Lehrstuhl für Festkörperchemie , Universität Augsburg , Universitätsstraße 1 , D-86159 Augsburg , Germany.
Inorg Chem. 2018 Jul 16;57(14):8530-8539. doi: 10.1021/acs.inorgchem.8b01234. Epub 2018 Jun 29.
The first magnesium, manganese, cobalt, nickel, and zinc borosulfates were synthesized employing solvothermal conditions starting from the superacid H[B(HSO)] and the respective metal powders (Mg, Ni, Zn) or oxides (MnO, CoO). α- M[BO(SO)] ( M = Mg, Mn, Co, Ni, Zn) crystallize isotypically in a new structure type in P3̅ (No. 147) with Z = 1, a = 793.59(4)-810.86(9) pm, and c = 743.98(4)-775.09(9) pm. The oligomeric anion comprises unprecedented dimeric open-branched quadruple tetrahedra { oB, 4 t}[BO(SO)], which are connected via MO dimers to give a three-dimensional network. Upon mild heating, we observed a phase change from α-Mg[BO(SO)] to β-Mg[BO(SO)], yielding a further new structure type in P3̅ (No. 147) with Z = 3, a = 1391.96(6) pm, and c = 748.54(3) pm. The reaction of MgB with SO yields Mg[B(SO)] crystallizing in C2/ c with Z = 4, a = 1744.28(10) pm, b = 531.45(3) pm, c = 1429.06(8) pm, and β = 126.323(2)° showing phyllosilicate topology. UV/vis spectroscopy on α- TM[BO(SO)] ( TM = Co, Ni) confirms the valence state of the TM and reveals that borosulfates are weakly coordinating host structures. Structure relationships between the presented crystal structures and similar borophosphates are shown. The results of vibrational spectroscopy as well as magnetic and thermal measurement investigations are discussed.
首次采用溶剂热条件，从超强酸 H[B(HSO)]和相应的金属粉末（Mg、Ni、Zn）或氧化物（MnO、CoO）出发，合成了第一组镁、锰、钴、镍和锌硼硫酸盐。α-M[BO(SO)]（M = Mg、Mn、Co、Ni、Zn）以新的结构类型在 P3̅（No.147）中同晶型结晶，Z = 1，a = 793.59(4)-810.86(9) pm，c = 743.98(4)-775.09(9) pm。聚合阴离子包含前所未有的双开叉四四面体{ oB，4 t}[BO(SO)]，通过 MO 二聚体连接形成三维网络。在温和加热下，我们观察到从α-Mg[BO(SO)]到β-Mg[BO(SO)]的相变，生成了另一种新的 P3̅（No.147）结构类型，Z = 3，a = 1391.96(6) pm，c = 748.54(3) pm。MgB 与 SO 的反应生成了在 C2/ c 中结晶的 Mg[B(SO)]，Z = 4，a = 1744.28(10) pm，b = 531.45(3) pm，c = 1429.06(8) pm，β = 126.323(2)°，显示出层状硅酸盐拓扑结构。α-TM[BO(SO)]（TM = Co、Ni）的 UV/vis 光谱证实了 TM 的价态，并表明硼硫酸盐是弱配位的主体结构。还展示了所提出的晶体结构与类似的硼磷酸盐之间的结构关系。讨论了振动光谱以及磁性和热测量研究的结果。
