Ag₃I[(MoO₃)₂(IO₃)₂]: a new polar material synthesized from the structural modulation of molybdenyl iodate architectures by polarizable cation (Ag⁺) and anion (I⁻)

Abstract

A new polar material AgI[(MoO)(IO)], which contains the extended 2D [(MoO)(IO)] molybdenyl iodate framework found in the known noncentrosymmetric material K[(MoO)(IO)], has been synthesized through the conventional hydrothermal method at 200 °C. It crystallizes in the orthorhombic system space group Pna2 with a = 8.0072(2) Å, b = 21.2678(6) Å, c = 7.3241(2) Å, and V = 1247.26(6) Å. Its structure features 2D corrugated [(MoO)(IO)] anionic layers with neighboring anionic layers stitched through 1D [IAg] cationic chains to form a 3D structure. The 1D [IAg] cationic chain acts as the template for parallel alignments of the polar iodate anions along the c axis in 2D [(MoO)(IO)] anionic layers, which leads to the polar structure of the material. Second-harmonic generation (SHG) measurements on AgI[(MoO)(IO)] show a moderate SHG efficiency of about 0.7 times that of the KDP reference under 1064 nm laser radiation. In addition, the thermogravimetric analyses (TGA) and optical measurements of the compound were also carried out.

K6(IO6H4)(HI2O6)(HIO3)2(IO3)4·2H2O: A Case of Iodate with Coexisting [I5+O3] and [I7+O6] Units

“…The I 5+ valence state is the one class with a high proportion (79.29%, 448), whereas the I 7+ valence state is followed by 17.17% (97). The mixed-valence states are discovered in the following 11 iodates: I­(OSO 2 F) 2 I (−1 and +3; Figure S5a), Ag 3 I­((MoO 3 ) 2 (IO 3 ) 2 ), Ag 9 I 3 (SeO 4 ) 2 (IO 3 ) 2 , Bi 3 (IO 3 ) 12 (Ag 4 I) (−1 and +5; Figure S5b–d), ((Cl 2 I)­OIO)­F 2 , (I 3 O 6 )­(HSO 4 ) (+3 and +5; Figure S6a,b), (IOF 2 )­(IO 2 F 4 ), I 4 O 12 , Th­(H 2 O)­(IO 3 ) 2 (I 0.6 V 1.76 O 7 (OH)), Bi 2 (IO 3 )­(IO 6 ) (+5 and +7; Figure S7a–d), and the title compound (+5 and +7).…”

SrTi(IO3)6·2H2O and SrSn(IO3)6: distinct arrangements of lone pair electrons leading to large birefringences

“…Therefore, some metal cations (Ti 4+ , V 5+ , Cr 6+ , Pt 4+ , Ge 4+ , Sn 4+ , Mo 6+ , Mo 4+ , Zr 4+ , and Nb 5+ ) and nonmetal cations (Se 4+ and Te 4+ ) have been introduced into iodates to enrich the structural chemistry and enhance the properties. 4 And interestingly, through introducing homo-valence Mo 4+ , Zr 4+ , Ge 4+ , Ti 4+ , Pt 4+ , and Sn 4+ metal cations into iodates, the similar [M(IO 3 ) 6 ] 2− clusters (M = Mo, Zr, Ge, Ti, Pt, and Sn) can be formed, which possess [MO 6 ] 8− (M = Mo, Zr, Ge, Ti, Pt, and Sn) octahedron connected with six [IO 3 ] − trigonal pyramids. The [M(IO 3 ) 6 ] 2− clusters (M = Mo, Zr, Ge, Ti, Pt, and Sn) can be isostructural when they have the same arrangement of [IO 3 ] − trigonal pyramids, which will be isostructural for metal iodates.…”