Fluoroiodate Explained
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]
Different ions include [IOF<sub>4</sub>]−, [IO<sub>2</sub>F<sub>2</sub>]−, [IO<sub>3</sub>F]2−, and [I<sub>2</sub>O<sub>5</sub>F<sub>2</sub>]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 [IO<sub>2</sub>F<sub>2</sub>]− and are almost opposite each other. The ∠OIF angle is close to 90° and the oxygen atoms ∠OFO are at about 102°, so they resemble an octahedral arrangement, with two adjacent positions deleted.[1]
List
| formula | crystal | space group | unit cell | volume | density | bandgapeV | SHG× KDP 1064 nm
| comment | reference |
|---|
| NH4IO2F2 | orthorhombic | Pca21 | a=8.639 b=6.166 c=8.629 Z=4 | 459.7 | | 4.53 | 1.2 | | [2] |
| (NH4)3(IO2F2)3·H2O | orthorhombic | Pnma | a=15.102 b=12.685 c=7.369 Z=4 | 1411.8 | | 4.55 | no | | |
| [C(NH<sub>2</sub>)<sub>3</sub>]+[IF<sub>2</sub>O<sub>2</sub>]– | triclinic | P | a = 6.6890 b = 10.2880 c = 10.30.92 α = 105.447 β = 108.568 γ = 91.051° Z=4 | 644.08 | 2.650 | 4.81 | | explosive; birefringence Δn = 0.110 | [3] [4] |
| (C(NH2)3)2(I2O5F)(IO3)(H2O) | monoclinic | P21/c | a=7.4388 b=19.2679 c=11.0753 β=106.289° Z=4 | 1523.70 | | 4.49 | | birefringence Δn = 0.068 | |
| NaIO2F2 | orthorhombic | Cmcm | a=6.929 b=7.274 c=7.350 Z=4 | 370.42 | | | 0 | | [5] |
| KIO2F2 | orthorhombic | Pca21 | a=8.3943 b=5.9792 c=8.4468 Z=4 | 423.95 | | | 0 | ferroelastic
- when compressed on 001 axis IO2F2 units rotate with abc transforming to cba;
| [6] [7] |
| CoIO3F | monoclinic | P21/n | a=4.9954 b=5.2110 c=12.5179 β=95.347° | | | | | | [8] |
| NiIO3F | monoclinic | P21/n | | | | | | | |
| ZnIO3F | monoclinic | P21/m | | | | 4.2 | 0.00 | birefringence 0.219 at 546 nm | |
| [GaF(H<sub>2</sub>O)][IO<sub>3</sub>F] | orthorhombic | Pca21 | a=13.954 b=6.9261 c=4.7629 | | | 4.34 | 10 | laser damage threshold 298.40 MW cm−2; decompose 300 °C; dipole moment density: 0.0908 D Å−3 | [9] |
| NaGaI3O9F | monoclinic | P21/c | _a=14.120 b=4.9149 c=13.63 β=112.968° Z=4 | 871.0 | 4.853 | 4.27 | 0 | ∞[Ga<sub>2</sub>(IO<sub>3</sub>F)<sub>2</sub>(IO<sub>3</sub>)<sub>4</sub>]2− layers sandwiching Na+; birefringence Δnexp ~ 0.203 at 1064 nm | [10] |
| RbIO2F2 | orthorhombic | Pca21 | a=8.567 b=6.151 c=8.652 Z=4 | 455.92 | | 4.2 | 4 | | |
| SrI2O5F2 | monoclinic | P21/c | a=10.462 b=7.272 c=8.306 β=109.699° Z=4 | 594.9 | | 3.68 | 0 | | [11] |
| Sr4O(IO3)3(I3O7F3)BF4 | | R3c | a=9.7216 c=38.759 | | | | | absorption band at 250 nm; decompose 380 °C | [12] |
| CdIO3F | | P212121 | | | | 4.22 | 6.2 | | |
| Rb2MoO2F3(IO2F2) | orthorhombic | Cmc21 | a 11.806 b 10.128 c 7.6661 | | | 3.77 | 5 | | [13] |
| CsIO2F2 | orthorhombic | Pca21 | a=8.781 b=6.377 c=8.868 Z=4 | 496.58 | | 4.5 | 3 | | |
| Cs3(IO2F2)3•H2O | | Pnma | | | | 3.37 | 0 | | |
| Cs(IO2F2)2•H2O•H3O | monoclinic | P21/c | | | | 2.77 | 0 | | |
| CsIO4 | | Pnma | | | | | 0 | | |
| Cs2VOF4(IO2F2) | orthorhombic | Cmc21 | a=12.188 b=10.349 c=7.779 Z=4 | 981.2 | 4.100 | 2.88 | 5 | yellow at 1064 nm | [14] |
| Cs2MoO2F3(IO2F2) | orthorhombic | Cmc21 | a =12.2153 b =10.4656 c =7.8560 | | | 3.43 | 4.5 | | |
| BaIO3F | monoclinic | P21/c | | | | 4.32 | 0 | | [15] |
| Ba(IO2F2)2 | monoclinic | P21/c | a=10.747 b=7.161 c=9.086 β=93.748° Z=4 | 697.7 | | 3.99 | 0 | UV cut off 230 nm | |
| BaI2O5F2 | monoclinic | P21/c | a=10.750 b=7.599 c=8.598 β=109.753° | | | | | birefringence Δn= 0.174 at 1064 nm | [16] |
| BaIO2F3 | orthorhombic | Cmca | a=6.334 b=6.343 c=23.300 | | | 4.27 | 0 | birefringence Δn=0.133 at 1064 nm | |
| Ba2[GaF<sub>5</sub>(IO<sub>3</sub>F)] | monoclinic | P21/c | a=7.5065 b=7.4160 c=14.5932 β=100.363° | | | | | birefringence Δn=0.068 at 550 nm; UV edge 230 nm; transparent 0.34–11.9 μm | [17] |
| CaCe(IO3)3(IO3F)F | orthorhombic | Pna21 | a=11.068 b=18.15 c=6.0301 Z=4 | 1211.3 | 5.033 | 2,72 | 5 | pale-yellow; birefringence 0.071 at 1064 nm SHG 5×KDP at 1064 nm | [18] |
| Rb2WO2F3(IO2F2) | orthorhombic | Cmc21 | a=11.726 b=10.188 c=7.666 | | | 4.42 | | | [19] |
| Cs2WO2F3(IO2F2) | orthorhombic | Cmc21 | a=12.1122 b=10.6192 c =7.8333 | | | 4.29 | | | |
| Pb4O(IO3)3(I3O7F3)BF4 | | R3c | a =9.8184 c =38.867 | | | | | absorption band at 283 nm; decompose 300 °C | |
| KBi2(IO3)2F5 | monoclinic | P21 | a=5.687 b = 5.864 c = 14.815 β=100.095º Z = 2 | 486.5 | 6.157 | | | colourless | [20] |
| RbBi2(IO3)2F5 | monoclinic | P21 | a=5.7347 b = 5.9095 c = 15.117 β=100.263º Z = 2 | 506.20 | 6.221 | | | colourless | |
| CsBi2(IO3)2F5 | monoclinic | P21 | a=5.750 b = 5.864 c = 15.640 β=100.509º Z = 2 | 523.8 | 6.313 | | | colourless | | |
Notes and References
- Gao . Dong . Wu . Hongping . Hu . Zhanggui . Wang . Jiyang . Wu . Yicheng . Yu . Hongwei . Recent advances in F-containing iodate nonlinear optical materials . Chinese Journal of Structural Chemistry . January 2023 . 42 . 1 . 100014 . 10.1016/j.cjsc.2023.100014. 255888212 . free .
- Huang . Jianlong . Guo . Fengjiao . Guo . Zhiyong . Chen . Jianbang . Dai . Bin . Yu . Feng . 2022-08-01 . NH 4 IO 2 F 2 and (NH 4) 3 (IO 2 F 2) 3 ·H 2 O: A Series of Ammonium-Containing Fluoroiodates with Wide Band Gaps . Inorganic Chemistry . en . 61 . 30 . 11803–11810 . 10.1021/acs.inorgchem.2c01540 . 35860841 . 250731650 . 0020-1669.
- Fischer . Dennis . Klapötke . Thomas M. . Stierstorfer . Jörg . May 2011 . Synthesis and Characterization of Guanidinium Difluoroiodate, [C(NH2)3]+[IF2O2]- and its Evaluation as an Ingredient in Agent Defeat Weapons‡ ]. Zeitschrift für anorganische und allgemeine Chemie . en . 637 . 6 . 660–665 . 10.1002/zaac.201100052.
- Cui . Juhui . Wang . Shibin . Tudi . Abudukadi . Gai . Minqiang . Yang . Zhihua . Pan . Shilie . 2023-12-22 . (C(NH 2) 3) 2 (I 2 O 5 F)(IO 3)(H 2 O) and C(NH 2) 3 IO 2 F 2 : Two Guanidine Fluorooxoiodates with Wide Band Gap and Large Birefringence . Inorganic Chemistry . en . 10.1021/acs.inorgchem.3c03551 . 38131323 . 266468595 . 0020-1669.
- Wang . Shibin . Zhang . Jie . Chen . Jianbang . Han . Peng . Lei . Na . Huang . Xuchu . Enhancement of birefringence and refractive index dispersion optimization from iodates to fluorooxoiodates . New Journal of Chemistry . 2023 . 47 . 26 . 12145–12151 . 10.1039/D3NJ01908J. 258852807 .
- Helmholz . Lindsay . Rogers . M. T. . June 1940 . The Crystal Structure of Potassium Fluoroiodate, KIO 2 F 2 . Journal of the American Chemical Society . en . 62 . 6 . 1537–1542 . 10.1021/ja01863a058 . 0002-7863.
- Abrahams . S. C. . Bernstein . J. L. . 1976-04-15 . Ferroelastic KIO2F2: Crystal structure and ferroelastic transformation . The Journal of Chemical Physics . en . 64 . 8 . 3254–3260 . 10.1063/1.432666 . 1976JChPh..64.3254A . 0021-9606.
- Liu . Hang . Wang . Yanhong . Zhou . Yadong . Li . Shuang . Dou . Yaling . Wang . Tao . Lu . Hongcheng . 2022-11-07 . MIO 3 F (M = Co and Ni): Magnetic Iodate Fluorides with Zigzag Chains . Inorganic Chemistry . en . 61 . 44 . 17838–17847 . 10.1021/acs.inorgchem.2c03167 . 36285503 . 253119337 . 0020-1669.
- Huang . Qian-Ming . Hu . Chun-Li . Yang . Bing-Ping . Fang . Zhi . Lin . Yuan . Chen . Jin . Li . Bing-Xuan . Mao . Jiang-Gao . 2021 . [GaF(H 2 O)][IO 3 F]
a promising NLO material obtained by anisotropic polycation substitution ]
. Chemical Science . en . 12 . 27 . 9333–9338 . 10.1039/D1SC01401C . 2041-6520 . 8278931 . 34349903.
- 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 . en . 50 . 33 . 11562–11567 . 10.1039/D1DT02122B . 34351353 . 236927523 . 1477-9226.
- 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 . en . 32 . 13 . 5723–5728 . 10.1021/acs.chemmater.0c01452 . 225712371 . 0897-4756.
- 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 . en . 21 . 12 . 7098–7103 . 10.1021/acs.cgd.1c00992 . 244426909 . 1528-7483.
- 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 . en . 33 . 14 . 5700–5708 . 10.1021/acs.chemmater.1c01434 . 237721401 . 0897-4756.
- 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 . en . 10 . 34 . 12197–12201 . 10.1039/D2TC02489F . 251185610 . 2050-7526.
- Okrasinski . S. . Jost . R. . Rakshapal . R. . Mitra . G. . January 1975 . Preparation and properties of barium monofluorotrioxoiodate(V), BaIO3F . Inorganica Chimica Acta . en . 12 . 1 . 247–249 . 10.1016/S0020-1693(00)89867-9.
- 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 . en . 8 . 12 . 3127–3133 . 10.1039/D1QI00383F . 236277200 . 2052-1553.
- Wang . Yu-Hang . Li . Fu-Ying . Jiao . Dong-Xue . Wei . Qi . Wei . Li . Yang . Guo-Yu . 2023-10-17 . Optically Anisotropic Mixed-Metal Fluoroiodate Ba 2 [GaF 5 (IO 3 F)] with a Wide Optical Transparent Window and a Moderate Birefringence ]. Inorganic Chemistry . 62 . 43 . 17691–17696 . en . 10.1021/acs.inorgchem.3c02213 . 264168584 . 0020-1669.
- 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 . en . 9 . 21 . 5478–5485 . 10.1039/D2QI01720B . 252232612 . 2052-1553.
- 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 . en . 13 . 35 . 10260–10266 . 10.1039/D2SC02137D . 2041-6520 . 9473499 . 36277635.
- 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 . en . 129 . 32 . 9620–9624 . 10.1002/ange.201705672. 2017AngCh.129.9620L .
