Synthesis and Characterization of the First Borosulfates of Magnesium, Manganese, Cobalt, Nickel, and Zinc

Netzsch, Philip; Groß, Peter; Takahashi, Hirotaka; Höppe, Henning A.

doi:10.1021/acs.inorgchem.8b01234

Cited by 33 publications

(90 citation statements)

References 41 publications

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“…There are already two polymorphs for magnesium, viz. α‐Mg 4 [B 2 O(SO 4 ) 6 ] and β‐Mg 4 [B 2 O(SO 4 ) 6 ], comprising molecular [B 2 O(SO 4 ) 6 ] 8– units and a further magnesium borosulfate Mg[B 2 (SO 4 ) 4 ] containing a layered anion . A very similar layered structure was described for calcium borosulfate Ca[B 2 (SO 4 ) 4 ] .…”

Section: Introductionmentioning

confidence: 90%

“…Synthetic Procedure: M [B 2 O(SO 4 ) 3 ] ( M = Sr, Pb) was synthesized on the basis of refs. , . 3 mmol B(OH) 3 were dissolved in 2.5 mL of H 2 SO 4 in a Schlenk flask under nitrogen flow at 200 °C for 1 h. After cooling down to 120 °C, 0.3 mL of Oleum (65 %) was added.…”

Section: Methodsmentioning

confidence: 99%

“…A relatively new representative of silicate‐analogous materials are borosulfates, consisting of corner‐sharing borate and sulfate tetrahedra . Besides their vast structural diversity, borosulfates feature weak ligand field splitting and weak nephelauxetic effects, confirmed by the absorption properties of transition metal borosulfates M 4 [B 2 O(SO 4 ) 6 ] ( M = Co, Ni) and the luminescence properties of RE 2 [B 2 (SO 4 ) 6 ] ( RE = Ce, Eu, Tb) . In this rapidly growing compound class, only a few main group metals remain for which borosulfates are not known yet.…”

Section: Introductionmentioning

confidence: 99%

“…Up to now, borosulfates of alkaline earth metals are known for magnesium, calcium and barium , , . There are already two polymorphs for magnesium, viz.…”

Section: Introductionmentioning

confidence: 99%

“…[9] double chains. Pb[B 2 O(SO 4 ) 3 ] crystallizes in a new structure type [P2 1 /m, Z = 2, a = 440.00(2) pm, b = 1210.19 (5) pm, c = 860.43(4) pm, = 103.587(2)°] closely related to Sr[B 2 O(SO 4 ) 3 ]. Both structures share the common supergroup Pnmm and basically differ by the orientation of adjacent anionic chains.…”

Section: Introductionmentioning

confidence: 99%

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Exploring Main Group Metal Borosulfates: Similarities and Differences of Two New Borosulfates M[B₂O(SO₄)₃] (M = Sr, Pb)

et al. 2019

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The first strontium borosulfate Sr[B2O(SO4)3] and a novel lead borosulfate Pb[B2O(SO4)3] were obtained by solvothermal reaction of the respective anhydrous metal chlorides MCl2 (M = Sr, Pb) with H[B(HSO4)4] at 300 °C. The crystal structure of Sr[B2O(SO4)3] [Pnma, Z = 4, a = 1657.38(27) pm, b = 1203.68(19) pm, c = 439.484(8) pm] is isotypic with Ba[B2O(SO4)3] and consists of chains, built up by three membered rings of two borate tetrahedra and a sulfate tetrahedron. These rings are further connected via corner‐sharing sulfate tetrahedra and hence can be classified as loop branched zweier double chains. Pb[B2O(SO4)3] crystallizes in a new structure type [P21/m, Z = 2, a = 440.00(2) pm, b = 1210.19(5) pm, c = 860.43(4) pm, β = 103.587(2) °] closely related to Sr[B2O(SO4)3]. Both structures share the common supergroup Pnmm and basically differ by the orientation of adjacent anionic chains. The coordination surrounding of Pb2+ indicates a lone pair activity and DFT calculations confirmed a weak polarizability. Moreover, the compounds were characterized by electrostatic calculations, vibrational spectroscopy and thermal analysis and broaden the structural and chemical diversity of borosulfates.

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Section: Introductionmentioning

confidence: 90%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…Up to now, borosulfates of alkaline earth metals are known for magnesium, calcium and barium , , . There are already two polymorphs for magnesium, viz.…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Exploring Main Group Metal Borosulfates: Similarities and Differences of Two New Borosulfates M[B₂O(SO₄)₃] (M = Sr, Pb)

et al. 2019

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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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Die ersten zwei Bismutborosulfate – eines davon enthält Oxonium und ein tektosilicatanaloges Anion

Hämmer

Bayarjargal²,

Höppe

2020

Angewandte Chemie

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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 I4 (no. 82) (a = 11.857(1), c = 8.149(1) , 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 threedimensional 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) , 3127 refl., 155 param., wR2 = 0.035). Moreover, the optical and thermal properties of both compounds are discussed.

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Synthesis and Characterization of the First Borosulfates of Magnesium, Manganese, Cobalt, Nickel, and Zinc

Cited by 33 publications

References 41 publications

Exploring Main Group Metal Borosulfates: Similarities and Differences of Two New Borosulfates M[B₂O(SO₄)₃] (M = Sr, Pb)

Exploring Main Group Metal Borosulfates: Similarities and Differences of Two New Borosulfates M[B₂O(SO₄)₃] (M = Sr, Pb)

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

Die ersten zwei Bismutborosulfate – eines davon enthält Oxonium und ein tektosilicatanaloges Anion

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Synthesis and Characterization of the First Borosulfates of Magnesium, Manganese, Cobalt, Nickel, and Zinc

Cited by 33 publications

References 41 publications

Exploring Main Group Metal Borosulfates: Similarities and Differences of Two New Borosulfates M[B2O(SO4)3] (M = Sr, Pb)

Exploring Main Group Metal Borosulfates: Similarities and Differences of Two New Borosulfates M[B2O(SO4)3] (M = Sr, Pb)

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

Die ersten zwei Bismutborosulfate – eines davon enthält Oxonium und ein tektosilicatanaloges Anion

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Exploring Main Group Metal Borosulfates: Similarities and Differences of Two New Borosulfates M[B₂O(SO₄)₃] (M = Sr, Pb)

Exploring Main Group Metal Borosulfates: Similarities and Differences of Two New Borosulfates M[B₂O(SO₄)₃] (M = Sr, Pb)