Luminescence Properties of Y3F[Si3O10]:Ln3+ (Ln = Eu, Tb, Er) with Thalenite-Type Host Lattice and Crystal Structure of Tm3F[Si3O10]

Schäfer, Marion C.; Petter, Michael; Hartenbach, Ingo; Locke, Ralf J. C.; Zhang, Shuang; Wickleder, Claudia; Schleid, Thomas

doi:10.3390/cryst13030511

Open AccessArticle

Luminescence Properties of Y₃F[Si₃O₁₀]:Ln³⁺ (Ln = Eu, Tb, Er) with Thalenite-Type Host Lattice and Crystal Structure of Tm₃F[Si₃O₁₀]

by

Marion C. Schäfer

^1,2,

Michael Petter

¹,

Ingo Hartenbach

^1,*,

Ralf J. C. Locke

¹,

Shuang Zhang

³,

Claudia Wickleder

^3,* and

Thomas Schleid

^1,*

¹

Institute for Inorganic Chemistry, University of Stuttgart, D-70569 Stuttgart, Germany

²

Patent Analyst at CPA Global (Clarivate), D-81541 München, Germany

³

Institute for Inorganic Chemistry, University of Siegen, D-57068 Siegen, Germany

^*

Authors to whom correspondence should be addressed.

Crystals 2023, 13(3), 511; https://doi.org/10.3390/cryst13030511

Submission received: 10 February 2023 / Revised: 9 March 2023 / Accepted: 14 March 2023 / Published: 16 March 2023

(This article belongs to the Special Issue Optical and Spectroscopic Properties of Rare-Earth-Doped Crystals (2nd Edition))

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Abstract

With Tm₃F[Si₃O₁₀], a new representative of the Ln₃F[Si₃O₁₀] series could be synthesized by the reaction of Tm₂O₃, TmF₃ and SiO₂ (molar ratio: 1:1:3), applying an excess of CsBr as a fluxing agent in gas-tightly sealed platinum crucibles for eight days at 750 °C, and designed to yield Tm₃F₃[Si₃O₉] or Cs₂TmF[Si₄O₁₀]. Single crystals of Tm₃F[Si₃O₁₀] (monoclinic, P2₁/n; a = 725.04(6), b = 1102.43(9), c = 1032.57(8) pm, β = 97.185(7)°; Z = 4) appear as pale celadon, transparent, air- and water-resistant rhombic plates. According to its thalenite-type structure, Tm₃F[Si₃O₁₀] contains catena-trisilicate anions [Si₃O₁₀]⁸⁻ and triangular [FTm₃]⁸⁺ cations. The three crystallographically different Tm³⁺ cations are coordinated by seven plus one (Tm1) or only seven anions (Tm2 and Tm3) exhibiting a single F⁻ anion for each polyhedron, additional to the majority of O²⁻ anions. Furthermore, the luminescence properties of the isotypic colorless compound Y₃F[Si₃O₁₀] doped with Eu³⁺ (red emission), Tb³⁺ (green emission) and Er³⁺ (yellow and infrared emission), respectively, are reported in presenting their different excitation and emission spectra.

Keywords:

oxosilicates; fluorides; thalenite; crystal structure; luminescence

1. Introduction

In the quaternary systems RE₂O₃–REF₃–SiO₂ (RE = rare-earth element), only six different types of compounds are known so far, which can be distinguished by the linkage of the involved [SiO₄]⁴⁻ tetrahedra via common vertices. The lanthanum fluoride oxosilicate La₃F₃[Si₃O₉] [1,2] contains cyclo-trisilicate units [Si₃O₉]⁶⁻ and therefore shows the highest degree of silicate connectivity. By breaking one of these bonds with an extra O²⁻ anion, the fluoride oxosilicates RE₃F[Si₃O₁₀] (RE = Y [3], Dy–Er [4,5]) with a thalenite-type structure [6,7] are realized, which comprise catena-trisilicate units [Si₃O₁₀]⁸⁻. Despite the assumption that only four representatives of this formula type [3,4,5] exist, it was recently possible to obtain the isotypic Tm₃F[Si₃O₁₀] by a different synthetic route. Furthermore, the compound RE₄F₂[Si₂O₇][SiO₄] (≡ “RE₄F₂(Si₃O₁₁”), RE = Y [8], Er [9]) is built-up by isolated ortho-oxosilicate ([SiO₄]⁴⁻) and oxodisilicate units ([Si₂O₇]⁶⁻) after another O²⁻ anion has torn the trisilicate chain fragment apart. Three isolated [SiO₄]⁴⁻ tetrahedra occur in the mixed-valent fluoride ortho-oxosilicate Eu₅F[SiO₄]₃ (≡ “Eu^II₂Eu^III₃F(Si₃O₁₂)”) [10] with apatite-type structure, where all Si–O–Si bridges are lost. Moreover, discrete ortho-oxosilicate anions also dominate the structures of some oxide-fluoride derivatives, such as La₇OF₇[SiO₄]₃ [11] and Sm₃OF₃[SiO₄] [12].

Silicate host lattices are very suitable for luminescence materials due to their generally excellent stability. Therefore, several different compounds doped with Eu³⁺, Tb³⁺ and Er³⁺ were described in the past [13,14,15,16,17,18,19,20]. In this work, we use Y₃F[Si₃O₁₀] as the host lattice for the Ln³⁺ cations mentioned above and present their luminescence properties for the first time. Furthermore, the crystal structure of Tm₃F[Si₃O₁₀], as a new compound of the thalenite series, is described in detail, since only lattice constants have been mentioned before [21].

2. Materials and Methods

Single crystals of Tm₃F[Si₃O₁₀] have been synthesized by the reaction of thulium oxide (Tm₂O₃, ChemPur, Karlsruhe, Germany: 99.9%), thulium trifluoride (TmF₃, ChemPur, Karlsruhe, Germany: 99.9%) and silicon dioxide (SiO₂, Merck, Darmstadt, Germany: silica gel, p. a.) in a molar ratio of 1:1:3 with an excess of cesium bromide (CsBr, ChemPur, Karlsruhe, Germany: 99.9%) as the fluxing agent in gas-tightly sealed platinum ampoules (Horst zu Jeddeloh GmbH, Winsen/Luhe, Germany) for eight days at 750 °C. The original target products were Tm₃F₃[Si₃O₉] or Cs₂TmF[Si₄O₁₀], if Cs⁺, as part of the flux, would become incorporated, as it happened in the case of Cs₂YF[Si₄O₁₀] [22]. Following cooling by 10 °C/h down to room temperature and washing the crude product with water, the compound emerged as light green, transparent, air- and water-resistant rhombic plates. Crystallographic data of Tm₃F[Si₃O₁₀] and details of its structural refinement, as well as atomic parameters and coefficients of the anisotropic thermal displacement factors are summarized in Table 1 and Table 2. Selected interatomic distances and angles fill Table 3 and Table 4 informs about the motifs of mutual adjunction [23,24].

The colorless samples for luminescence investigations Y₃F[Si₃O₁₀]:Ln³⁺ (Ln = Eu, Tb, Er) could be synthesized via the classical route [3]. For this purpose, mixtures of yttrium oxide (Y₂O₃, ChemPur, Karlsruhe, Germany: 99.9%), yttrium trifluoride (YF₃, ChemPur, Karlsruhe, Germany: 99.9%) and silicon dioxide (SiO₂, Merck, Darmstadt, Germany: silica gel, p. a.) in the molar ratio 1:4:9 with a slight excess of cesium chloride (CsCl, ChemPur, Karlsruhe, Germany: 99.9%) as fluxing agent, and doped with 3% of the lanthanoid trifluorides LnF₃ (Ln = Eu, Tb, Er; each ChemPur, Karlsruhe, Germany: 99.9%) replacing YF_3, were heated in arc-sealed tantalum ampoules (Plansee, Reutte, Austria) for seven days at 700 °C. For example, to yield circa 500 mg of (Y_2.9Er_0.1)F[Si₃O₁₀], 271.36 mg of Y₂O₃ was mixed with 43.83 mg of YF₃, 2.25 mg of ErF₃ as dopant, and 168.06 mg of SiO₂ and a slight excess of cesium bromide (550 mg). The lack of color for Y₃F[Si₃O₁₀] results from the fact that all included ions (Y³⁺ and Si⁴⁺ as well as F⁻ and O²⁻) exhibit electronic closed-shell configurations ([Ne] for the anions and Si⁴⁺, [Kr] for Y³⁺). As no visible charge-transfer processes from the anions to the cations are active, there is no way to show any color within the 380–750-nm region. So consequently, all components or combinations, such as Y₂O₃, SiO₂, YF₃, SiF₄, YOF, SiOF₂ and Y₂Si₂O₇ appear colorless as well, no matter if covalent or ionic. For this reason, their huge band gaps feature the key property for energy preservation after irradiation followed by transfer processes and avoid thermal quenching. Since Y³⁺ as a non-lanthanoid cation exhibits the same ionic radius (r_i(Y³⁺) = 96–102 pm for C.N. = 7–8) [25] as the mid-size Ln³⁺ cations, despite being so much lighter in weight, yttrium(III) compounds with “hard anions”, such as F⁻ and O²⁻ according to the Pearson concept [26], provide perfect host materials for doping with luminescent Ln³⁺ guests with similar ionic radii, but open-shell representatives (e.g., Eu³⁺: [Xe]4f ⁶, r_i = 101–107 pm; Tb³⁺: [Xe]4f ⁸, r_i = 98–104 pm; Er³⁺: [Xe]4f ¹¹, r_i = 95–100 pm) [25] harvest the visible light upon UV irradiation from electronic f–f transitions.

Quick satisfying phase-purity checks with PXRD of each product were made with a STADI-P powder X-ray diffractometer (Stoe & Cie, Darmstadt, Germany; Cu-K_α radiation), but no Rietveld refinement appeared to be necessary (Figure 1). Semi-quantitative EDXS checks were made with an electron-beam X-ray microprobe (SX-100, Cameca, Gennevilliers, France) and Figure 2 shows a scanning electron micrograph of Tm₃F[Si₃O₁₀]. Photoluminescence emission and excitation spectra of each sample were recorded at room temperature on a Jobin Yvon fluorescence spectrometer (Fluorolog 3, Horiba, Kyoto, Japan) equipped with two 0.22 m double monochromators (SPEX, 1680, Horiba, Kyoto, Japan) and a 450 W xenon lamp. The emission spectra were corrected for photomultiplier sensitivity, the excitation spectra for lamp intensity and both for the transmission of the monochromators.

3. Results and Discussion

3.1. Structure Description

Instead of the expected hypothetical quinary thulium oxosilicate with the formula Cs₂TmF[Si₄O₁₀], that was scheduled to form analogously to Cs₂YF[Si₄O₁₀] [22], Tm₃F[Si₃O₁₀] was surprisingly obtained in several experiments, which represents an extension of the domain of existence in the thalenite-type series (RE₃F[Si₃O₁₀]; RE = Dy, Ho, Er and Y [4,5]). Tm₃F[Si₃O₁₀] crystallizes isotypically to monoclinic Y₃F[Si₃O₁₀] [3] in space group P2₁/n with a = 725.04(6), b = 1102.43(9), c = 1032.57(8) pm, β = 97.185(7)° and four formula units per unit cell. The three crystallographically independent [SiO₄]⁴⁻ tetrahedra are linked via common vertices to an open, horseshoe-shaped chain fragment [Si₃O₁₀]⁸⁻ (Figure 3), which has to be addressed as a catena-oxotrisilicate unit. The tetrahedra are aligned and eclipsed in respect to the O4 bridge ( Crystals 13 00511 i001

(Si1–O4–Si2) = 133°), but staggered considering the O7 connection ( Crystals 13 00511 i001

(Si2–O7–Si3) = 138°). In the unit cell, the opening of the [Si₃O₁₀]⁸⁻ horseshoes is arranged alternatingly to the left and the right (Figure 4) along the [010] direction. The Si–O distances with values of 160–165 pm match very well with the distances of the two known types of thulium oxodisilicates (e.g., B-type Tm₂Si₂O₇: d(Si–O) = 160–165 pm [30] or C-type Tm₂Si₂O₇: d(Si–O) = 161–164 pm [31]). The triangular, almost planar, isolated [FTm₃]⁸⁺ units (d(F–Tm) = 220–235 pm; Figure 5) are located between the [Si₃O₁₀]⁸⁻ chain fragments (Figure 2). The deflection of the F⁻ anion from the (Tm³⁺)₃ triangle amounts to 20 pm and the Tm–F–Tm angles range from 110 to 134°. In the structure, three crystallographically distinguishable Tm³⁺ cations are found. (Tm1)³⁺ is surrounded by one F⁻ and six plus one O²⁻ anions in the shape of a distorted square antiprism. The coordination polyhedra of (Tm2)³⁺ can be described as a strongly distorted monocapped trigonal antiprism, consisting of one fluorine and six oxygen atoms and (Tm3)³⁺ shows an environment of one F⁻ and six O²⁻ anions arranged as a distorted monocapped trigonal prism (Figure 5). The Tm–O distances with values of 220–268 plus 292 pm correspond excellently with those in thulium oxodisilicates, oxide ortho-oxosilicate or sulfide oxodisilicate, respectively (e.g., B-type Tm₂Si₂O₇: d(Tm–O) = 220–274 + 287 pm [30], Tm₂O[SiO₄]: d(Tm–O) = 218–250 + 322 pm [32], Tm₄S₃[Si₂O₇]: d(Tm–O) = 225–251 + 317 pm [33]). The distances between thulium and fluorine (d(Tm–F) = 220–235 pm) are also in good agreement with the separations in, for example, BaTm₂F₈ (d(Tm–F) = 222–231 pm) [34] or TmF[AuF₄]₂ (d(Tm–F) = 212–238 pm) [35]. For visualization of the crystal-structure features, Figure 3, Figure 4 and Figure 5 were created using the DIAMOND [36] program.

3.2. Spectroscopy

In the Y₃F[Si₃O₁₀]:Ln³⁺ phosphors (Ln = Eu, Tb, Er), the doping Ln³⁺ cations are obviously able to replace all three different Y³⁺-cation sites. The emission spectrum of Y₃F[Si₃O₁₀]:Eu³⁺ detected at 390 nm (Figure 6, top) presents strong peaks due to the ⁵D₀ → ⁷F₂ transition, as well as the peaks for the ⁵D₀ → ⁷F₁ transition. The ⁷F₁ level is split into nine components due to three different sites and the low symmetry for Eu³⁺ in the crystal structure. The existence of a weak ⁵D₀ → ⁷F₀ peak indicates that only C_n, C_nv or C_s symmetries are possible. The bands for ⁵D₁ → ⁷F_J transitions were also observed. A weak broad band at 442 nm was detected, which suggests the occurrence of the charge-transfer transition O^2–-2p → Eu³⁺-5d. The excitation spectrum detected at 585 nm (Figure 6, bottom) shows f–f transitions of the Eu³⁺ cation together with a broad band peaking at 316 nm, which can be assigned again to the O²⁻ → Eu³⁺ charge-transfer process.

In the emission spectrum of Y₃F[Si₃O₁₀]:Tb³⁺ at 370 nm (Figure 7, top), broad bands were detected for the ⁵D₃ → ⁷F_J and ⁵D₄ → ⁷F_J transitions. Due to the lot of degeneration possibilities of the f–f transitions, these bands usually appear to be broad. The excitation spectrum of Y₃F[Si₃O₁₀]:Tb³⁺ detected at 485 nm (Figure 7, bottom) shows the ⁵D₃ → ⁷F₆ transition of Tb³⁺ together with an obvious strong broad band, which results from the allowed transition from the 4f⁸ to the 4f⁷5d¹ configuration.

A large number of bands between 536 and 550 nm were detected for ⁴S_3/2 → ⁴I_15/2 in the emission spectrum of Y₃F[Si₃O₁₀]:Er³⁺ at 375 nm (Figure 8, top). The excitation spectrum (Figure 8, bottom) recorded at 536 nm shows strong peaks due to f–f transitions. This indicates that the luminescence of Er³⁺ is almost exclusively owed to f–f transitions of the Er³⁺ cations.

Figure 9 shows that Y₃F[Si₃O₁₀]:Er³⁺ also offers infrared emission bands, the strongest at 850 nm (≡ 11765 cm⁻¹), 1000 nm (≡ 10000 cm⁻¹), 1200 nm (≡ 8333 cm⁻¹) and 1500 nm (≡ 6667 cm⁻¹), which can be attributed to ⁴S_3/2 → ⁴I_13/2, ⁴I_11/2 → ⁴I_15/2, ⁴F_9/2 → ⁴I_13/2 and ⁴I_13/2 → ⁴I_15/2 transitions, respectively. However, this special kind of Er³⁺ IR-luminescence seems more suitable for living tissue probing [37] than for lighting applications.

4. Conclusions

The crystal structure of Tm₃F[Si₃O₁₀] is presented for the first time with the so far heaviest Ln³⁺ cation of the Ln₃F[Si₃O₁₀] series (Ln = Dy–Tm), exhibiting the monoclinic thalenite-type arrangement of Y₃F[Si₃O₁₀]. The latter itself was used for doping experiments with selected Ln³⁺ cations replacing 3% of its Y³⁺ content. With Eu³⁺ as dopant, the typical red luminescence resulting from ⁵D₀ → ⁷F₂ and ⁵D₀ → ⁷F₁ transitions could be detected and interpreted, while the Tb³⁺- and Er³⁺-doped YF₃[Si₃O₁₀] samples shine green and yellow light, respectively, accompanied by rather strong emissions in the infrared region for the Er³⁺ case.

Author Contributions

Conceptualization, M.C.S. and T.S.; methodology, M.C.S., M.P. and S.Z.; software, M.C.S. and S.Z.; validation, M.C.S., T.S. and C.W.; formal analysis, M.C.S., T.S. and C.W.; investigation, M.C.S., T.S. and C.W.; resources, T.S. and C.W.; data curation, M.C.S., T.S., S.Z. and C.W.; writing—original draft preparation, M.C.S., I.H., R.J.C.L., C.W. and T.S.; writing—review and editing, M.C.S., I.H., R.J.C.L., C.W. and T.S.; visualization, M.C.S., S.Z., R.J.C.L. and I.H.; supervision, T.S.; project administration, T.S.; funding acquisition, C.W. and T.S. All authors have read and agreed to the published version of the manuscript.

Funding

We gratefully acknowledge the State of Baden-Württemberg (Stuttgart) for financial support. Moreover, we are thankful for the funding from the Deutsche Forschungsgemeinschaft (Bonn) within the SFB 1166 priority program “lanthanoid-specific functionalities in molecule and material”.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

All the data supporting the conclusions are included within the manuscript and available upon request from the corresponding authors.

Acknowledgments

We thank Falk Lissner for the single-crystal X-ray diffraction measurement.

Conflicts of Interest

The authors declare no conflict of interest.

References

Müller-Bunz, H.; Schleid, T. La₃F₃[Si₃O₉]: Ein Fluorid-cyclo-Trisilicat des Lanthans. Z. Kristallogr. 1997, S12, 141. [Google Scholar]
Müller-Bunz, H.; Schleid, T. La₃F₃[Si₃O₉]: Das erste Fluoridsilicat aus dem tenären System LaF₃/La₂O₃/SiO₂. Z. Anorg. Allg. Chem. 1999, 625, 1377–1383. [Google Scholar] [CrossRef]
Schleid, T.; Müller-Bunz, H. Einkristalle von Y₃F[Si₃O₁₀] im Thalenit-Typ. Z. Anorg. Allg. Chem. 1998, 624, 1082–1084. [Google Scholar] [CrossRef]
Schleid, T.; Müller-Bunz, H. Er₃F[Si₃O₁₀]: Ein Fluorid-catena-Trisilicat des Erbiums. Z. Kristallogr. 1997, S12, 134. [Google Scholar]
Müller-Bunz, H.; Schleid, T. Darstellung und Aufbau der Lanthanoidfluorid-catena-Trisilicate M₃F[Si₃O₁₀] (M = Dy, Ho, Er) im Fluorthalenit-Typ (Y₃F[Si₃O₁₀]). Z. Anorg. Allg. Chem. 2000, 626, 845–852. [Google Scholar] [CrossRef]
Kornev, A.N.; Batalieva, N.G.; Maksimov, B.A.; Ilyukhin, V.V.; Belov, N.V. Crystalline structure of thalenite, Y₃[Si₃O₁₀](OH). Dokl. Akad. Nauk SSSR 1972, 202, 1324–1327. [Google Scholar]
Yakubovich, O.V.; Voloshin, A.V.; Pakhomovskii, Y.A.; Simonov, M.A. Refined crystal structure of thalenite. Kristallografiya 1988, 33, 605–608. [Google Scholar]
Schäfer, M.C.; Hartenbach, I.; Schleid, T. Tetrayttrium difluoride disilicate orthosilicate, Y₄F₂[Si₂O₇][SiO₄]. Acta Crystallogr. 2013, E69, i71. [Google Scholar] [CrossRef]
Müller-Bunz, H.; Schleid, T. Er₄F₂[Si₂O₇][SiO₄]: Das erste Selten-Erd-Fluoridsilicat mit zwei verschiedenen Silicat-Anionen. Z. Anorg. Allg. Chem. 2001, 627, 218–223. [Google Scholar] [CrossRef]
Wickleder, C.; Hartenbach, I.; Lauxmann, P.; Schleid, T. Eu₅F[SiO₄]₃ und Yb₅S[SiO₄]₃. Z. Anorg. Allg. Chem. 2002, 628, 1602–1606. [Google Scholar] [CrossRef]
Müller-Bunz, H.; Schleid, T. La₇OF₇[SiO₄]₃: Das erste Selten-Erd-Oxidfluorid-ortho-Silicat. Z. Kristallogr. 2002, S19, 115. [Google Scholar]
Zimmerhofer, F.; Netzer, F.; Tribus, M.; Huppertz, H. Crystal strucuture determination and characterization of Sm₃SiO₅F₃. Z. Naturforsch. 2022, 77b, 657–665. [Google Scholar] [CrossRef]
Cannas, C.; Mainas, M.; Musinu, A.; Piccaluga, G.; Speghini, A.; Bertinelli, M. Nanocrystalline luminescent Eu³⁺-doped Y₂SiO₅ prepared by sol-gel technique. Opt. Mater. 2005, 27, 1506–1510. [Google Scholar] [CrossRef]
Zhang, W.; Xie, P.; Duan, C.; Yan, K.; Yin, M.; Lou, L.; Xia, S.; Krupa, J.-C. Preparation and size effect on concentration quenching of nanocrystalline Y₂SiO₅:Eu. Chem. Phys. Lett. 1998, 292, 133–136. [Google Scholar] [CrossRef]
Ananias, D.; Ferdov, S.; Paz, F.A.A.; Sa Ferreira, R.A.; Ferreira, A.; Geraldes, C.F.G.C.; Carlos, L.D.; Lin, Z.; Rocha, J. Photoluminescent Layered Lanthanide Silicate Nanoparticles. Chem. Mater. 2008, 20, 205–212. [Google Scholar] [CrossRef]
Reichardt, J.; Stiebler, M.; Hirrle, R.; Kemmler-Sack, S. Cathodo- and Photoluminescence in Oxyorthosilicates of X₁ and X₂ Type: System Y_2−xGd_xSiO₅: Tb³⁺. Phys. Stat. Sol. 1990, A119, 631–642. [Google Scholar] [CrossRef]
Lammers, M.J.J.; Blasse, G. Luminescence of Tb³⁺-and Ce³⁺-Activated Rare Earth Silicates. J. Electrochem. Soc. 1987, 134, 2068–2072. [Google Scholar] [CrossRef]
Ding, Y.; Zhao, G.; Xu, X. Crystal growth and spectroscopic properties of erbium doped Lu₂SiO₅. J. Cryst. Growth 2010, 312, 2103–2106. [Google Scholar] [CrossRef]
Hayhurst, T.; Shalimoff, G.; Edelstein, N.M.; Boatner, L.A.; Abraham, M.M. Optical spectra and Zeeman effect for Er³⁺ in LuPO₄ and HfSiO₄. J. Chem. Phys. 1981, 74, 5449–5452. [Google Scholar] [CrossRef]
Oskam, K.D.; Kaspers, K.A.; Meijerink, A.; Müller-Bunz, H.; Schleid, T. Luminescence of La₃F₃[Si₃O₉]:Ce³⁺. J. Lumin. 2002, 99, 101–105. [Google Scholar] [CrossRef]
Schleid, T.; Müller-Bunz, H.; Janka, O. Geo-Inspired Phosphors Based on Rare-Earth Metal(III) Fluorides with Complex Oxoanions: I. Fluoride Oxocarbonates and Oxosilicates. In Minerals as Advanced Materials II; Krivovichev, S.V., Ed.; Springer: Berlin, Heidelberg, Germany, 2011; pp. 353–366. [Google Scholar]
Schäfer, M.C.; Schleid, T. Synthese und Kristallstruktur des Fluorid-ino-Oxosilicats Cs₂YFSi₄O₁₀. Z. Anorg. Allg. Chem. 2007, 633, 1018–1023. [Google Scholar] [CrossRef]
Hoppe, R. The Coordination Number — An “Inorganic Chameleon”. Angew. Chem. Int. Ed. 1970, 9, 25–34. [Google Scholar] [CrossRef]
Hoppe, R. On the Symbolic Language of the Chemist. Angew. Chem. Int. Ed. 1980, 19, 110–125. [Google Scholar] [CrossRef]
Shannon, R.D. Revised Effective Ionic Radii and Systematic Studies of Interatomic Distances in Halides and Chalcogenides. Acta Crystallogr. 1975, A32, 751–767. [Google Scholar] [CrossRef]
Pearson, R.G. Hard and Soft Acids and Bases. J. Am. Chem. Soc. 1963, 85, 3533–3539. [Google Scholar] [CrossRef]
Herrendorf, W.; Bärnighausen, H. HABITUS: Program for the Optimization of the Crystal Shape for Numerical Absorption Correction in X-SHAPE; Version 1.06; Fa. Stoe: Darmstadt, Germany, 1999. [Google Scholar]
Sheldrick, G.M. SHELXS-97 and SHELXL-97: Programs for Solution and Refinement of Crystal Structures from X-ray Diffraction Data; University of Göttingen: Göttingen, Germany, 1997. [Google Scholar]
Wilson, A.J.C. (Ed.) International Tables for Crystallography, 2nd edit.; Kluwer Academic Publishers: Boston, MA, USA; Dordrecht, The Netherlands; London, UK, 1992; Volume C. [Google Scholar]
Hartenbach, I.; Lissner, F.; Schleid, T. Crystal Structure of B-Type Tm₂Si₂O₇ (≡ Tm₄[Si₃O₁₀][SiO₄]). Z. Naturforsch. 2003, 58b, 925–927. [Google Scholar] [CrossRef]
Felsche, J. Polymorphism and crystal data of the rare-earth disilicates of type RE₂Si₂O₇. J. Less-Common Met. 1970, 21, 1–14. [Google Scholar] [CrossRef]
Müller-Bunz, H.; Schleid, T. Über die Oxidsilicate M₂O[SiO₄] der schweren Lanthanoide (M = Dy–Lu) im A-Typ. Z. Anorg. Allg. Chem. 1999, 625, 613–618. [Google Scholar] [CrossRef]
Sieke, C.; Hartenbach, I.; Schleid, T. Sulfidisch derivatisierte Oxodisilicate der schweren Lanthanide vom Formeltyp M₄S₃[Si₂O₇] (M = Gd–Tm). Z. Naturforsch. 2002, 57b, 1427–1432. [Google Scholar] [CrossRef]
Izotova, O.E.; Aleksandrov, V.B. Crystalline Structure of BaTm₂F₈. Dokl. Akad. Nauk SSSR 1970, 192, 1037–1039. [Google Scholar]
Engelmann, U.; Müller, B.G. Tetrafluoroaurate(III) der Lanthaniden MF[AuF₄]₂ (M = Tm, Yb, Lu). Z. Anorg. Allg. Chem. 1993, 619, 1661–1668. [Google Scholar] [CrossRef]
Crystal Impact GbR. DIAMOND: Visual Crystal Structure Information System; Crystal Impact GbR: Bonn, Germany, 1999. [Google Scholar]
Cao, C.; Xie, Y.; Li, S.-W.; Hong, C. Er³⁺-Ions-Doped Multiscale Nanoprobes for Fluorescence Imaging in Cellular and Living Mice. Nanomaterials 2021, 11, 2676. [Google Scholar] [CrossRef] [PubMed]

Figure 1. Powder X-ray diffractogram of (Y_2.9Er_0.1)F[Si₃O₁₀] (top: measured in orange, bottom: calculated in blue with data from [3]).

Figure 2. Scanning electron micrograph (SEM) of the measured, in this case bar-shaped, single crystal of Tm₃F[Si₃O₁₀].

Figure 3. The horseshoe-shaped catena-oxotrisilicate anion [Si₃O₁₀]⁸⁻ in Tm₃F[Si₃O₁₀].

Figure 4. View at the monoclinic crystal structure of Tm₃F[Si₃O₁₀] along [100] emphasizing the discrete [FTm₃]⁸⁺ and [Si₃O₁₀]⁸⁻ units.

Figure 5. Coordination of the polyhedra of the three crystallographically independent Tm³⁺ cations and the triangular [FTm₃]⁸⁺ unit in Tm₃F[Si₃O₁₀].

Figure 6. Emission spectrum of Y₃F[Si₃O₁₀]:Eu³⁺ excited at 390 nm at room temperature (top). Excitation spectrum of Y₃F[Si₃O₁₀]:Eu³⁺ detected at the emission energy of 585 nm at room temperature (bottom).

Figure 7. Emission spectrum of Y₃F[Si₃O₁₀]:Tb³⁺ excited at 370 nm at room temperature (top). Excitation spectrum of Y₃F[Si₃O₁₀]:Tb³⁺ detected at the emission energy of 485 nm at room temperature (bottom).

Figure 8. Emission spectrum of Y₃F[Si₃O₁₀]:Er³⁺ excited at 375 nm at room temperature (top). Excitation spectrum of Y₃F[Si₃O₁₀]:Er³⁺ detected at the emission energy of 536 nm at room temperature (bottom).

Figure 9. Emission spectrum of Y₃F[Si₃O₁₀]:Er³⁺ excited at 375 nm at room temperature (dotted curve) and 80 K (solid curve); excitation spectrum inserted of Y₃F[Si₃O₁₀]:Er³⁺ detected at the emission energy of 536 nm at room temperature.

Table 1. Tm₃F[Si₃O₁₀]: Crystallographic data and details of the structure refinement.

Crystal system and space group		monoclinic, P2₁/n (no. 14)
Lattice parameters,	a/pm	725.04(6)
	b/pm	1102.43(9)
	c/pm	1032.57(8)
	β/°	97.185(7)
Formula units, Z		4
Calculated density, D_x/g∙cm⁻³		6.246
Molar volume, V_m/cm³∙mol⁻¹		123.28
Diffractometer and wavelength		κ-CCD (Bruker-Nonius), Mo-K_α: λ = 71.07 pm
±h_max/±k_max/±l_max		9/14/13
Θ_max/°		28.36
Electron sum, F(000)/e⁻		1352
Absorption coefficient, μ/mm⁻¹		32.73
Absorption correction		HABITUS [27]
Reflections (unique)		23467 (2046)
R_int/R_σ		0.082/0.037
Reflections with \|F_o\| ≥ 4σ(F_o)		2007
Structure determination and refinement		Programs SHELXS-97 and SHELXL-97 [28]
Scattering factors		International Tables, Vol. C [29]
R₁/R₁ with \|F_o\| ≥ 4σ(F_o)		0.027/0.026
wR₂/Goodness of Fit (GooF)		0.060/1.181
Extinction coefficient, ε		0.0031(1)
Residual electron density, ρ_max/min/e⁻ · 10⁶ pm⁻³		2.32/−2.65
CSD number		380467

Table 2. Atomic parameters and coefficients of the anisotropic thermal displacement factors (U_ij/pm²) for Tm₃F[Si₃O₁₀] (all atoms reside at the Wyckoff position 4e).

Atom	x/a	y/b	z/c	U₁₁	U₂₂	U₃₃	U₂₃	U₁₃	U₁₂	U_eq^a/pm²
Tm1	0.30151(4)	0.40156(3)	0.49629(3)	45(5)	79(2)	53(2)	0(1)	0(1)	−14(1)	60(1)
Tm2	0.40500(4)	0.27124(3)	0.81112(3)	50(2)	63(2)	42(2)	−2(1)	6(1)	4(1)	52(1)
Tm3	0.26348(4)	0.03200(3)	0.51734(3)	50(2)	72(2)	49(2)	−1(1)	1(1)	8(1)	57(1)
F	0.1957(6)	0.2150(4)	0.4397(4)	62(18)	62(20)	150(22)	17(15)	−21(15)	−7(15)	94(8)
Si1	0.0247(3)	0.0861(2)	0.7410(2)	32(8)	64(20)	32(8)	−5(6)	9(6)	3(6)	42(3)
Si2	0.2321(3)	0.2447(2)	0.1107(2)	23(8)	75(8)	47(8)	11(6)	11(6)	−5(6)	48(3)
Si3	0.4943(3)	0.0367(2)	0.2079(2)	24(8)	57(8)	47(8)	3(6)	6(6)	−4(6)	42(3)
O1	0.0134(7)	0.0252(5)	0.3630(5)	45(22)	73(23)	85(23)	−6(18)	−27(17)	−10(17)	71(9)
O2	0.0423(7)	0.0501(5)	0.8934(5)	44(21)	93(23)	46(21)	16(17)	−13(17)	44(17)	62(9)
O3	0.2099(7)	0.1431(5)	0.6967(5)	51(21)	84(23)	70(22)	7(18)	−7(17)	−29(18)	70(9)
O4	0.3448(7)	0.3225(5)	0.2319(5)	94(23)	103(24)	60(22)	9(19)	26(17)	−16(19)	84(9)
O5	0.2695(7)	0.3198(5)	0.9829(5)	123(23)	80(24)	49(22)	−2(19)	46(18)	11(19)	81(9)
O6	0.0155(7)	0.2277(4)	0.1200(5)	81(23)	83(24)	41(21)	0(17)	32(17)	−8(18)	66(9)
O7	0.3194(7)	0.1082(5)	0.1224(5)	45(21)	79(23)	97(23)	8(18)	−10(17)	5(17)	75(9)
O8	0.1860(7)	0.3946(5)	0.6927(5)	83(23)	72(23)	70(22)	12(18)	19(18)	17(18)	74(9)
O9	0.4666(7)	0.0208(5)	0.3621(5)	43(21)	127(24)	50(22)	11(18)	23(17)	2(18)	72(9)
O10	0.0267(7)	0.4103(5)	0.3721(5)	42(20)	81(24)	40(21)	17(18)	−16(16)	−35(17)	56(9)

^a U_eq = ¹/₃ [U₂₂ + 1/sin² β(U₁₁ + U₃₃ + 2U₁₃∙cosβ)].

Table 3. Selected interatomic distances (d/pm) and bond angles ( Crystals 13 00511 i001

/°) for Tm₃F[Si₃O₁₀].

Table 3. Selected interatomic distances (d/pm) and bond angles ( Crystals 13 00511 i001

/°) for Tm₃F[Si₃O₁₀].

	d/pm		d/pm		d/pm
Tm1–F	224.7(4)	Tm2–F	235.1(4)	Tm3–F	220.4(4)
Tm1–O2	221.9(5)	Tm2–O5	219.9(5)	Tm3–O9	226.0(5)
Tm1–O2′	222.2(5)	Tm2–O6	222.1(5)	Tm3–O1	226.1(5)
Tm1–O10	223.3(4)	Tm2–O3	223.0(5)	Tm3–O3	229.4(5)
Tm1–O8	229.0(5)	Tm2–O10	224.5(5)	Tm3–O9′	231.2(5)
Tm1–O6	236.1(5)	Tm2–O8	232.0(5)	Tm3–O5	235.2(5)
Tm1–O7	268.2(5)	Tm2–O1	241.6(5)	Tm3–O1′	256.4(5)
Tm1–O4	292.0(5)
Si1–O3	160.0(5)	Si2–O6	159.6(5)	Si3–O8	160.8(5)
Si1–O2	161.2(5)	Si2–O5	160.9(5)	Si3–O10	161.7(5)
Si1–O1	163.1(5)	Si2–O7	163.1(5)	Si3–O9	163.9(5)
Si1–O4	164.2(5)	Si2–O4	164.7(5)	Si3–O7	165.2(5)
	/°		/°		/°
O2–Si1–O4	99.9(3)	O4–Si2–O5	103.7(3)	O7–Si1–O10	97.0(3)
O1–Si1–O3	100.7(3)	O6–Si2–O7	105.2(3)	O7–Si1–O8	109.8(3)
O1–Si1–O4	110.9(3)	O4–Si2–O7	105.9(3)	O8–Si1–O9	111.0(3)
O2–Si1–O3	114.1(3)	O5–Si2–O6	112.2(3)	O8–Si1–O10	112.5(3)
O3–Si1–O4	115.6(3)	O4–Si2–O6	114.4(3)	O9–Si1–O10	112.9(3)
O1–Si1–O2	116.3(3)	O5–Si2–O7	115.6(3)	O7–Si1–O9	113.0(3)
Si1–O4–Si2	132.7(2)	Tm1–F–Tm2	109.9(2)
Si2–O7–Si3	138.1(3)	Tm2–F–Tm3	114.1(2)
		Tm1–F–Tm3	133.6(2)

Table 4. Motifs of mutual adjunction [23,24] for the Tm₃F[Si₃O₁₀] structure.

	F	O1	O2	O3	O4	O5	O6	O7	O8	O9	O10	C.N.
Tm1	1/1	0/0	2/2	0/0	0 + 1/0 + 1	0/0	1/1	1/1	1/1	0/0	1/1	7 + 1
Tm2	1/1	1/1	0/0	1/1	0/0	1/1	1/1	0/0	1/1	0/0	1/1	7
Tm3	1/1	2/2	0/0	1/1	0/0	1/1	0/0	0/0	0/0	2/2	0/0	7
Si1	0/0	1/1	1/1	1/1	1/1	0/0	0/0	0/0	0/0	0/0	0/0	4
Si2	0/0	0/0	0/0	0/0	1/1	1/1	1/1	1/1	0/0	0/0	0/0	4
Si3	0/0	0/0	0/0	0/0	0/0	0/0	0/0	1/1	1/1	1/1	1/1	4
C.N.	3	4	3	3	2 + 1	3	3	3	3	3	3

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MDPI and ACS Style

Schäfer, M.C.; Petter, M.; Hartenbach, I.; Locke, R.J.C.; Zhang, S.; Wickleder, C.; Schleid, T. Luminescence Properties of Y₃F[Si₃O₁₀]:Ln³⁺ (Ln = Eu, Tb, Er) with Thalenite-Type Host Lattice and Crystal Structure of Tm₃F[Si₃O₁₀]. Crystals 2023, 13, 511. https://doi.org/10.3390/cryst13030511

AMA Style

Schäfer MC, Petter M, Hartenbach I, Locke RJC, Zhang S, Wickleder C, Schleid T. Luminescence Properties of Y₃F[Si₃O₁₀]:Ln³⁺ (Ln = Eu, Tb, Er) with Thalenite-Type Host Lattice and Crystal Structure of Tm₃F[Si₃O₁₀]. Crystals. 2023; 13(3):511. https://doi.org/10.3390/cryst13030511

Chicago/Turabian Style

Schäfer, Marion C., Michael Petter, Ingo Hartenbach, Ralf J. C. Locke, Shuang Zhang, Claudia Wickleder, and Thomas Schleid. 2023. "Luminescence Properties of Y₃F[Si₃O₁₀]:Ln³⁺ (Ln = Eu, Tb, Er) with Thalenite-Type Host Lattice and Crystal Structure of Tm₃F[Si₃O₁₀]" Crystals 13, no. 3: 511. https://doi.org/10.3390/cryst13030511

APA Style

Schäfer, M. C., Petter, M., Hartenbach, I., Locke, R. J. C., Zhang, S., Wickleder, C., & Schleid, T. (2023). Luminescence Properties of Y₃F[Si₃O₁₀]:Ln³⁺ (Ln = Eu, Tb, Er) with Thalenite-Type Host Lattice and Crystal Structure of Tm₃F[Si₃O₁₀]. Crystals, 13(3), 511. https://doi.org/10.3390/cryst13030511

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