ABSTRACT
Recently, sulfates have attracted attention as materials for non-linear optical applications. This compound class is extended by Tb(HSO4)(SO4), which is solvothermally synthesised from Tb4O7 and sulfuric acid. The compound crystallises in the non-centrosymmetric space group P21 (Z = 2, a = 665.03(5) pm, b = 659.41(5) pm, c = 680.24(5) pm, and ß = 104.640(2)°) and is homeotypic with Ni2In. The terbium ions adopt the indium sites and the sulfate and hydrogen sulfate anions are situated on the nickel sites. The compound shows green luminescence based on f-f-transitions and the positions of the f-d-excitation bands reveal a weak coordination behaviour of the sulfate anions. Tb(HSO4)(SO4) exhibits a second harmonic generation response comparable to KH2PO4 (KDP). Furthermore, the material is characterised by electrostatic calculations, infrared spectroscopy and thermal analysis.
ABSTRACT
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, ß = 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 (Ca2Al2Sn[Si6O18](OH)2·2H2O) 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.
