A full palette: Crystal chemistry, polymorphism, synthetic strategies, and functional applications of lanthanide oxyhalides

Udayakantha, Malsha; Schofield, Parker; Waetzig, Gregory R.; Banerjee, Sarbajit

doi:10.1016/j.jssc.2018.12.017

Cited by 29 publications

(36 citation statements)

References 206 publications

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“…and is followed by ac ondensation reaction forming oxo and chloride bridges with the elimination of alkyl iodide and isopropyl ether as per: [3,26] 3LaI 3 ðsoln:Þþ3LaðO i PrÞ 3 ðsoln:Þ¼6LaOIðsÞþ3 i PrIðsoln:Þþ…”

Section: Resultsmentioning

confidence: 99%

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Halide Replacement with Complete Preservation of Crystal Lattice in Mixed‐Anion Lanthanide Oxyhalides

et al. 2021

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Ac hallenge in anion control in periodic solids is to preserve the crystal lattice while substituting for different anions of widely varying sizea nd hardness.P ost-synthetic modification routes that place cations or anions in nonequilibrium configurations are promising;h owever,s uch methods remain relatively unexplored for anion placement. Here,w er eport the synthesis of LaOI nanocrystals by an onhydrolytic sol-gel condensation reaction and their transformation into LaOBr,LaOCl, and LaOF nanocrystals along hardsoft acid-base principles using post-synthetic metathesis reactions with ammonium halides.A nion displacement proceeds along halide planes,p reserving the tetragonal matlockite structure.E nergy-variant X-raye xcited optical luminesce signatures of alloyed Tb 3+ -ions is asensitive quantum reporter of the preservation of the cation sublattice and hardening of the crystal structure upon anion replacement.

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Section: Resultsmentioning

confidence: 99%

“…and is followed by a condensation reaction forming oxo and chloride bridges with the elimination of alkyl iodide and isopropyl ether as per: [3, 26]

true 3 LaI_{3} (soln .) + 3 La (O^{i} \Pr)_{3} (soln .) = 6 LaOI (s) + 3^{i} PrI (soln .) + 3^{i} PrO^{i} \Pr (I) ...

…”

Section: Resultsmentioning

confidence: 99%

Halide Replacement with Complete Preservation of Crystal Lattice in Mixed‐Anion Lanthanide Oxyhalides

et al. 2021

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“…Furthermore, LaOCl is thermally stable at temperatures as high as 1200°C. LaOCl holds the tetragonal PbFCl‐type structure, in which two adjacent Cl − layers are separated by fluorite‐type LaO 2 layers perpendicular to the c ‐axis . In our previous papers, the La 3+ ion site in LaOCl was substituted by lower‐valent Mg 2+ or Ca 2+ to form Cl − ion vacancies due to a charge compensation.…”

Section: Introductionmentioning

confidence: 99%

Structural environment of chloride ion‐conducting solids based on lanthanum oxychloride

et al. 2019

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The effect of the structural environment on the Cl− ion conductivity was demonstrated in LaOCl‐based solid electrolytes. By replacing the La3+ site with lower‐valent Mg2+ or Ca2+ ions, the conductivity was enhanced owing to the formation of a Cl− ion vacancy. Despite the same dopant content, the conductivity of La0.8Ca0.2OCl0.8 was considerably greater than La0.8Mg0.2OCl0.8. This enhancement of the conductivity was influenced by the high ionicity of the Cl− ions, which facilitated the weakening of the La‐Cl bond cleavage to conduct inside the lattice. The elongation of the La‐La distance, associated with the Cl− ion conduction, could also cause an increase of the conductivity.

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“… 12 − 14 Additionally, high quantum yield has been reported for Eu 3+ -doped LaOCl, 13 , 14 thereby rendering this material of high interest toward exploring its photoluminescence properties when doped with other ions, such as Nd 3+ , since nanothermometry applications require a high enough photoluminescence (PL) signal to be reliably detected within complex environments. Another important factor behind the choice of this particular host lattice is the perceived simplicity of reported synthesis methods at low temperature, 15 which result in highly monodispersed, about 10 nm, crystalline nanoparticles. Additionally, the reported optical properties compare favorably with respect to other systems like CaF 2 : Nd 3+ , Y 3+ or the β-phase of NaGdF 4 doped with trivalent rare earth ions (RE 3+ ).…”

Section: Introductionmentioning

confidence: 99%

Nd³⁺-Doped Lanthanum Oxychloride Nanocrystals as Nanothermometers

et al. 2021

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The development of optical nanothermometers operating in the near-infrared (NIR) is of high relevance toward temperature measurements in biological systems. We propose herein the use of Nd 3+ -doped lanthanum oxychloride nanocrystals as an efficient system with intense photoluminescence under NIR irradiation in the first biological transparency window and emission in the second biological window with excellent emission stability over time under 808 nm excitation, regardless of Nd 3+ concentration, which can be considered as a particular strength of our system. Additionally, surface passivation through overgrowth of an inert LaOCl shell around optically active LaOCl/Nd 3+ cores was found to further enhance the photoluminescence intensity and also the lifetime of the 1066 nm, 4 F 3/2 to 4 I 11/2 transition, without affecting its (ratiometric) sensitivity toward temperature changes. As required for biological applications, we show that the obtained (initially hydrophobic) nanocrystals can be readily transferred into aqueous solvents with high, long-term stability, through either ligand exchange or encapsulation with an amphiphilic polymer.

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A full palette: Crystal chemistry, polymorphism, synthetic strategies, and functional applications of lanthanide oxyhalides

Cited by 29 publications

References 206 publications

Halide Replacement with Complete Preservation of Crystal Lattice in Mixed‐Anion Lanthanide Oxyhalides

Halide Replacement with Complete Preservation of Crystal Lattice in Mixed‐Anion Lanthanide Oxyhalides

Structural environment of chloride ion‐conducting solids based on lanthanum oxychloride

Nd³⁺-Doped Lanthanum Oxychloride Nanocrystals as Nanothermometers

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A full palette: Crystal chemistry, polymorphism, synthetic strategies, and functional applications of lanthanide oxyhalides

Cited by 29 publications

References 206 publications

Halide Replacement with Complete Preservation of Crystal Lattice in Mixed‐Anion Lanthanide Oxyhalides

Halide Replacement with Complete Preservation of Crystal Lattice in Mixed‐Anion Lanthanide Oxyhalides

Structural environment of chloride ion‐conducting solids based on lanthanum oxychloride

Nd3+-Doped Lanthanum Oxychloride Nanocrystals as Nanothermometers

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Product

Resources

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Nd³⁺-Doped Lanthanum Oxychloride Nanocrystals as Nanothermometers