Die Borosulfate K4[BS4O15(OH)], Ba[B2S3O13] und Gd2[B2S6O24]

Groß, Peter; Kirchhain, Arno; Höppe, Henning A.

doi:10.1002/ange.201510612

Cited by 18 publications

(4 citation statements)

References 27 publications

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“…52) with the lattice parameters a = 1251.60(7), b = 1251.20(7), c = 730.15(4) pm, resulting in a cell volume of 114.42(1) nm 3 . No isotypical structures are known in literature, whereby the structure is very similar to that of A [B(SO 4 ) 2 ] ( A = K, NH 4 , H 3 O, Ag),, however clearly different to the already literature known borosulfates of divalent cations Ba[B 2 S 3 O 13 ] and CaB 2 S 4 O 16 …”

Section: Resultsmentioning

confidence: 95%

Synthesis and Characterization of the First Lead(II) Borosulfate Pb[B₂(SO₄)₄]

Schönegger

Bruns

Gartner

et al. 2018

Zeitschrift anorg allge chemie

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The first lead(II) borosulfate Pb[B2(SO4)4] was synthesized under harsh conditions via a solvothermal reaction of PbO2 with H3BO3 and oleum (20 % SO3). The compound crystallizes in the orthorhombic space group Pnna (no. 52) with the lattice parameters a = 1251.6(7), b = 1252.1(7), and c = 730.2(4) pm (Z = 4). The structure of Pb[B2(SO4)4] is constructed of one‐dimensional infinite anionic chains according to 1∞[B(SO4)4/2]– and charge compensated by Pb2+ cations, which are coordinated to the chain terminating oxygen atoms of the (SO4) tetrahedra. The lone pair of electrons of the Pb2+ cations is sterically not active. Pb[B2(SO4)4] was characterized by means of single‐crystal and powder X‐ray diffraction, as well as vibrational spectroscopy.

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Section: Resultsmentioning

confidence: 95%

Synthesis and Characterization of the First Lead(II) Borosulfate Pb[B₂(SO₄)₄]

Schönegger

Bruns

Gartner

et al. 2018

Zeitschrift anorg allge chemie

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“…[ 32 ] The lanthanum atoms occupy the special 4 c Wyckoff positions and are ninefold coordinated by oxygen atoms in form of a distorted tricapped trigonal prism with C s site symmetry. Y 2 [B 2 (SO 4 ) 6 ] crystallizes in the Gd 2 [B 2 (SO 4 ) 6 ] structure type [ 33 ] in the monoclinic crystal system with space group C 2/ c (No. 15).…”

Section: Resultsmentioning

confidence: 99%

Beyond the Energy Gap Law: The Influence of Selection Rules and Host Compound Effects on Nonradiative Transition Rates in Boltzmann Thermometers

Netzsch

Hämmer

Turgunbajew

et al. 2022

Advanced Optical Materials

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range from biothermal imaging, [5,6] temperature monitoring in catalysis, [7][8][9][10] microelectronics, [11] or molecular logics [12] to the investigation of fundamental thermodynamic phenomena [13] at the micro-and nanoscale. One of the conceptually simplest ways of optical temperature sensing, also in terms of the required setup, is the exploitation of the luminescence intensity ratio (LIR) of two emission bands due to radiative transitions from two thermally coupled excited levels of an ensemble of non-interacting ions. In case of efficient thermal coupling between these levels by (multi) phonon transitions, the LIR follows Boltzmann's law. [14] Trivalent lanthanoid ions with the rich energy level structure arising from their partially filled 4f n (n = 1-13) configuration are primary representatives for this type of luminescence thermometry, with Er 3+ and its green-emitting 2 H 11/2 and 4 S 3/2 levels being the most prominent examples. [7,15] Boltzmann-type equilibrium between the two excited levels critically depends on the interplay between the depopulating radiative decay and the nonradiative multiphonon thermalization pathways. [14,16] The rate-determining step is the Apart from the energy gap law, control parameters over nonradiative transitions are so far only scarcely regarded. In this work, the impact of both covalence of the lanthanoid-ligand bond and varying bond distance on the magnitude of the intrinsic nonradiative decay rate between the excited 6 P 5/2 and 6 P 7/2 spin-orbit levels of Gd 3+ is investigated in the chemically related compounds Y 2 [B 2 (SO 4 ) 6 ] and LaBO 3 . Analysis of the temperature-dependent luminescence spectra reveals that the intrinsic nonradiative transition rates between the excited 6 P J ( J = 5/2, 7/2) levels are of the order of only 10 ms −1 (Y 2 [B 2 (SO 4 ) 6 ]:Gd 3+ : 8.9 ms −1 ; LaBO 3 :Gd 3+ : 10.5 ms −1 ) and differ due to the different degree of covalence of the GdO bonds in the two compounds. Comparison to the established luminescent Boltzmann thermometer Er 3+ reveals, however, that the nonradiative transition rates between the excited levels of Gd 3+ are over three orders of magnitude slower despite a similar energy gap and the presence of a single resonant phonon mode. This hints to a fundamental magnetic dipolar character of the nonradiative coupling in Gd 3+ . These findings can pave a way to control nonradiative transition rates and how to tune the dynamic range of luminescent Boltzmann thermometers.

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“…For the latter, the only reported compound so far is Li[B(SO 4 ) 2 ] [11] despite the huge number of reported borosulfates in the last eight years. Further, borosulfates feature simple cations like in Li[B(SO 4 ) 2 ] [11] or R 2 [B 2 (SO 4 ) 6 ] (R = Y, La-Nd, Sm-Lu) [8,12] but also molecular cations as observed in H 3 O[B(SO 4 ) 2 ] [13] or (NH 4 ) 3 [B(SO 4 ) 3 ]. [5] ] are the only borosulfates containing two different cations up to date and, apparently, here they all exhibit the same charge.…”

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The First Bismuth Borosulfates Comprising Oxonium and a Tectosilicate‐Analogous Anion

2020

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The first bismuth borosulfate (H 3 O)Bi[B(SO 4 ) 2 ] 4 is only the second featuring a three‐dimensional anion, the first tectosilicate‐analogous borosulfate synthesised solvothermally without a precursor (from Bi(NO 3 ) 3 ⋅5 H 2 O and B(OH) 3 in oleum); moreover, it is the first comprising two differently charged cations and crystallises in a new structure type in space group I (no. 82) (a=11.857(1), c=8.149(1) Å, 1947 refl., 111 param., wR2=0.037), confirmed by a second harmonic generation (SHG) measurement. The B(SO 4 ) 4 supertetrahedra are connected via all four sulfate tetrahedra resulting in a three‐dimensional anion with both H 3 O + and Bi 3+ cations in channels. Additionally, the crystal structure of a further bismuth borosulfate, Bi 2 [B 2 (SO 4 ) 6 ], is elucidated crystallising isotypically to the rare‐earth borosulfates R 2 [B 2 (SO 4 ) 6 ] in space group C2/c (No. 15) (a=13.568(2), b=11.490(2), c=11.106(2) Å, 3127 refl., 155 param., wR2=0.035). Moreover, the optical and thermal properties of both compounds are discussed.

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Die Borosulfate K₄[BS₄O₁₅(OH)], Ba[B₂S₃O₁₃] und Gd₂[B₂S₆O₂₄]

Cited by 18 publications

References 27 publications

Synthesis and Characterization of the First Lead(II) Borosulfate Pb[B₂(SO₄)₄]

Synthesis and Characterization of the First Lead(II) Borosulfate Pb[B₂(SO₄)₄]

Beyond the Energy Gap Law: The Influence of Selection Rules and Host Compound Effects on Nonradiative Transition Rates in Boltzmann Thermometers

The First Bismuth Borosulfates Comprising Oxonium and a Tectosilicate‐Analogous Anion

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Die Borosulfate K4[BS4O15(OH)], Ba[B2S3O13] und Gd2[B2S6O24]

Cited by 18 publications

References 27 publications

Synthesis and Characterization of the First Lead(II) Borosulfate Pb[B2(SO4)4]

Synthesis and Characterization of the First Lead(II) Borosulfate Pb[B2(SO4)4]

Beyond the Energy Gap Law: The Influence of Selection Rules and Host Compound Effects on Nonradiative Transition Rates in Boltzmann Thermometers

The First Bismuth Borosulfates Comprising Oxonium and a Tectosilicate‐Analogous Anion

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Die Borosulfate K₄[BS₄O₁₅(OH)], Ba[B₂S₃O₁₃] und Gd₂[B₂S₆O₂₄]

Synthesis and Characterization of the First Lead(II) Borosulfate Pb[B₂(SO₄)₄]

Synthesis and Characterization of the First Lead(II) Borosulfate Pb[B₂(SO₄)₄]