Lehrstuhl für Festkörperchemie, Universität Augsburg, Universitätsstraße 1, 86159 Augsburg, Germany.
Dalton Trans. 2019 Mar 26;48(13):4387-4397. doi: 10.1039/c9dt00445a.
The rare earth borosulfates RE2[B2(SO4)6] with RE = Y, La-Nd, Sm, Eu and Tb-Lu were synthesised under solvothermal conditions starting from the metal chlorides (Pr, Nd, Eu), the metal oxides (Y, La, Ce, Sm, Tb, Dy, Er, Tm, Lu), or the metal powders (Ho, Yb). They crystallize isotypically with Gd2[B2(SO4)6] in space group C2/c (Z = 4, a = 1346.9(3)-1379.24(17) pm, b = 1136.4(3)-1158.87(14) pm, c = 1079.9(3)-1139.54(14) pm, β = 93.369(8)-93.611(4)°). The anionic structure consists of an open-branched vierer single ring {oB, 1r}[B2S2O12(SO3)4]6-, similar to the mineral eakerite (Ca2Al2SnSi6O182·2H2O) which contains {oB, 1r}[Si4O12(SiO3)2]12- moieties. The fluorescence spectroscopy of the samples with RE = Ce, Eu and Tb features emissions in the deep UV, the red, and the green part of the spectrum and furthermore revealed a weak coordination behaviour of the borosulfate anion. Thermal analysis of Eu2[B2(SO4)6] showed the highest thermal stability observed for borosulfates so far; respective trends within the borosulfate family are discussed. Additionally, the compounds were characterised by magnetic measurements, vibrational and 151Eu Mößbauer spectroscopy.
采用溶剂热法，以金属氯化物（Pr、Nd、Eu）、金属氧化物（Y、La、Ce、Sm、Tb、Dy、Er、Tm、Lu）或金属粉末（Ho、Yb）为原料，合成了稀土硼硫酸盐 RE2[B2(SO4)6]（RE = Y、La-Nd、Sm、Eu 和 Tb-Lu）。这些化合物与 Gd2[B2(SO4)6] 在 C2/c 空间群中具有同型结构（Z = 4，a = 1346.9(3)-1379.24(17) pm，b = 1136.4(3)-1158.87(14) pm，c = 1079.9(3)-1139.54(14) pm，β = 93.369(8)-93.611(4)°）。阴离子结构由一个开放式分支四元单环 {oB, 1r}[B2S2O12(SO3)4]6- 组成，类似于矿物 eakerite（Ca2Al2SnSi6O182·2H2O），其中包含 {oB, 1r}[Si4O12(SiO3)2]12- 基团。样品的荧光光谱显示，RE = Ce、Eu 和 Tb 发出深紫外、红色和绿色光谱的发射，并且还揭示了硼硫酸盐阴离子的弱配位行为。Eu2[B2(SO4)6] 的热分析显示，硼硫酸盐迄今为止表现出最高的热稳定性；讨论了硼硫酸盐家族内的相应趋势。此外，还通过磁性测量、振动和 151Eu Mößbauer 光谱对化合物进行了表征。
