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Synthesis and Crystal Structure of Rare-Earth Metal Compounds

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Inorganic Chemistry".

Deadline for manuscript submissions: 31 May 2025 | Viewed by 3971

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Guest Editor
Institute for Inorganic Chemistry, University of Stuttgart, 70569 Stuttgart, Germany
Interests: rare-earth metal compounds with mixed anions; luminescent materials; compounds with lone-pair oxoanions; hydroborates; thermoanalysis and phase and structure elucidation via X-ray diffraction
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Special Issue Information

Dear Colleagues,

In 1887, Sir William Crookes stated that "these elements perplex us in our researches, baffle us in our speculations, and haunt us in our very dreams. They stretch like an unknown sea before us—mocking, mystifying, and murmuring strange revelations and possibilities". These words—almost 140 years old yet still true—come from a pioneer in rare-earth metals, who contributed greatly to the commercial use of science. "The Fraternal Fifteen", as "mister rare earth" Karl A. Gschneidner Jr. called the most similar ones among them (Ln = La + Ce – Lu) in his 1966 book, were brought before a broader public in the 20th century, with their benefits demonstrated to humankind. Even now, with it being common knowledge that rare earths are “Neither Rare, Nor Earths” (BBC World Service, 2014), we encourage authors in the field to contribute to this Special Issue of Molecules with syntheses and crystal structures of rare-earth metal compounds (RE = Sc, Y, La – Lu) for readers in both academia and industry. Moreover, as children of the 21st century, we would happily include actinides (An = Ac + Th – Lr) in the realm of rare-earth elements.

Prof. Dr. Thomas Schleid
Guest Editor

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Keywords

  • synthesis
  • crystal structure
  • luminescence
  • magnetism
  • catalysts
  • optical properties

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Related Special Issue

Published Papers (4 papers)

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Research

19 pages, 9394 KiB  
Article
Dual Visible and NIR Emission, Mechanoluminescence, and Magnetic Properties of PPh4[LnL4] Chelates with Diphenyl-N-Benzoylamidophosphate
by Nataliia Kariaka, Dmytro Panasiuk, Viktor Trush, Sergii Smola, Nataliia Rusakova, Viktoriya Dyakonenko, Svitlana Shishkina, Aneta Lipa, Alina Bienko, Justyna Nasalska, Paula Gawryszewska and Volodymyr Amirkhanov
Molecules 2025, 30(6), 1245; https://doi.org/10.3390/molecules30061245 - 10 Mar 2025
Viewed by 473
Abstract
The design, synthesis, and study of lanthanide coordination compounds with luminescent and magnetic properties attractive in modern technologies is still a pressing and challenging task. In the present work, a series of coordination compounds of tetrakis-carbacylamidophosphate PPh4[LnL4] [...] Read more.
The design, synthesis, and study of lanthanide coordination compounds with luminescent and magnetic properties attractive in modern technologies is still a pressing and challenging task. In the present work, a series of coordination compounds of tetrakis-carbacylamidophosphate PPh4[LnL4] (where HL = diphenyl-N-benzoylamidophosphate) with several lanthanide ions such as NdIII, SmIII, DyIII, and TmIII was prepared and studied by X-ray analysis and luminescence spectroscopy at 293 and 77 K, as well as by magnetic measurements. Coordination compounds are not isostructural, but the type of coordination is the same. All of them have intense sensitized emission. PPh4[SmL4], PPh4[DyL4], and PPh4[TmL4] chelates are characterized by dual visible and infrared emission and mechanoluminescence. In addition, PPh4[DyL4] has multifunctional properties such as Vis and NIR emissions, brilliant mechanoluminescence and single-ion molecular magnet (SIM) properties. This type of compound holds great promise in multifunctional magnetic radiation converters. Full article
(This article belongs to the Special Issue Synthesis and Crystal Structure of Rare-Earth Metal Compounds)
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14 pages, 6651 KiB  
Article
Sensitivity Enhancement of Thermometry in Tb3+-Doped KY(CO3)2:Sm3+ by Energy Transfer
by Shijian Sun, Jian Qian, Zheng Li, Lei Huang and Dechuan Li
Molecules 2025, 30(4), 767; https://doi.org/10.3390/molecules30040767 - 7 Feb 2025
Cited by 2 | Viewed by 544
Abstract
Sm3+ and Tb3+ co-doped KY(CO3)2 temperature sensing materials were prepared via the hydrothermal method. X-ray diffraction results confirmed the monoclinic phase in KY(CO3)2:Sm3+,Tb3+ samples. In this KY(CO3)2 host, [...] Read more.
Sm3+ and Tb3+ co-doped KY(CO3)2 temperature sensing materials were prepared via the hydrothermal method. X-ray diffraction results confirmed the monoclinic phase in KY(CO3)2:Sm3+,Tb3+ samples. In this KY(CO3)2 host, Tb3+ transfers energy to Sm3+ through cross-relaxation. Notably, a 20 mol% concentration of Tb3+ increases the emission intensity of Sm3+ by 7.1 times. The fluorescence emission intensities of 5D4 (Tb3+) and 4G5/2 (Sm3+) vary significantly with temperature. Both Sm3+-Sm3+ and Tb3+-Sm3+ pairs act as effective emission centers in KY(CO3)2:Sm3+,Tb3+ for optical temperature measurement. The relationship between fluorescence intensity ratio (I542/I567) and temperature reveals that the maximum absolute sensitivity and relative sensitivity of KY(CO3)2:Sm3+,Tb3+ are 0.031 K−1 and 0.46%K−1 at room temperature of 298 K, respectively. In contrast, KY(CO3)2:Sm3+ has a maximum absolute sensitivity of only 0.00051 K−1 and a relative sensitivity of 0.11%K−1 at 498 K. These results highlight the significant role of Tb3+ in enhancing Sm3+ emission intensities, making Tb3+ doped KY(CO3)2:Sm3+ a promising candidate for thermometry. Full article
(This article belongs to the Special Issue Synthesis and Crystal Structure of Rare-Earth Metal Compounds)
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12 pages, 5955 KiB  
Article
A Novel Synthesis Method of Dumbbell-like (Gd1−xTbx)2O(CO3)2·H2O Phosphor for Latent Fingerprint
by Lei Huang, Jian Qian, Shijian Sun, Zheng Li and Dechuan Li
Molecules 2024, 29(16), 3846; https://doi.org/10.3390/molecules29163846 - 14 Aug 2024
Viewed by 887
Abstract
A novel method for synthesizing dumbbell-shaped (Gd1−xTbx)2O(CO3)2·H2O (GOC:xTb3+) phosphors using sodium carbonate was investigated. An amount of 1 mmol of stable fluorescent powder can be widely [...] Read more.
A novel method for synthesizing dumbbell-shaped (Gd1−xTbx)2O(CO3)2·H2O (GOC:xTb3+) phosphors using sodium carbonate was investigated. An amount of 1 mmol of stable fluorescent powder can be widely prepared using 3–11 mmol of Na2CO3 at a pH value of 8.5–10.5 in the reaction solution. The optimal reaction conditions for the phosphors were determined to be 7 mmol for the amount of sodium carbonate and a pH of 9.5 in the solution. Mapping analysis of the elements confirmed uniform distribution of Gd3+ and Tb3+ elements in GOC:xTb3+. The analysis of fluorescence intensity shows that an optimal excitation wavelength of 273 nm is observed when the concentration of Tb3+ is between 0.005 and 0.3. The highest emission intensity was observed for GOC:0.05Tb3+ with a 57.5% maximum quantum efficiency. The chromaticity coordinates show that the color of GOC:Tb3+ is stable and suitable for fluorescence recognition. Latent fingerprint visualization reveals distinctive features like whorls, hooks, and bifurcations. Therefore, the sodium carbonate method offers an effective alternative to traditional urea chemical reaction conditions for preparing GOC:Tb3+. Full article
(This article belongs to the Special Issue Synthesis and Crystal Structure of Rare-Earth Metal Compounds)
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14 pages, 3273 KiB  
Article
The Structure and Optical Properties of Luminescent Europium Terephthalate Antenna Metal–Organic Frameworks Doped by Yttrium, Gadolinium, and Lanthanum Ions
by Oleg S. Butorlin, Anna S. Petrova, Yulia N. Toikka, Ilya E. Kolesnikov, Sergey N. Orlov, Mikhail N. Ryazantsev, Nikita A. Bogachev, Mikhail Yu. Skripkin and Andrey S. Mereshchenko
Molecules 2024, 29(15), 3558; https://doi.org/10.3390/molecules29153558 - 28 Jul 2024
Cited by 3 | Viewed by 1389
Abstract
New heterometallic antenna terephthalate MOFs, namely, (EuxM1−x)2bdc3·4H2O (M = Y, La, Gd) (x = 0.001–1), were synthesized by a one-step method from aqueous solutions. The resulting compounds are isomorphic to each other; the [...] Read more.
New heterometallic antenna terephthalate MOFs, namely, (EuxM1−x)2bdc3·4H2O (M = Y, La, Gd) (x = 0.001–1), were synthesized by a one-step method from aqueous solutions. The resulting compounds are isomorphic to each other; the crystalline phase corresponds to Ln2bdc3∙4H2O. Upon 300 nm excitation to the singlet excited state of terephthalate ions, all compounds exhibit a bright red emission corresponding to the of 5D07FJ (J = 0–4) f-f transitions of Eu3+ ions. The Eu(III) concentration dependence of the photophysical properties was carefully studied. We revealed that Gd-doping results in photoluminescence enhancement due to the heavy atom effect. To quantitatively compare the antenna effect among different compounds, we proposed the new approach, where the quantum yield of the 5D0 formation is used to characterize the efficiency of energy transfer from the ligand antenna to the Eu3+ emitter. Full article
(This article belongs to the Special Issue Synthesis and Crystal Structure of Rare-Earth Metal Compounds)
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