Th(VO₃)₂(SeO₃) and Ln(VO₃)₂(IO₃) (Ln = Ce, Pr, Nd, Sm, and Eu): unusual cases of aliovalent substitution

Abstract

Th(VO3)2(SeO3) and Ln(VO3)2(IO3) (Ln = Ce, Pr, Nd, Sm, and Eu) have been prepared and characterized. Surprisingly, these compounds are isotypic and rather extreme examples of aliovalent substitution (Th(IV)vs. Ln(III); Se(IV)O3(2-)vs. I(V)O3(-)) are possible in this structure type.

[NaCl][Cu(HSeO3)2], NaCl-intercalated Cu(HSeO3)2: synthesis, crystal structure and comparison with related compounds

“…Transition metal selenites have been the focus of a number of recent studies due to their interesting physical properties, arising in part due to the interplay between the stereochemical activity of lone pairs of electrons on the Se 4+ cations and electronic properties of transition metal cations [1][2][3][4][5][6][7][8][9]. The interest has also been stimulated by the attempts to understand purely fundamental reasons for structural diversity in selenites and its underlying crystal chemical mechanisms [10][11][12].…”

Recent advances on second-order NLO materials based on metal iodates

“…). Three types of compounds were isolated in the Ln V I O systems, namely, LaVO(IO 3 ) 5 , LnV 2 O 6 (IO 3 ) (Ln = La, Ce, Pr, Nd, Sm, and Eu), and LaVO 2 (IO 3 ) 4 ·H 2 O[103,104]. LaV IV O(IO 3 ) 5 (P2 1 /n, CS) is isostructural with LaTiO(IO 3 ) 5 and its structure contains a 0D [VO(IO 3 ) 5 ] 3− anionic unit composed of one VO 6 octahedron linked to five IO 3 groups.…”

Bi(IO3)F2: The First Metal Iodate Fluoride with a Very Strong Second Harmonic Generation Effect

“…[1][2][3][4][5][6][7][8][9][10] Owing to the presence of stereochemically active lone-pair electrons on I V ions,t he IO 3 unit is af avorable NLO-active anionic group with large microscopic second-order NLO susceptibility. [1][2][3][4][5][6][7][8][9][10] Owing to the presence of stereochemically active lone-pair electrons on I V ions,t he IO 3 unit is af avorable NLO-active anionic group with large microscopic second-order NLO susceptibility.…”

“…[1] Thea lignment of IO 3 units in polar or non-centrosymmetric (NCS) crystal structures may result in materials with excellent second harmonic generation (SHG) properties. [3][4][5][6][7][8][9][10] These research efforts afforded alarge number of metal iodates with excellent SHG properties,i ncluding BaNbO(IO 3 ) 5 , [6a] BiOIO 3 , [8a] and AgI 3 O 8 . [3][4][5][6][7][8][9][10] These research efforts afforded alarge number of metal iodates with excellent SHG properties,i ncluding BaNbO(IO 3 ) 5 , [6a] BiOIO 3 , [8a] and AgI 3 O 8 .…”

“…Metal iodates are of great importance in the investigation of nonlinear optical (NLO) materials. [1][2][3][4][5][6][7][8][9][10] Owing to the presence of stereochemically active lone-pair electrons on I V ions,t he IO 3 unit is af avorable NLO-active anionic group with large microscopic second-order NLO susceptibility. [1] Thea lignment of IO 3 units in polar or non-centrosymmetric (NCS) crystal structures may result in materials with excellent second harmonic generation (SHG) properties.…”