03 Fakultät Chemie

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Author: search.filters.author.Schleid, ThomasStart date: 2020

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    ItemOpen Access
    New crystal structures of rare‐earth metal(III) oxotellurates(IV) RE2Te3O9: A1‐type (RE=La, Ce) and A2‐type (RE=Pr, Nd)
    (2021) Chou, Sheng‐Chun; Höss, Patrick; Russ, Philip L.; Strobel, Sabine; Schleid, Thomas
    The new rare-earth metal(III) oxotellurates(IV) RE2Te3O9 (RE=La-Nd) of the so far unknown A-type structure can be obtained as needle-shaped single crystals through solid-state reactions of the corresponding binary oxides. Their crystal structures were determined as A1-type for RE=La and Ce or A2-type for RE=Pr and Nd by single-crystal X-ray diffraction. Both structure types crystallize in the monoclinic crystal system, but in two different non-centrosymmetric space groups: the A1-type with Z=8 in space group P21 (La2Te3O9: a=569.54(3), b=2230.12(13), c=1464.71(4) pm, β=101.205(3)°; Ce2Te3O9: a=567.02(3), b=2222.61(13), c=1457.13(9) pm, β=101.134(3)°) or the A2-type with Z=16 in space group Cc (Pr2Te3O9: a=2838.61(16), b=563.89(3), c=2522.08(15) pm, β=118.816(3)°; Nd2Te3O9: a=2826.38(16), b=561.47(3), c=2511.94(15) pm, β=118.841(3)°). In spite of the differences in the unit-cell parameters and the symmetry, both structures consist of quite similar fundamental building blocks (FBBs) consisting of eight crystallographically distinct rare-earth metal-oxygen polyhedra with C.N.(RE3+) from seven to nine and always twelve different ψ1-tetrahedral oxotellurate(IV) anions [TeO3]2-, which show a high number of secondary bonding interactions (SBIs) with each other in all four cases.
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    On the thermal dimorphy of the strontium perrhenate Sr[ReO4]2
    (2024) Conrad, Maurice; Bette, Sebastian; Dinnebier, Robert E.; Schleid, Thomas
    Hygroscopic single crystals of a new hexagonal high‐temperature modification of Sr[ReO4]2 were prepared from a melt of Sr[ReO4]2 ⋅ H2O and SrCl2 ⋅ 6 H2O. The structure analysis of the obtained crystals by X‐ray diffraction revealed that the title compound crystallizes in the ThCd[MoO4]3‐type structure with the hexagonal space group P63/m and the lattice parameters a=1023.81(7) pm and c=646.92(4) pm (c/a=0.632) for Z=2 in its quenchable high‐temperature form. Two crystallographically independent Sr2+ cations are coordinated by oxygen atoms forming either octahedra or tricapped trigonal prisms, whereas the Re7+ cations are found in the centers of discrete tetrahedral meta‐perrhenate units [ReO4]-. Temperature‐dependent in‐situ PXRD studies of dry powder samples of Sr[ReO4]2 exhibited its thermal dimorphy with a phase‐transition temperature at 500-550 °C from literature‐known m‐Sr[ReO4]2 into the newly discovered h‐Sr[ReO4]2 (hexagonal).
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    Luminescence properties of Y3F[Si3O10]:Ln3+ (Ln = Eu, Tb, Er) with thalenite-type host lattice and crystal structure of Tm3F[Si3O10]
    (2023) Schäfer, Marion C.; Petter, Michael; Hartenbach, Ingo; Locke, Ralf J. C.; Zhang, Shuang; Wickleder, Claudia; Schleid, Thomas
    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.
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    Two light-metal dihydrogenisocyanurate hydrates linked by diagonal relationship : syntheses, crystal structures, and vibrational spectra of Li[H2N3C3O3]·1.75 H2O and Mg[H2N3C3O3]2·8 H2O
    (2020) Reckeweg, Olaf; Lissner, Falk; Blaschkowski, Björn; Gross, Peter; Höppe, Henning A.; Schleid, Thomas
    Single‐crystalline materials of Li[H2N3C3O3]·1.75 H2O and Mg[H2N3C3O3]2·8 H2O were obtained by dissolving stoichiometric amounts of the respective carbonates with cyanuric acid in boiling water followed by gentle evaporation of excess water after cooling to room temperature. Even though both of these compounds crystallize in the triclinic space group P1 according to X‐ray structure analyses of their colorless and transparent single crystals, they adopt two new different structure types. Li[H2N3C3O3]·1.75 H2O exhibits the unit‐cell parameters a = 884.71(6) pm, b = 905.12(7) pm, c = 964.38(7) pm, α = 67.847(2)°, β = 62.904(2)° and γ = 68.565(2)° (Z = 4), whereas the lattice parameters for Mg[H2N3C3O3]2·8 H2O are a = 691.95(5) pm, b = 1055.06(8) pm, c = 1183.87(9) pm, α = 85.652(2)°, β = 83.439(2)° and γ = 79.814(2)° (Z = 2). In both cases, the singly deprotonated isocyanuric acid forms monovalent anions consisting of cyclic [H2N3C3O3]– units, which are arranged in ribbons typical for most hitherto known monobasic isocyanurate hydrates. The structures are governed by the oxophilic strength of the respective cation which means that they fulfil their oxophilic coordination requirements either solely with water molecules ([Mg(OH2)6]2+ for Mg2+) or with crystal water and one or two direct coordinative contacts to carbonyl oxygen atoms (O(cy)) of [H2N3C3O3]– anions ([(Li(OH2)2-3(O(cy)1-2]+ for Li+). In both structures occur dominant hydrogen bonds N-H···O within the anionic [H2N3C3O3]- ribbons as well as hydrogen bonds O-H···O between these ribbons and the hydrated Li+ and Mg2+ cations.
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    Sulfurized polypropylene as low‐cost cathode material for high‐capacity lithium‐sulfur batteries
    (2022) Du, Qian; Benedikter, Mathis; Küster, Kathrin; Acartürk, Tolga; Starke, Ulrich; Hoslauer, Jean‐Louis; Schleid, Thomas; Buchmeiser, Michael R.
    Among ‘beyond lithium ion’ energy storage, lithium sulfur (Li-S) batteries are one of the most promising technologies, as a result of the potential for high theoretical energy capacity at low cost. A key obstacle in exploiting the vast potential of Li-S batteries is the formation of soluble polysulfide species. Here, we report sulfurized polypropylene (S/PP‐500) synthesized in one‐step by reacting polypropylene (PP) with sulfur as a new polysulfide shuttle‐free cathode material for Li-S batteries. It exhibits a reversible capacity as high as 1000 mAh/gsulfur at 0.1 C and a sulfur loading of up to 68 wt%, which in turn allows for high sulfur loadings up to 47 % in the final cathode. The low‐cost starting materials together with the simple synthetic procedure and the good electrochemical performance in combination with a commercially available eslectrolyte make the S/PP‐500 a very promising cathode material for Li‐S batteries.
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    The crystal structures of two hydro-closo-borates with divalent tin in comparison : Sn(H2O)3[B10H10] · 3 H2O and Sn(H2O)3[B12H12] · 4 H2O
    (2021) Kleeberg, Fabian M.; Zimmermann, Lucas W.; Schleid, Thomas
    Single crystals of Sn(H2O)3[B10H10] · 3 H2O and Sn(H2O)3[B12H12] · 4 H2O are easily accessible by reactions of aqueous solutions of the acids (H3O)2[B10H10] and (H3O)2[B12H12] with an excess of tin metal powder after isothermal evaporation of the clear brines. Both compounds crystallize with similar structures in the triclinic system with space group P1¯ and Z = 2. The crystallographic main features are electroneutral 1∞{Sn(H2O)3/1[B10H10]3/3} and 1∞{ Sn(H2O)3/1[B12H12]3/3} double chains running along the a-axes. Each Sn2+ cation is coordinated by three water molecules of hydration (d(Sn-O) = 221-225 pm for the B10 and d(Sn-O) = 222-227 pm for the B12 compound) and additionally by hydridic hydrogen atoms of the three nearest boron clusters (d(Sn-H) = 281-322 pm for the B10 and d(Sn-H) = 278-291 pm for the B12 compound), which complete the coordination sphere. Between these tin(II)-bonded water and the three or four interstitial crystal water molecules, classical bridging hydrogen bonds are found, connecting the double chains to each other. Furthermore, there is also non-classical hydrogen bonding between the anionic [BnHn]2- (n = 10 and 12) clusters and the crystal water molecules pursuant to B-Hδ-⋯δ+H-O interactions often called dihydrogen bonds.
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    Sr[ReO4]2 : the first single crystals of an anhydrous alkaline‐earth metal meta‐perrhenate
    (2020) Conrad, Maurice; Russ, Philip L.; Schleid, Thomas
    Colorless single crystals of Sr[ReO4]2 were obtained from halide melts at 1123 K in open corundum crucibles. X‐ray diffraction revealed that Sr[ReO4]2 crystallizes in the monoclinic space group P21/n with the lattice parameters a = 627.31(4) pm, b = 1004.56(7) pm, c = 1271.25(9) pm and β = 97.118(3)° for Z = 4. The crystal structure contains a unique Sr2+‐cation site surrounded by eight crystallographically different oxygen atoms forming distorted bicapped trigonal prisms. All corners of these [SrO8]14- polyhedra (d(Sr-O) = 259-268 pm) are shared with tetrahedral meta‐perrhenate units [ReO4]- (d(Re-O) = 166-173 pm) formed from two crystallographically different Re7+ cations surrounded by four O2- anions each, building up the three‐dimensional mosaic‐like structure of Sr[ReO4]2. Single‐crystal Raman data confirm the presence of two different kinds of symmetry‐free meta‐perrhenate units [ReO4]- and match well with results known from literature.
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    Syntheses and patterns of changes in structural parameters of the new quaternary tellurides EuRECuTe3 (RE = Ho, Tm, and Sc) : experiment and theory
    (2024) Ruseikina, Anna V.; Grigoriev, Maxim V.; Locke, Ralf J. C.; Chernyshev, Vladimir A.; Schleid, Thomas
    The layered orthorhombic quaternary tellurides EuRECuTe3 (RE = Ho, Tm, Sc) with Cmcm symmetry were first synthesized. Single crystals of the compounds up to 500 μm in size were obtained by the halide-flux method at 1120 K from elements taken in a ratio of Eu/RE/Cu/Te = 1:1:1:3. In the series of compounds, the changes in lattice parameters were in the ranges a = 4.3129(3)-4.2341(3) Å, b = 14.3150(9)-14.1562(9) Å, c = 11.2312(7)-10.8698(7) Å, V = 693.40(8)-651.52(7) Å3. In the structures, the cations Eu2+, RE3+ (RE = Ho, Tm, Sc), and Cu+ occupied independent crystallographic positions. The structures were built with distorted copper tetrahedra forming infinite chains [CuTe4]7− and octahedra [RETe6]9- forming two-dimensional layers along the a-axis. These coordination polyhedra formed parallel two-dimensional layers CuRETe32-∞2. Between the layers, along the a-axis, chains of europium trigonal prisms [EuTe6]10- were located. Regularities in the variation of structural parameters and the degree of distortion of coordination polyhedra depending on the ionic radius of the rare-earth metal in the compounds EuRECuCh3 (RE = Ho, Er, Tm, Lu, Sc; Ch = S, Se, Te) were established. It is shown that with a decrease in the ionic radius ri(RE3+) in the compounds EuRECuTe3, the unit-cell volume, bond length d(RE-Te), distortion degree [CuTe4]7-, and crystallographic compression of layers [RECuTe3]2- decreased. The distortion degree of tetrahedral polyhedra [CuCh4]7-, as well as the structural parameters in europium rare-earth copper tellurides EuRECuTe3, were higher than in isostructural quaternary chalcogenides. Ab initio calculations of the crystalline structure, phonon spectrum, and elastic properties of compounds EuRECuTe3 (RE = Ho, Tm, and Sc) ere conducted. The types and wave numbers of fundamental modes were determined, and the involvement of ions in IR and Raman modes was assessed. The calculated data of the crystal structure correlated well with the experimental results.
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    Synthesis, crystal structure and properties of the new laminar quaternary tellurides SrLnCuTe3 (Ln = Sm, Gd-Tm and Lu)
    (2023) Ruseikina, Anna V.; Grigoriev, Maxim V.; Molokeev, Maxim S.; Garmonov, Alexander A.; Elyshev, Andrey V.; Locke, Ralf J. C.; Schleid, Thomas
    This paper reports for the first time on the new laminar quaternary orthorhombic heterometallic quaternary tellurides SrLnCuTe3, the fabrication of which has been a challenge until this work. Data on the crystal structure of tellurides complete the series of quaternary strontium chalcogenides SrLnCuCh3 (Ch = S, Se, Te). Single crystals of the compounds were synthesized from the elements by the halogenide-flux method at 1070 K. The compounds are crystallizing in two space groups Pnma (Ln = Sm, Gd and Tb) and Cmcm (Ln = Dy-Tm and Lu). For SrSmCuTe3 (a = 11.4592(7), b = 4.3706(3), c = 14.4425(9) Å, space group: Pnma) with the largest lanthanoid cation, Sr2+ shows C.N. = 7, whereas Sm3+ reveals a diminished coordination number C.N. = 6. For SrLuCuTe3 (a = 4.3064(3), b = 14.3879(9), c = 11.1408(7) Å, space group: Cmcm) with the smallest lanthanoid cation, coordination numbers of six are realized for both high-charged cations (Sr2+ and Lu3+: C.N. = 6). The cations Sr2+, Ln3+, Cu+ each take independent positions. The structures are built by distorted [CuTe4]7- tetrahedra, forming the infinite chains {∞1[Cu(Te1)1/1t(Te2)1/1t(Te3)2/2e]5−} along [010] in SrLnCuTe3 (Ln = Sm, Gd and Tb) and [100] in SrLnCuTe3 (Ln = Dy-Tm and Lu). The distortion of the polyhedra [CuTe4]7- was compared for the whole series SrLnCuTe3 by means of τ4-descriptor for the four coordinating Te2- anions, which revealed a decrease in the degree of distortion with a decreasing radius at Ln3+. The distorted octahedra [LnTe6]9- form layers {∞2[Ln(Te1)2/2(Te2)2/2(Te3)2/2]3−}. The distorted octahedra and tetrahedra fuse to form parallel layers {∞2[CuLnTe3]2−} and between them, the Sr2+ cations providing three-dimensionality of the structure are located. In the SrLnCuTe3 (Ln = Sm, Gd and Tb) structures, the Sr2+ cations center capped the trigonal prisms [SrTe6+1]12−, united in infinite chains {∞1[Sr(Te1)2/2(Te2)3/3(Te3)2/2]4−} along the [100] direction. The domains of existence of the Ba2MnS3, BaLaCuS3, Eu2CuS3 and KZrCuS3 structure types are defined in the series of orthorhombic chalcogenides SrLnCuCh3 (Ch = S, Se and Te). The tellurides SrLnCuTe3 (Ln = Tb-Er) of both structure types in the temperature range from 2 up to 300 K are paramagnetic, without showing clear signs of a magnetic phase transition.
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    The triclinic lanthanoid(III) halide oxidoarsenates(III) Sm3Cl2[As2O5][AsO3] and Tm3Br2[As2O5][AsO3]
    (2020) Goerigk, Felix C.; Schander, Svetlana; Wickleder, Mathias S.; Schleid, Thomas
    Pale yellow single crystals of the composition Ln3X2[As2O5][AsO3] (Ln = Tm for X = Br and Ln = Sm for X = Cl) were obtained via solid‐state reactions in the systems Ln2O3/As2O3 from sealed silica ampoules using different halides as fluxing agents. Sm3Cl2[As2O5][AsO3] and Tm3Br2[As2O5][AsO3] crystallize isotypically in the triclinic space group P1 with Z = 2 and cell parameters of a = 543.51(4) pm, b = 837.24(6) pm, c = 1113.45(8) pm, α = 90.084(2)°, β = 94.532(2)°, γ = 90.487(2)° for the samarium and a = 534.96(4) pm, b = 869.26(6) pm, c = 1081.84(8) pm, α = 90.723(2)°, β = 94.792(2)° γ = 90.119(2)° for the thulium compound. The isotypic crystal structure of both representatives exhibits three crystallographically different Ln3+ cations, each with a coordination number of eight. (Ln1)3+ and (Ln2)3+ are only coordinated by three oxygen atoms, whereas (Ln3)3+ shows additional contacts to halide anions in forming square [LnO4X4]9- antiprisms. All As3+ cations are surrounded by three oxygen atoms in the shape of isolated [AsO3]3- ψ1‐tetrahedra. They occur either isolated or condensed as pyroanionic [As2O5]4- units with a bridging oxygen atom. In both anions, non‐binding lone‐pair electrons are present at the As3+ cations with a pronounced stereochemically active function.