Issue 18, 2023

Ce3F4(SO4)4: cationic framework assembly for designing polar nonlinear optical material through fluorination degree modulation

Abstract

Noncentrosymmetric (NCS) structure is the paramount precondition for producing second-harmonic generation (SHG) of crystalline materials. Herein, a fluorine-enriched-induced centrosymmetric-to-noncentrosymmetric transformation strategy was employed in CS Ce2F2(SO4)3ยท2H2O, leading to the discovery of new NCS cerium fluoride sulfate, Ce3F4(SO4)4. Ce3F4(SO4)4 crystallizes in polar space group C2, and features a 2D-layered framework constructed from [CeO5F3] and [CeO6F2] polyhedra, extending to a final 3D framework linked via two crystallographically independent [SO4] units. Ce3F4(SO4)4 displays a phase-matchable SHG effect of about 1.0 times that of KDP and sufficient experimental birefringence (0.141@546 nm) in fluorine-containing sulfate-based NLO materials. Structural analysis and first-principle calculations suggest that the ordered arrangement of fluorinated cerium-centered polyhedra ([CeO5F3] and [CeO6F2]) as well as [SO4] tetrahedra play a significant role in SHG activity and birefringence. Our study illustrates that the introduction of metal-centered polyhedra with a high degree of fluorination is conducive to the formation of NCS structure and is a valuable method for designing novel nonlinear optical materials.

Graphical abstract: Ce3F4(SO4)4: cationic framework assembly for designing polar nonlinear optical material through fluorination degree modulation

Supplementary files

Article information

Article type
Research Article
Submitted
18 Mar 2023
Accepted
01 May 2023
First published
03 May 2023

Inorg. Chem. Front., 2023,10, 5270-5277

Ce3F4(SO4)4: cationic framework assembly for designing polar nonlinear optical material through fluorination degree modulation

T. Wu, X. Jiang, C. Wu, Z. Lin, Z. Huang, M. G. Humphrey and C. Zhang, Inorg. Chem. Front., 2023, 10, 5270 DOI: 10.1039/D3QI00513E

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