REI5O14 (RE=Y and Gd): Promising SHG Materials Featuring the Semicircle‐Shaped I5O143− Polyiodate Anion

• Published in: Angewandte Chemie International Edition Vol. 58; no. 34; pp. 11666 - 11669
• Main Authors: Chen, Jin, Hu, Chun‐Li, Mao, Fei‐Fei, Yang, Bing‐Ping, Zhang, Xiao‐Han, Mao, Jiang‐Gao
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 19.08.2019
• Edition: International ed. in English
• Subjects: Anions; Gadolinium; Harmonic generations; Hydrothermal reactions; hydrothermal synthesis; Laser radiation; Phosphoric acid; Polyhedra; polyiodate anions; Potassium phosphate; Potassium phosphates; SHG materials; Signal generation; theoretical calculations
• DOI: 10.1002/anie.201904383
• ISSN: 1433-7851

The first examples of rare‐earth polyiodates, namely, REI5O14 (RE=Y and Gd), have been prepared by hydrothermal reactions of RE2O3 and H5IO6 in H3PO4 (≥85 wt % in H2O), with extremely high yields (>95 %). They crystalize in the polar space group Cm and feature a brand‐new semicircle‐shaped [I5O14]3− pentameric polyiodate anion composed of two IO3 and three IO4 polyhedra. Remarkably, both compounds exhibit very large second‐harmonic generation (SHG) signals (14× and 15×KH2PO4 (KDP) upon 1064 nm laser radiation for Y and Gd compounds, respectively). Our work shows that the hydrothermal reaction in a phosphoric acid medium facilitates the formation of rare‐earth polyiodates. Going in semicircles: The first examples of rare‐earth polyiodates, namely, REI5O14 (RE=Y and Gd), feature a brand‐new semicircle‐shaped [I5O14]3− pentameric polyiodate anion and exhibit very large second‐harmonic generation signals (14× and 15×KDP).