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Stefan Sutorius Dr. David van Gerven Dr. Selina Olthof Dr. Bertold Rasche Dr. Jörn Bruns 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(22):e202200004
(SO4)-rich silicate analogue borosulfates are able to stabilise cationic cluster-like and chain-like aggregates. Single crystals of [Au3Cl4][B(S2O7)2] and [Au2Cl4][B(S2O7)2](SO3) were obtained by solvothermal reaction with SO3, and the electronic properties were investigated by means of density functional theory–based calculations. [Au3Cl4][B(S2O7)2] exhibits a cluster-like cation, and the cationic gold-chloride strands in [Au2Cl4][B(S2O7)2](SO3) are found to resemble one-dimensional metallic wires. This is confirmed by polarisation microscopy. 相似文献
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Dipl.‐Chem. Michael Daub Dr. Karolina Kazmierczak Prof. Dr. Henning A. Höppe Prof. Dr. Harald Hillebrecht 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(50):16954-16962
The structural principles of borosulfates derived from the B/S ratio are confirmed and extended to new representatives of this class showing novel motifs. According to the composition, Na[B(S2O7)2] (P21/c; a=10.949(6), b=8.491(14), c=12.701(8) Å; β=110.227(1)°; Z=4) and K[B(S2O7)2] (Cc; a=11.3368(6), b=14.662(14), c=13.6650(8) Å; β=94.235(1)°; Z=8) contain isolated [B(S2O7)2]? ions, in which the central BO4 tetrahedron is coordinated by two disulfate units. The alkali cations have coordination numbers of 7 (Na) and 8 (K), respectively. The structure of Cs[B(S2O7)(SO4)] (P21/c; a=10.4525(6), b=11.3191(14), c=8.2760(8) Å; β=103.206(1); Z=4) combines, for the first time, sulfate and disulfate units into a chain structure. Cs has a coordination number of 12. The same structural units were found in H[B(S2O7)(SO4)] (P21/c; a=15.6974(6), b=11.4362(14), c=8.5557(8) Å; β=90.334(3)°; Z=8). This compound represents the first example of a polyacid. The hydrogen atoms were located and connect the chains to form layers through hydrogen‐bonding bridges. H3O[B(SO4)2] (P4/ncc; a=9.1377(6), c=7.3423(8) Å; Z=4) is the first oxonium compound of this type to be found. The BO4 tetrahedra are linked by SO4 tetrahedra to form linear chains similar to those in SiS2. The chains form a tetragonal rod packing structure with H3O+ between the rods. The structures of borosulfates can be classified following the concept described by Liebau for silicates, which was extended to borophosphates by Kniep et al. In contrast to these structures, borosulfates do not comprise B‐O‐B bonds but instead contain S‐O‐S connections. All compounds were obtained as colourless, moisture‐sensitive single crystals by reaction of B2O3 and the appropriate alkali salt in oleum. 相似文献
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Inside Cover: Cu[B2(SO4)4] and Cu[B(SO4)2(HSO4)]—Two Silicate Analogue Borosulfates Differing in their Dimensionality: A Comparative Study of Stability and Acidity (Angew. Chem. Int. Ed. 30/2018) 下载免费PDF全文
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Cu[B2(SO4)4] and Cu[B(SO4)2(HSO4)]—Two Silicate Analogue Borosulfates Differing in their Dimensionality: A Comparative Study of Stability and Acidity 下载免费PDF全文
Dr. Jörn Bruns Dr. Maren Podewitz Prof. Dr. Klaus R. Liedl Priv.‐Doz. Dr. Oliver Janka Prof. Dr. Rainer Pöttgen Prof. Dr. Hubert Huppertz 《Angewandte Chemie (International ed. in English)》2018,57(30):9548-9552
Borosulfates are an ever‐expanding class of compounds and the extent of their properties is still elusive. Herein, the first two copper borosulfates Cu[B2(SO4)4] and Cu[B(SO4)2(HSO4)] are presented, which are structurally related but show different dimensionalities in their substructure: While Cu[B2(SO4)4] reveals an anionic chain, [B(SO4)4/2]?, with both a twisted and a unique chair conformation of the B(SO4)2B subunits, Cu[B(SO4)2(HSO4)] reveals isolated [B2(SO4)4(HSO4)2]4? anions showing exclusively a twisted conformation. The complex anion can figuratively be obtained as a cut‐out from the anionic chain by protons. Comparative DFT calculations based on magnetochemical measurements complement the experimental studies. Calculation of the pKa values of the two conformers of the [B2(SO4)4(HSO4)2]4? anion revealed them to be more similar to silicic than to sulfuric acid, highlighting the close relationship to silicates. 相似文献
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Philip Netzsch Dr. Florian Pielnhofer Prof. Dr. Robert Glaum Prof. Dr. Henning A. Höppe 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(64):14745-14753
Increased synthetic control in borosulfate chemistry leads to the access of various new compounds. Herein, the polymorphism of phyllosilicate-analogous borosulfates is unraveled by adjusting the oleum (65 % SO3) content. The new polymorphs β-Mg[B2(SO4)4] and α-Co[B2(SO4)4] both consist of similar layers of alternating borate and sulfate tetrahedra, but differ in the position of octahedrally coordinated cations. The α-modification comprises cations between the layers, whereas in the β-modification cations are embedded within the layers. With this new synthetic approach, phase-pure compounds of the respective polymorphs α-Mg[B2(SO4)4] and β-Co[B2(SO4)4] were also achieved. Tanabe–Sugano analysis of the Co2+ polymorphs reveal weak ligand field splitting and give insights into the coordination behavior of the two-dimensional borosulfate anions for the first time. DFT calculations confirmed previous in silico experiments and enabled an assignment of the polymorphs by comparing the total electronic energies. The compounds are characterized by single-crystal XRD, PXRD, FTIR, and UV/Vis/NIR spectroscopy, thermogravimetric analysis (TGA), and density functional theory (DFT) calculations. 相似文献
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Peter Gross Arno Kirchhain Henning A. Höppe 《Angewandte Chemie (International ed. in English)》2016,55(13):4353-4355
K4[BS4O15(OH)], Ba[B2S3O13], and Gd2[B2S6O24] were obtained by a new synthetic approach. The strategy involves initially synthesizing the complex acid H[B(HSO4)4] which is subsequently reacted in an open system with anhydrous chlorides of K, Ba, and Gd to the respective borosulfates and a volatile molecule (HCl). Furthermore, protonated borosulfates should be accessible by appropriate stoichiometry of the starting materials, particularly in closed systems, which inhibit deprotonation of H[B(HSO4)4] via condensation and dehydration. This approach led to the successful synthesis of the first divalent and trivalent metal borosulfates (Ba[B2S3O13] with band‐silicate topology and Gd2[B2S6O24] with cyclosilicate topology) and the first hydrogen borosulfate K4[BS4O15(OH)]. 相似文献
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Dr. Jörn Bruns Prof. Dr. Henning A. Höppe Dr. Michael Daub Prof. Dr. Harald Hillebrecht Prof. Dr. Hubert Huppertz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(36):7966-7980
Borosulfates are oxoanionic compounds consisting of condensed sulfur- and boron-centered tetrahedra. Hitherto, they were mostly achieved from solvothermal syntheses in SO3-enriched sulfuric acid, or from reactions with the superacid H[B(HSO4)4]. The crystal structures are very similar to those of the corresponding class of silicates and their substitution variants, especially regarding the typical structural motif of corner-sharing tetrahedra. However, the borosulfates are supposed to be even more versatile, because (BO3) units might also be part of the anionic network. The following article deals with detailed reports on the different synthesis strategies, the crystal chemistry of borosulfates in comparison to silicates, and their hitherto identified properties. 相似文献
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