Issue 1, 2023

LiRE(SO4)2 (RE = Y, Gd, Eu): noncentrosymmetric chiral rare-earth sulfates with very large band gaps

Abstract

Three new ternary lithium rare earth metal sulfates, LiRE(SO4)2 (RE = Y, Gd, and Eu), have been synthesized via high temperature solid-state and solvothermal reactions. The reported materials crystallizing in the noncentrosymmetric (NCS) nonpolar tetragonal space group, P[4 with combining macron]n2 (no. 118) exhibit three-dimensional structures consisting of REO8, LiO4, and SO4 groups. Ultraviolet-visible diffuse reflectance spectra and density functional theory calculations indicate that the title materials exhibit very large band gaps of ca. 6.7 eV. The frameworks of the sulfates reveal high thermal stabilities of up to 873–1073 K depending on the constituting rare earth cations. Powder second-harmonic generation (SHG) measurements reveal that the sulfates with NCS structures have mild SHG responses of ca. 13 × α-SiO2 and are non-phase matchable. Photoluminescence experiments on LiEu(SO4)2 revealing a bright orange emission show multiple peaks originating from f–f transitions. Detailed synthetic procedures, crystal structures, and full characterization studies of the new sulfates are presented.

Graphical abstract: LiRE(SO4)2 (RE = Y, Gd, Eu): noncentrosymmetric chiral rare-earth sulfates with very large band gaps

Supplementary files

Article information

Article type
Research Article
Submitted
26 Sep 2022
Accepted
21 Oct 2022
First published
30 Nov 2022

Mater. Chem. Front., 2023,7, 65-71

LiRE(SO4)2 (RE = Y, Gd, Eu): noncentrosymmetric chiral rare-earth sulfates with very large band gaps

S. Cho and K. M. Ok, Mater. Chem. Front., 2023, 7, 65 DOI: 10.1039/D2QM00983H

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