Fluoroiodate

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A fluorooxoiodate or fluoroiodate is a chemical compound or ion derived from iodate, by substituting some of the oxygen by fluorine. They have iodine in the +5 oxidation state. The iodine atoms have a stereochemically active lone-pair of electrons. Many are non-centrosymmetric, and are second harmonic generators (SHG) of intense light shining through them. They are under investigation as materials for non-linear optics, such as for generating ultraviolet light from visible or infrared lasers. [1]

Contents

Different ions include [IOF4]−, [IO2F2]−, [IO3F]2−, and [I2O5F2]2−.

They are distinct from the fluoride iodates which are mixed anion compounds that do not have fluorine-iodine bonds. [1]

Properties

Fluoroiodates are transparent in visible, longer wave ultraviolet and some of the infrared electromagnetic bands. [1]

Compared to iodate, the I-O bonds are shorter, and I-F bonds are longer in fluoroiodates. The I-F bond is about 0.2 Å longer than the I-O bond. The fluorine atoms repel each other in [IO2F2]− and are almost opposite each other. The ∠OIF angle is close to 90° and the oxygen atoms ∠OFO are at about 102°, [2] so they resemble an octahedral arrangement, with two adjacent positions deleted. [1]

List

formulacrystalspace groupunit cellvolumedensityband

gap eV

SHG

× KDP

1064 nm

commentreference
NH4IO2F2orthorhombicPca21a=8.639 b=6.166 c=8.629 Z=4459.74.531.2 [2]
(NH4)3(IO2F2)3·H2OorthorhombicPnmaa=15.102 b=12.685 c=7.369 Z=41411.84.55no [2]
[C(NH2)3]+[IF2O2]–triclinicP1a = 6.6890 b = 10.2880 c = 10.30.92 α = 105.447 β = 108.568 γ = 91.051°644.082.650explosive; [3]
NaIO2F2orthorhombicCmcma=6.929 b=7.274 c=7.350 Z=4370.420 [4]
KIO2F2orthorhombicPca21a=8.3943 b=5.9792 c=8.4468 Z=4423.950 ferroelastic; when compressed on 001 axis IO2F2 units rotate with abc transforming to cba; [4] [5] [6]
CoIO3FmonoclinicP21/na=4.9954 b=5.2110 c=12.5179 β=95.347° [7]
NiIO3FmonoclinicP21/n [7]
ZnIO3FmonoclinicP21/m4.20.00birefringence 0.219 at 546 nm [1]
[GaF(H2O)][IO3F]orthorhombicPca21a=13.954 b=6.9261 c=4.76294.3410 laser damage threshold 298.40 MW cm−2; decompose 300 °C; dipole moment density: 0.0908 D Å−3 [8]
NaGaI3O9FmonoclinicP21/c_a=14.120 b=4.9149 c=13.63 β=112.968° Z=4871.04.8534.270∞[Ga2(IO3F)2(IO3)4]2− layers sandwiching Na+; birefringence Δnexp ~ 0.203 at 1064 nm [9]
RbIO2F2orthorhombicPca21a=8.567 b=6.151 c=8.652 Z=4455.924.24 [4]
SrI2O5F2monoclinicP21/ca=10.462 b=7.272 c=8.306 β=109.699° Z=4594.93.680 [10]
Sr4O(IO3)3(I3O7F3)BF4R3ca=9.7216 c=38.759absorption band at 250 nm; decompose 380 °C [11]
CdIO3FP2121214.226.2 [1]
Rb2MoO2F3(IO2F2)orthorhombicCmc21a 11.806 b 10.128 c 7.66613.775 [1] [12]
CsIO2F2orthorhombicPca21a=8.781 b=6.377 c=8.868 Z=4496.584.53 [4]
Cs3(IO2F2)3•H2OPnma3.370 [1]
Cs(IO2F2)2•H2O•H3OmonoclinicP21/c2.770 [1]
CsIO4Pnma0 [1]
Cs2VOF4(IO2F2)orthorhombicCmc21a=12.188 b=10.349 c=7.779 Z=4981.24.1002.885yellow at 1064 nm [13]
Cs2MoO2F3(IO2F2)orthorhombicCmc21a =12.2153 b =10.4656 c =7.85603.434.5 [1] [12]
BaIO3FmonoclinicP21/c4.320 [14]
Ba(IO2F2)2monoclinicP21/ca=10.747 b=7.161 c=9.086 β=93.748° Z=4697.73.990UV cut off 230 nm [10]
BaI2O5F2monoclinicP21/ca=10.750 b=7.599 c=8.598 β=109.753°birefringence Δn= 0.174 at 1064 nm [15]
BaIO2F3orthorhombicCmcaa=6.334 b=6.343 c=23.3004.270birefringence Δn=0.133 at 1064 nm [15]
CaCe(IO3)3(IO3F)ForthorhombicPna21a=11.068 b=18.15 c=6.0301 Z=41211.35.0332,725pale-yellow; birefringence 0.071 at 1064 nm SHG 5×KDP at 1064 nm [16]
Rb2WO2F3(IO2F2)orthorhombicCmc21a=11.726 b=10.188 c=7.6664.42 [17]
Cs2WO2F3(IO2F2)orthorhombicCmc21a=12.1122 b=10.6192 c =7.83334.29 [17]
Pb4O(IO3)3(I3O7F3)BF4R3ca =9.8184 c =38.867absorption band at 283 nm; decompose 300 °C [11]
KBi2(IO3)2F5monoclinicP21a=5.687 b = 5.864 c = 14.815 β=100.095º Z = 2486.56.157colourless [18]
RbBi2(IO3)2F5monoclinicP21a=5.7347 b = 5.9095 c = 15.117 β=100.263º Z = 2506.206.221colourless [18]
CsBi2(IO3)2F5monoclinicP21a=5.750 b = 5.864 c = 15.640 β=100.509º Z = 2523.86.313colourless [18]

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References

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  6. ↑ Abrahams, S. C.; Bernstein, J. L. (1976-04-15). "Ferroelastic KIO2F2: Crystal structure and ferroelastic transformation". The Journal of Chemical Physics. 64 (8): 3254–3260. Bibcode:1976JChPh..64.3254A. doi:10.1063/1.432666. ISSN   0021-9606.
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  9. ↑ Wang, Dandan; Gong, Pifu; Zhang, Xinyuan; Lin, Zheshuai; Hu, Zhanggui; Wu, Yicheng (2021). "NaGaI 3 O 9 F: a new alkali metal gallium iodate combined with IO 3 − and IO 3 F 2− units". Dalton Transactions. 50 (33): 11562–11567. doi:10.1039/D1DT02122B. ISSN   1477-9226. PMID   34351353. S2CID   236927523.
  10. 1 2 Gai, Minqiang; Tong, Tinghao; Wang, Ying; Yang, Zhihua; Pan, Shilie (2020-07-14). "New Alkaline-Earth Metal Fluoroiodates Exhibiting Large Birefringence and Short Ultraviolet Cutoff Edge with Highly Polarizable (IO 3 F) 2– Units". Chemistry of Materials. 32 (13): 5723–5728. doi:10.1021/acs.chemmater.0c01452. ISSN   0897-4756. S2CID   225712371.
  11. 1 2 Xu, Yiyi; Zhou, Yuqiao; Lin, Chensheng; Li, Bingxuan; Hao, Xia; Ye, Ning; Luo, Min (2021-12-01). "M 4 O(IO 3 ) 3 (I 3 O 7 F 3 )BF 4 (M = Pb, Sr): Promising Nonlinear Optical Materials Featuring the Unprecedented Windmill-Shaped [I 3 O 7 F 3 ] 2– Polyfluoroiodate Anion". Crystal Growth & Design. 21 (12): 7098–7103. doi:10.1021/acs.cgd.1c00992. ISSN   1528-7483. S2CID   244426909.
  12. 1 2 Hu, Yilei; Jiang, Xingxing; Wu, Chao; Huang, Zhipeng; Lin, Zheshuai; Humphrey, Mark G.; Zhang, Chi (2021-07-27). "A 2 MoO 2 F 3 (IO 2 F 2 ) ( A = Rb, Cs): Strong Nonlinear Optical Responses and Enlarged Band Gaps through Fluorine Incorporation". Chemistry of Materials. 33 (14): 5700–5708. doi:10.1021/acs.chemmater.1c01434. ISSN   0897-4756. S2CID   237721401.
  13. ↑ Ding, Mengmeng; Wu, Hongping; Hu, Zhanggui; Wang, Jiyang; Wu, Yicheng; Yu, Hongwei (2022). "Cs 2 VOF 4 (IO 2 F 2 ): Rationally designing a noncentrosymmetric early-transition-metal fluoroiodate". Journal of Materials Chemistry C. 10 (34): 12197–12201. doi:10.1039/D2TC02489F. ISSN   2050-7526. S2CID   251185610.
  14. ↑ Okrasinski, S.; Jost, R.; Rakshapal, R.; Mitra, G. (January 1975). "Preparation and properties of barium monofluorotrioxoiodate(V), BaIO3F". Inorganica Chimica Acta. 12 (1): 247–249. doi:10.1016/S0020-1693(00)89867-9.
  15. 1 2 Zhu, Liang; Gai, Minqiang; Jin, Wenqi; Yang, Yun; Yang, Zhihua; Pan, Shilie (2021). "Barium fluoroiodate crystals with a large band gap and birefringence". Inorganic Chemistry Frontiers. 8 (12): 3127–3133. doi:10.1039/D1QI00383F. ISSN   2052-1553. S2CID   236277200.
  16. ↑ Ma, Nan; Hu, Chun-Li; Chen, Jin; Fang, Zhi; Huang, Yu; Li, Bing-Xuan; Mao, Jiang-Gao (2022). "CaCe(IO 3 ) 3 (IO 3 F)F: a promising nonlinear optical material containing both IO 3 − and IO 3 F 2− anions". Inorganic Chemistry Frontiers. 9 (21): 5478–5485. doi:10.1039/D2QI01720B. ISSN   2052-1553. S2CID   252232612.
  17. 1 2 Hu, Yilei; Jiang, Xingxing; Wu, Tianhui; Xue, Yanyan; Wu, Chao; Huang, Zhipeng; Lin, Zheshuai; Xu, Jun; Humphrey, Mark G.; Zhang, Chi (2022). "Wide bandgaps and strong SHG responses of hetero-oxyfluorides by dual-fluorination-directed bandgap engineering". Chemical Science. 13 (35): 10260–10266. doi:10.1039/D2SC02137D. ISSN   2041-6520. PMC   9473499 . PMID   36277635.
  18. 1 2 3 Liu, Hongming; Wu, Qi; Jiang, Xingxing; Lin, Zheshuai; Meng, Xianggao; Chen, Xingguo; Qin, Jingui (2017-08-01). "ABi 2 (IO 3 ) 2 F 5 (A=K, Rb, and Cs): A Combination of Halide and Oxide Anionic Units To Create a Large Second-Harmonic Generation Response with a Wide Bandgap". Angewandte Chemie. 129 (32): 9620–9624. doi:10.1002/ange.201705672.
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