New Molybdenyl Iodates: Hydrothermal Preparation and Structures of Molecular K2MoO2(IO3)4 and Two-Dimensional β-KMoO3(IO3)

Hydrothermal synthesis and structures of the homoleptic iodate complexes [M(IO3)6]2− (M = Mo, Zr)

“…This work has provided the first evidence for the stabilization of Mo(IV) by iodate, which has previously only been found with Mo(VI) (16,17). Assignment of the formal oxidation state for Mo can be made with some confidence given that Rb 2 [Mo(IO 3 ) 6 ] (1) is isostructural with Rb 2 [Zr(IO 3 ) 6 ] (2) and Cs 2 [Zr(IO 3 ) 6 ] (3) where the oxidation state of the transition metal can be unambiguously assigned.…”

“…In each compound there is likely a symmetric elongation of the M O bonds along a single three-fold axis that is observed in the O M O bond angles being distorted from orthogonality by 4.30 (16) • , 4.05(13) • , and 4.10(9) • in 1, 2, and 3, respectively. As a d 2 ion Mo(IV) might be expected to exhibit Jahn-Teller distortions that could potentially result in this distortion.…”

LiMoO3(IO3): A new molybdenyl iodate based on WO3-type sheets with large SHG response

“…If a SOJT distorted high-valent transition metal and anions containing nonbonding electron pairs were combined in the same crystal, and furthermore, they were arranged in a manner favorable for producing a large NLO effect, a new class of NLO materials would be expected. Based on this idea, Sykora et al have recently prepared several molybdenyl iodates, ␣-and ␤-KMoO 3 (IO 3 ) as well as AMoO 3 (IO 3 ) (A = Rb, Cs), among which two K-containing polymorphs crystallize in the centrosymmetric space groups, Pbca and P2 1 /n, respectively, thus no NLO effects being observed, whereas Rb and Cs-phases show large second-harmonic-generation (SHG) responses of about 400 × ␣-SiO 2 [4,5].…”

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

“…LiMoO 3 (IO 3 ) and AMoO 3 (IO 3 ) (A = Rb + , Cs + ) with similar chemical formulae are NCS and SHG-active [111,112], whereas ␣-and ␤-KMoO 3 (IO 3 ), A 2 MoO 2 (IO 3 ) 4 (A= K + , Ag + ) and Rb 2 Mo(IO 3 ) 6 are CS [91,112,113]. The structures of ␣-and ␤-KMoO 3 (IO 3 ) exhibit similar 2D [MoO 3 (IO 3 )] − anionic layers in which the MoO 6 octahedra are interconnected into a 1D chain via corner-sharing and these chains are then bridged by the iodate anions [113]. These 2D layers are separated by the K + cations.…”

“…Reports on the metal chromium(VI) iodates are much fewer and no metal tungsten(VI) iodates has been reported so far. The A cations include alkali, alkaline earth, lanthanide(III), actinide, and silver(I) [106][107][108][109][110][111][112][113][114][115][116].…”