CsVO₂F(IO₃): An Excellent SHG Material Featuring an Unprecedented 3D [VO₂F(IO₃)]⁻ Anionic Framework

Abstract

The first alkali‐metal vanadium iodate fluoride, CsVO2F(IO3), with a novel 3D anionic framework, has been rationally designed and hydrothermally synthesized. The 3D [VO2F(IO3)]− framework in CsVO2F(IO3) is built from 0D Λ‐shaped cis‐[VO3F(IO3)2]4− polyanions via corner‐sharing of oxo anions and bridging of the iodate groups. CsVO2F(IO3) displays both a strong second‐harmonic generation (SHG) 1.1 times as strong as KTiOPO4 (KTP) under 2.05 μm laser radiation and high laser‐induced damage threshold (LIDT) of 107.9 MW cm−2. This work provides a new route to design SHG crystals with stable 3D anionic structures from low‐dimensional structural building units.

Cs2VOF4(IO2F2): Rationally designing a noncentrosymmetric early-transition-metal fluoroiodate

“…29–32 Besides them, F-containing early-transition-metal (ETM) iodates have gradually become a new focus because of their large SHG responses and wide transmission region from UV to mid-IR. 33–36…”

“…The UV cutoff edge of Cs 2 VOF 4 (IO 2 F 2 ) is around 257 nm, which is obviously shorter than that of vanadium iodates such as K(VO) 2 O 2 (IO 3 ) 3 (∼650 nm), 60 α, β-Ba 2 [VO 2 F 2 (IO 3 ) 2 ]IO 3 , (∼500 nm), 33 and CsVO 2 F(IO 3 ) (∼525 nm). 36 This indicates that the I–F bonds in fluoroiodates may be helpful to blue-shift the cutoff edges of materials.…”