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Issue 13, 2019
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RE 2[B2(SO4)6] (RE = Y, La–Nd, Sm, Eu, Tb–Lu): a silicate-analogous host structure with weak coordination behaviour

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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, 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 (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.

Graphical abstract: RE 2[B2(SO4)6] (RE = Y, La–Nd, Sm, Eu, Tb–Lu): a silicate-analogous host structure with weak coordination behaviour

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Publication details

The article was received on 30 Jan 2019, accepted on 04 Mar 2019 and first published on 04 Mar 2019


Article type: Paper
DOI: 10.1039/C9DT00445A
Dalton Trans., 2019,48, 4387-4397

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    RE 2[B2(SO4)6] (RE = Y, La–Nd, Sm, Eu, Tb–Lu): a silicate-analogous host structure with weak coordination behaviour

    P. Netzsch, M. Hämmer, P. Gross, H. Bariss, T. Block, L. Heletta, R. Pöttgen, J. Bruns, H. Huppertz and H. A. Höppe, Dalton Trans., 2019, 48, 4387
    DOI: 10.1039/C9DT00445A

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