Observation of Intense X-ray Scintillation in a Family of Mixed Anion Silicates, Cs3RESi4O10F2 (RE = Y, Eu–Lu), Obtained via an Enhanced Flux Crystal Growth Technique

Morrison, Gregory; Latshaw, Allison M.; Spagnuolo, Nicholas R.; Loye, Hans-Conrad zur

doi:10.1021/jacs.7b08559

Cited by 51 publications

(25 citation statements)

References 49 publications

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“…Materials containing two different lanthanide ions are attractive for the construction of a self-referencing thermometer 10 . Lanthanide luminescent materials have sharp emission bands 11 , 12 and a large energy shift between the antenna absorption and lanthanide emission 13 , which distinguishes them from other luminescent materials, such as organic dyes or quantum dots 14 . In addition to these properties, lanthanide luminescence has a long lifetime, allowing time-gated techniques to increase the signal-to-noise ratio 15 .…”

Section: Introductionmentioning

confidence: 99%

A stoichiometric terbium-europium dyad molecular thermometer: energy transfer properties

et al. 2018

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The optical thermometer has shown great promise for use in the fields of aeronautical engineering, environmental monitoring and medical diagnosis. Self-referencing lanthanide thermo-probes distinguish themselves because of their accuracy, calibration, photostability, and temporal dimension of signal. However, the use of conventional lanthanide-doped materials is limited by their poor reproducibility, random distance between energy transfer pairs and interference by energy migration, thereby restricting their utility. Herein, a strategy for synthesizing hetero-dinuclear complexes that comprise chemically similar lanthanides is introduced in which a pair of thermosensitive dinuclear complexes, cycTb-phEu and cycEu-phTb, were synthesized. Their structures were geometrically optimized with an internuclear distance of approximately 10.6Å. The sensitive linear temperature-dependent luminescent intensity ratios of europium and terbium emission over a wide temperature range (50–298K and 10–200K, respectively) and their temporal dimension responses indicate that both dinuclear complexes can act as excellent self-referencing thermometers. The energy transfer from Tb3+ to Eu3+ is thermally activated, with the most important pathway involving the 7F1 Eu3+ J-multiplet at room temperature. The energy transfer from the antenna to Eu3+ was simulated, and it was found that the most important ligand contributions to the rate come from transfers to the Eu3+ upper states rather than direct ligand–metal transfer to 5D1 or 5D0. As the first molecular-based thermometer with clear validation of the metal ratio and a fixed distance between the metal pairs, these dinuclear complexes can be used as new materials for temperature sensing and can provide a new platform for understanding the energy transfer between lanthanide ions.

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Section: Introductionmentioning

confidence: 99%

A stoichiometric terbium-europium dyad molecular thermometer: energy transfer properties

et al. 2018

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“…Mixed anion compounds that contain more than two anionic species in a single phase have drawn attention as new functional materials . Among them, oxyfluorides that contain O 2– and F – as principal anion components have been studied for a wide range of applications, including superconductors, ion conductors, electron conductors, antiferromagnets, dielectric materials, batteries, phosphors, scintillators, (photo)catalysts, − and photoelectrodes …”

Section: Introductionmentioning

confidence: 99%

Oxyfluoride Pb₂Ti₄O₉F₂ as a Stable Anode Material for Photoelectrochemical Water Oxidation

et al. 2019

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An oxyfluoride, Pb 2 Ti 4 O 9 F 2 , was examined as an electrode material for water splitting, and the electrochemical band edge potentials were compared with those of an analogous oxide, Bi 2 Ti 4 O 11 . Pb 2 Ti 4 O 9 F 2 with a band gap of 3.0 eV, which is slightly smaller than that of Bi 2 Ti 4 O 11 (3.1 eV), worked as an n-type semiconductor anode for water oxidation upon band-gap photoexcitation (λ < 420 nm) in the presence of a CoO x cocatalyst to produce O 2 without noticeable degradation. Mott−Schottky analysis and photocurrent onset potential measurement showed that the flat-band potential of Pb 2 Ti 4 O 9 F 2 was positioned at around −0.5 V versus NHE at pH 7.0, which was 0.2 V more negative than that of Bi 2 Ti 4 O 11 . Results of physicochemical analyses, together with previous first-principles calculations, suggest that the relatively negative flat-band potential of Pb 2 Ti 4 O 9 F 2 is due to the stronger orbital interaction between Pb-6s and O-2p in the valence band than that between Bi-6s and O-2p in Bi 2 Ti 4 O 11 because the difference in the orbital energy between metal-6s and O-2p is smaller in the former than in the latter. This stronger Pb-6s/O-2p interaction increases the valence band maximum and conduction band minimum, which causes Pb 2 Ti 4 O 9 F 2 to be operable as a photoanode at lower applied potential. The O-2p orbitals that constitute the valence band maximum of Pb 2 Ti 4 O 9 F 2 also appear to be essential for the realization of stable water oxidation to form O 2 .Article pubs.acs.org/JPCC

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“…There are no silicate-germanates with Tb in the nature or synthetic compounds according to [1,2]. However, there are a lot of original synthetic Tb-silicates with different anionic radicals [2,3]: ortho-NaTb 9 (SiO 4 ) 6 O 2 [4], KTb 9 (SiO 4 ) 6 O 2 and Cd 2 Tb 8 (SiO 4 ) 6 O 2 [5] (structural type of apatite), Na 5 Tb 4 (OH)[SiO 4 ] 4 [6]; diortho-Tb 2 Si 2 O 7 [7], K 3 TbSi 2 O 7 [8], Tb 4 S 3 Si 2 O 7 [9]; triortho-K 3 TbSi 3 O 8 (OH) 2 [10]; tetraortho-groups Ba 2 Tb 2 Si 4 O 13 [11]; six-membered rings Na 3 Tb 3 Si 6 O 18 •H 2 O (synthetic gerenite) [12]; chains-unbranched Rb 2 TbGaSi 4 O 12 [13], wollastonite Na 2 Tb 1.08 Ca 2.92 Si 6 O 18 H 0.8 [14] and spiral Na 3 TbSi 3 O 9 •3H 2 O [15]; layers in Cs 3 TbSi 4 O 10 F 2 [16] [19]. For some of these compounds, the luminescence properties were investigated [6,10,[13][14][15]18,19].…”

Section: Introductionmentioning

confidence: 99%

Rb1.66Cs1.34Tb[Si5.43Ge0.57O15]·H2O, a New Member of the OD-Family of Natural and Synthetic Layered Silicates: Topology-Symmetry Analysis and Structure Prediction

et al. 2021

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Crystals of new silicate-germanate Rb1.66Cs1.34Tb[Si5.43Ge0.57O15]·H2O have been synthesized hydrothermally in a multi-component system TbCl3:GeO2:SiO2 = 1:1:5 at T = 280 °C and P = 100 atm. K2CO3, Rb2CO3 and Cs2CO3 were added to the solution as mineralizers. The crystal structure was solved using single crystal X-ray data: a = 15.9429(3), b = 14.8407(3), c = 7.2781(1) Å, sp. gr. Pbam. New Rb,Cs,Tb-silicate-germanate consists of a [Si5.43Ge0.57O15]∞∞ corrugated tetrahedral layer combined by isolated TbO6 octahedra into the mixed microporous framework as in synthetic K3Nd[Si6O15]·2H2O, K3Nd[Si6O15] and K3Eu[Si6O15]·2H2O with the cavities occupied by Cs, Rb atoms and water molecules. Luminescence spectrum on new crystals was obtained and analysed. A comparison with the other representatives of related layered natural and synthetic silicates was carried out based on the topology-symmetry analysis by the OD (order-disorder) approach. The wollastonite chain was selected as the initial structural unit. Three symmetrical ways of forming ribbon from such a chain and three ways of further connecting ribbons to each other into the layer were revealed and described with symmetry groupoids. Hypothetical structural variants of the layers and ribbons in this family were predicted.

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Observation of Intense X-ray Scintillation in a Family of Mixed Anion Silicates, Cs₃RESi₄O₁₀F₂ (RE = Y, Eu–Lu), Obtained via an Enhanced Flux Crystal Growth Technique

Cited by 51 publications

References 49 publications

A stoichiometric terbium-europium dyad molecular thermometer: energy transfer properties

A stoichiometric terbium-europium dyad molecular thermometer: energy transfer properties

Oxyfluoride Pb₂Ti₄O₉F₂ as a Stable Anode Material for Photoelectrochemical Water Oxidation

Rb1.66Cs1.34Tb[Si5.43Ge0.57O15]·H2O, a New Member of the OD-Family of Natural and Synthetic Layered Silicates: Topology-Symmetry Analysis and Structure Prediction

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Observation of Intense X-ray Scintillation in a Family of Mixed Anion Silicates, Cs3RESi4O10F2 (RE = Y, Eu–Lu), Obtained via an Enhanced Flux Crystal Growth Technique

Cited by 51 publications

References 49 publications

A stoichiometric terbium-europium dyad molecular thermometer: energy transfer properties

A stoichiometric terbium-europium dyad molecular thermometer: energy transfer properties

Oxyfluoride Pb2Ti4O9F2 as a Stable Anode Material for Photoelectrochemical Water Oxidation

Rb1.66Cs1.34Tb[Si5.43Ge0.57O15]·H2O, a New Member of the OD-Family of Natural and Synthetic Layered Silicates: Topology-Symmetry Analysis and Structure Prediction

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Observation of Intense X-ray Scintillation in a Family of Mixed Anion Silicates, Cs₃RESi₄O₁₀F₂ (RE = Y, Eu–Lu), Obtained via an Enhanced Flux Crystal Growth Technique

Oxyfluoride Pb₂Ti₄O₉F₂ as a Stable Anode Material for Photoelectrochemical Water Oxidation