Ce(IO₃)₃F and Ce(IO₃)₂(NO₃): Two Mixed-Anion Cerium Iodates with Good Nonlinear Optical and Birefringent Properties

Abstract

Two new mixed-anion cerium iodates, namely, Ce­(IO3)3F and Ce­(IO3)2(NO3), have been rationally designed through the integration of hybrid anionic functional building blocks (FBBs). The structure of Ce­(IO3)3F features a novel [Ce­(IO3)3F] bilayer, and the material exhibits large birefringence (0.225 @546 nm). The structure of Ce­(IO3)2(NO3) features [Ce3(IO3)6]3+ triple layers that are further linked by planar NO3 – units. Ce­(IO3)2(NO3) shows a moderate SHG response (1 × KDP) and a high laser-induced damage threshold value (22 × AgGaS2). This work demonstrates that the rich coordination geometries of cerium cations facilitate tuning of the structures of related compounds through modulating anionic FBBs.

New iodate fluoride Rb2Ce(IO3)5F with nonlinear optical properties

“…The main feature of the compounds listed above is the presence of cerium iodate-fluoride layers linked to 3D structures by IO 3 − groups. The estimation of NLO properties from DFT calculations 23–25 reveals that the main signal is related to the IO 3 − groups and the main role in the NLO response is played by the iodate group distribution and topology in the crystal structure. From this point of view, the most important problem in this field is to identify the influence of the nature of various cations introduced into cerium iodate-fluorides on the final characteristics of the compound.…”

“…About 50 iodate fluorides and fluoroiodates known from the literature 18 decisively prove the fruitfulness of the combination of iodate units with 4f-elements, with many of these compounds (up to 69%) possessing NCS crystal structures. 18,20 As far as works featuring Ce 4+ derivatives are concerned, such as Ce(IO 3 ) 2 F 2 ·H 2 O, 21 Li 2 Ce(IO 3 ) 4 F 2 , 22 Ce(IO 3 ) 2 F 2 , 23 Ce(IO 3 ) 3 F, 24 and CaCe(IO 3 ) 3 (IO 3 F)F, 25 this group is the most representative.…”

Anhydrous Aluminum Iodate: Strong Second Harmonic Generation Effect Contributed by Unbonded and Antibonding Orbitals

“…This includes metal iodate fluorides synthesized using a mixed anion strategy, such as Ce­(IO 3 ) 3 F, Bi­(IO 3 )­F 2 , and ABi 2 (IO 3 ) 2 F 5 (A = K, Rb, and Cs), as well as mixed-metal iodates formed by introducing other additional metal ions, such as LiMg­(IO 3 ) 3 and LiM II (IO 3 ) 3 (M II = Zn and Cd), AgLn­(IO 3 ) 4 (Ln = Pr, Sm, Dy, Er, and Tm) . In addition, some iodates containing HIO 3 molecules were also discovered, such as Sm 3 (IO 3 ) 9 (HIO 3 ) 4 , M­(IO 3 ) 2 (HIO 3 ) (M = Ca and Sr), and La­(IO 3 ) 3 (HIO 3 ) .…”

Chromium iodate: the structure and origin of optical second harmonic generation

“…Given the excellent infrared NLO properties of iodates, researchers have made significant efforts in synthesizing numerous metal iodates. Relevant material design strategies primarily involve incorporating various anions and/or cations into the structure to form NLO crystals with superior performance, such as Ce(IO 3 ) 3 F, 1 Bi(IO 3 )F 2 , 2 ABi 2 (IO 3 ) 2 F 5 (A = K, Rb, and Cs), 3 Li 2 Ge(IO 3 ) 6 , 4 LiMg(IO 3 ) 3 , 5 LiM II (IO 3 ) 3 (M II = Zn and Cd), 6 and AgLn(IO 3 ) 4 (Ln = Pr, Sm, Dy, Er, and Tm). 7…”