The very first thorough investigation of the rare earth borosulfates RE2[B2(SO4)6] with RE = Y, La–Nd, Sm, Eu and Tb–Lu focusses on synthetic aspects and especially optical properties.

Borosulfates are a rapidly expanding class of silicate analogue materials, where the structural diversity is expected to be at least as large as known for silicates. However, borosulfates with cross-linking of the anionic network into two or even three dimensions are still very rare. Herein, we present two new representatives with phyllosilicate analogue topology. Through solvothermal reactions of ZnO and MnCl2∙4H2O with boric acid in oleum (65% SO3), we obtained single-crystals of Mn[B2(SO4)4] (monoclinic, P21/n, Z = 2, a = 8.0435(4), b = 7.9174(4), c = 9.3082(4) Å, β = 110.94(1)°, V = 553.63(5) Å3) and Zn[B2(SO4)4] (monoclinic, P21/n, Z = 2, a = 7.8338(4), b = 8.0967(4), c = 9.0399(4) Å, β = 111.26(1)°, V = 534.36(5) Å3). The crystal structures reveal layer-like anionic networks with alternating vierer- and zwölfer-rings formed exclusively by corner-linked (SO4)- and (BO4)-tetrahedra.

SO4)5] to (NO)2[Pt(S2O7)3] by Oxidation with SO 3. -(NO)4[Pt2(SO4)5] (I)is obtained by the reaction of elemental Pt, oleum (65% SO 3), and fuming HNO3 (sealed glass ampoules, 350 C, 2 d; cooling to 25 C within 79 h). The compound crystallizes in the triclinic space group P1 (Z = 4, single crystal XRD) and contains dumbbell-shaped [Pt 2] moieties surrounded by four chelating SO 4 groups forming a "paddlewheel" motif which is connected via two terminal monodentate SO 4 to infinite anionic chains. The reaction of (I) with neat SO3 in sealed glass ampoules at 120 C (30 h; cooling to 25 C within 150 h) yields single crystals of (NO)2[Pt(S2O7)3] (II) (triclinic, P1, Z = 2) with Pt coordinated by three bidentate S 2O7 groups forming an octahedral oxygen coordination sphere around Pt. Magnetic susceptibility of (II) reveals diamagnetism proving the electronic d 6 low-spin configuration of Pt 4+ . TG/DSC measurements of both compounds are also reported. -(BRUNS, J.; NIEHAUS, O.; POETTGEN, R.; WICKLEDER*, M. S.; Z. Anorg. Allg. Chem. 641 (2015) 6, 1002-1008, http://dx.