / Sapov, Alexander A.; Tarasenko, Maria S.; Kuratieva, Natalia V. и др.
в: Journal of Solid State Chemistry, Том 363, 11.2026, стр. 126219.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Layered RbLnGeS4 (ln = Ce, Pr, Nd, Sm, Gd)
T2 - Crystal structures, Rb-site disorder–order transition, and structure–property correlations
AU - Sapov, Alexander A.
AU - Tarasenko, Maria S.
AU - Kuratieva, Natalia V.
AU - Syrokvashin, Mikhail M.
AU - Ryadun, Alexey A.
AU - Troitskii, Dmitry Y.
AU - Yushina, Irina V.
AU - Naumov, Nikolay G.
N1 - Alexander A. Sapov, Maria S. Tarasenko, Natalia V. Kuratieva, Mikhail M. Syrokvashin, Alexey A. Ryadun, Dmitry Y. Troitskii, Irina V. Yushina, Nikolay G. Naumov, Layered RbLnGeS4 (ln = Ce, Pr, Nd, Sm, Gd): crystal structures, Rb-site disorder–order transition, and structure–property correlations, Journal of Solid State Chemistry, Volume 363, 2026, 126219, ISSN 0022-4596, https://doi.org/10.1016/j.jssc.2026.126219. This work was supported by the Ministry of Science and Higher Education of the Russian Federation project FWUZ-2025-002.
PY - 2026/11
Y1 - 2026/11
N2 - Rare-earth thiogermanates built from isolated {GeS4} tetrahedra are attractive as optical host lattices, yet rubidium members remain insufficiently explored. Here we report the synthesis of the new members of the RbLnGeS4 series (Ln = Ce, Pr, Nd, Sm, Gd) by a high-temperature reactive flux route and their comprehensive structural and spectroscopic characterization. All compounds crystallize in the non-centrosymmetric orthorhombic space group P212121 and feature anionic [LnGeS4]− layers separated by interlayer Rb+ cations. Single-crystal X-ray diffraction reveals a split Rb position at room temperature, whereas low-temperature data together with DSC measurements indicate suppression of the rubidium positional disorder upon cooling, consistent with a kinetically limited order–disorder process. Raman spectra are dominated by modes of isolated {GeS4} tetrahedra and show systematic Ln–S-related shifts across the series. Diffuse reflectance spectra of representative compounds RbLnGeS4 (Ln = Pr, Gd) yield optical band gaps of ≥3.3 eV. In addition, Sm3+-doped RbGdGeS4 exhibits red f–f emission consistent with a low-symmetry Sm3+ environment in this host lattice.
AB - Rare-earth thiogermanates built from isolated {GeS4} tetrahedra are attractive as optical host lattices, yet rubidium members remain insufficiently explored. Here we report the synthesis of the new members of the RbLnGeS4 series (Ln = Ce, Pr, Nd, Sm, Gd) by a high-temperature reactive flux route and their comprehensive structural and spectroscopic characterization. All compounds crystallize in the non-centrosymmetric orthorhombic space group P212121 and feature anionic [LnGeS4]− layers separated by interlayer Rb+ cations. Single-crystal X-ray diffraction reveals a split Rb position at room temperature, whereas low-temperature data together with DSC measurements indicate suppression of the rubidium positional disorder upon cooling, consistent with a kinetically limited order–disorder process. Raman spectra are dominated by modes of isolated {GeS4} tetrahedra and show systematic Ln–S-related shifts across the series. Diffuse reflectance spectra of representative compounds RbLnGeS4 (Ln = Pr, Gd) yield optical band gaps of ≥3.3 eV. In addition, Sm3+-doped RbGdGeS4 exhibits red f–f emission consistent with a low-symmetry Sm3+ environment in this host lattice.
KW - редкоземельные элементы
KW - тиогерманаты
KW - рубидий
KW - рамановская спектроскопия
KW - спектроскопия диффузного отражения
KW - оптическая ширина запрещенной зоны
KW - фотолюминесценция Sm3+
KW - нецентросимметричные сульфиды
KW - переход порядок-беспорядок
KW - Rare-earth elements
KW - Thiogermanates
KW - Rubidium
KW - Raman spectroscopy
KW - Diffuse reflectance spectroscopy
KW - Optical band gap
KW - Sm3+ photoluminescence
KW - Non-centrosymmetric sulfides
KW - Order–disorder transition
UR - https://www.mendeley.com/catalogue/50f35183-0895-38e3-b004-8509a1ebcb63/
UR - https://www.scopus.com/pages/publications/105045287824
U2 - 10.1016/j.jssc.2026.126219
DO - 10.1016/j.jssc.2026.126219
M3 - Article
VL - 363
SP - 126219
JO - Journal of Solid State Chemistry
JF - Journal of Solid State Chemistry
SN - 0022-4596
ER -
ID: 82776653