Trends in rare earth thiophosphate syntheses: Rb3Ln(PS4)2 (Ln = La, Ce, Pr), Rb3−xNaxLn(PS4)2 (Ln = Ce, Pr; x = 0.50, 0.55), and RbEuPS4 obtained by molten flux crystal growth

Breton, Logan S.; Smith, Mark D.; Loye, Hans-Conrad zur

doi:10.1039/d1ce00703c

Cited by 4 publications

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“…Finally, to demonstrate the versatility of [Cs 6 X ] A Ga 6 Q 12 structure for creating new optical materials, we also explored doping with other popular luminescence centers, such as Ce 3+ and Eu 2+ , which resulted in the typical blue and green emissions, respectively (see the Experimental Section for more details, Figures S49–S51). − …”

Section: Resultsmentioning

confidence: 99%

Tunable Salt-Inclusion Chalcogenides for Ion Exchange, Photoluminescence, and Scintillation

et al. 2023

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Salt-inclusion chalcogenides (SICs) consisting of covalent and ionic building blocks have emerged as functional materials exhibiting novel topologies that result from the combination of the chalcogenide-based frameworks and the salt inclusions contained within them. Nine compositions of a novel family of SICs [Cs6 X]AGa6 Q 12 (A = Na, K, and Rb; X = F, Cl, and Br; Q = S and Se) were synthesized via halide/polychalcogenide flux crystal growth and structurally characterized. Ex situ powder X-ray diffraction analysis was used to determine the optimal synthesis temperatures at which the titled SIC materials crystallized in the flux. Density functional theory calculations coupled with convex hull construction were performed to predict the stability of [Cs6 X]AGa6 Q 12 compositions as a function of X, A, and Q and to identify their decomposition pathways. A combination of single-crystal X-ray diffraction and energy-dispersive spectroscopy was used to study single-crystal-to-single-crystal (SC-SC) ion-exchange-reaction, a process that also allowed for the synthesis of two additional members of this family, [Cs6F]NaGa6S12 and [Cs6–x Rb x Br]RbGa6S12, which did not form during the direct flux crystal growth. Furthermore, single crystals of [Cs6 X]AGa6 Q 12:Mn2+ were obtained through direct flux crystal growth and SC-SC ion-exchange reactions and studied for their photoluminescent behavior using individual single crystals. The emission profile changed as a function of Mn2+-content, the A cation identity, and the synthesis method used. Finally, radioluminescence measurements were carried out on [Cs6Cl]NaGa6S12:Mn2+ bulk samples, resulting in bright orange scintillation.

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Section: Resultsmentioning

confidence: 99%

Tunable Salt-Inclusion Chalcogenides for Ion Exchange, Photoluminescence, and Scintillation

et al. 2023

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“…[ 29 ] Such a structural transition also occurs in Rb 3 CeP 2 Q 8 (Q = S, Se) and Rb 4 Ln 2 (P 2 S 6 )(PS 4 ) 2 (Ln = La, Ce, Pr, Nd, Sm, Gd). [ 30 ] The symmetric center part of KLaP 2 Se 6 is the La 2 Se 2 parallelogram. While in 1 , the symmetric center is broken as the quadrilateral Sm 2 Se 2 is distorted and not in a plane ( Figure ), which can be proved by the RE−Se bond distances and the RE−Se−RE and Se−RE−Se bond angles (Figure 2a,d).…”

Section: Resultsmentioning

confidence: 99%

KREP₂Se₆ (RE = Sm, Gd, Tb): The First Rare‐Earth Selenophosphates with Remarkable Nonlinear Optical Activities Realized by Synergistic Effect of RE‐ and P‐Based Motifs

Chen

Zhao

et al. 2022

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factor beneficial for increasing bandgap and LIDT usually tend to decrease the NLO coefficient. [5] MIR NLO crystals are important components for outputting MIR lasers. However, according to these requirements, AGS and ZGP cannot satisfy the increasing market's needs in view of their low LIDTs and harmful doublephoton absorption. [6] Therefore, how to maintain the balance between high LIDT and strong NLO response is the main concern for researchers in this field. After years of exploration, MIR NLO materials with superior comprehensive properties are still scarce. Therefore, the discovery of novel ones with balanced comprehensive properties is urgent while challenging.Hitherto, MIR NLO materials are mainly metal chalcogenides, and also several mixed-anionic materials, such as oxyhalides

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“…Chalcometallates, one class of chalcogenides, result from the combination of the chalcogens with certain main group elements that yield complex anionic framework structures. The zur Loye group, utilizing the molten flux synthetic method, has explored the synthesis of single crystals of a variety of chalcometallate materials, including thiophosphates, thiogermanates, and thiosilicates, to explore their magnetic and optical properties. , A major obstacle to the synthesis of these compounds is the lack of commercially available rare earth sulfide-starting materials, which necessitates their preparation in the laboratory prior to exploring the syntheses of chalcometallate compounds. Recently, we have demonstrated the use of the boron chalcogen mixture (BCM) method to synthesize single crystals of LnBS 3 (Ln = La, Ce, Pr, Nd) and measured their nonlinear optical properties .…”

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confidence: 99%

Crystal Structures and Property Measurements of Rare Earth Magnesium Thiosilicates Synthesized via Flux Crystal Growth Utilizing the Boron Chalcogen Mixture (BCM) Method

et al. 2023

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Nine new rare earth magnesium-containing thiosilicates of the formula RE3Mg0.5SiS7 (Ln = Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er) were synthesized in an alkali halide flux using the boron chalcogen mixture (BCM) method. Crystals of high quality were produced, and their structures were determined by single-crystal X-ray diffraction. The compounds crystallize in the hexagonal crystal system in the P63 space group. Phase pure powders of the compounds were used for magnetic susceptibility measurements and for second-harmonic generation (SHG) measurements. Magnetic measurements indicate that Ce3Mg0.5SiS7, Sm3Mg0.5SiS7, and Dy3Mg0.5SiS7 exhibit paramagnetic behavior with a negative Weiss temperature over the 2–300 K temperature range. SHG measurements of La3Mg0.5SiS7 demonstrated SHG activity with an efficiency of 0.16 times the standard potassium dihydrogen phosphate (KDP).

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Trends in rare earth thiophosphate syntheses: Rb₃Ln(PS₄)₂ (Ln = La, Ce, Pr), Rb_3−xNa_xLn(PS₄)₂ (Ln = Ce, Pr; x = 0.50, 0.55), and RbEuPS₄ obtained by molten flux crystal growth

Abstract: Single crystals of new rubidium rare earth thiophosphates with the formulas Rb3Ln(PS4)2 (Ln = La, Pr, Ce), Rb3-xNaxLn(PS4)2 (Ln = Pr, Ce; x = 0.50, 0.55), and RbEuPS4 were crystallized...

Cited by 4 publications

References 50 publications

Tunable Salt-Inclusion Chalcogenides for Ion Exchange, Photoluminescence, and Scintillation

Tunable Salt-Inclusion Chalcogenides for Ion Exchange, Photoluminescence, and Scintillation

KREP₂Se₆ (RE = Sm, Gd, Tb): The First Rare‐Earth Selenophosphates with Remarkable Nonlinear Optical Activities Realized by Synergistic Effect of RE‐ and P‐Based Motifs

Crystal Structures and Property Measurements of Rare Earth Magnesium Thiosilicates Synthesized via Flux Crystal Growth Utilizing the Boron Chalcogen Mixture (BCM) Method

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Trends in rare earth thiophosphate syntheses: Rb3Ln(PS4)2 (Ln = La, Ce, Pr), Rb3−xNaxLn(PS4)2 (Ln = Ce, Pr; x = 0.50, 0.55), and RbEuPS4 obtained by molten flux crystal growth

Abstract: Single crystals of new rubidium rare earth thiophosphates with the formulas Rb3Ln(PS4)2 (Ln = La, Pr, Ce), Rb3-xNaxLn(PS4)2 (Ln = Pr, Ce; x = 0.50, 0.55), and RbEuPS4 were crystallized...

Cited by 4 publications

References 50 publications

Tunable Salt-Inclusion Chalcogenides for Ion Exchange, Photoluminescence, and Scintillation

Tunable Salt-Inclusion Chalcogenides for Ion Exchange, Photoluminescence, and Scintillation

KREP2Se6 (RE = Sm, Gd, Tb): The First Rare‐Earth Selenophosphates with Remarkable Nonlinear Optical Activities Realized by Synergistic Effect of RE‐ and P‐Based Motifs

Crystal Structures and Property Measurements of Rare Earth Magnesium Thiosilicates Synthesized via Flux Crystal Growth Utilizing the Boron Chalcogen Mixture (BCM) Method

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Trends in rare earth thiophosphate syntheses: Rb₃Ln(PS₄)₂ (Ln = La, Ce, Pr), Rb_3−xNa_xLn(PS₄)₂ (Ln = Ce, Pr; x = 0.50, 0.55), and RbEuPS₄ obtained by molten flux crystal growth

KREP₂Se₆ (RE = Sm, Gd, Tb): The First Rare‐Earth Selenophosphates with Remarkable Nonlinear Optical Activities Realized by Synergistic Effect of RE‐ and P‐Based Motifs