Tb(HSO4)(SO4) – a green emitting hydrogensulfate sulfate with second harmonic generation response

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 β = 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.