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 [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
editFluoroiodates 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
edit| formula | crystal | space group | unit cell | volume | density | band
gap eV |
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 | [2] | ||
| [C(NH2)3]+[IF2O2]– | triclinic | P1 | 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 | [4] | ||
| 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; | [5][6][7] | ||
| CoIO3F | monoclinic | P21/n | a=4.9954 b=5.2110 c=12.5179 β=95.347° | [8] | |||||
| NiIO3F | monoclinic | P21/n | [8] | ||||||
| ZnIO3F | monoclinic | P21/m | 4.2 | 0.00 | birefringence 0.219 at 546 nm | [1] | |||
| [GaF(H2O)][IO3F] | 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 | ∞[Ga2(IO3F)2(IO3)4]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 | [5] | ||
| 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 | [1] | |||||
| Rb2MoO2F3(IO2F2) | orthorhombic | Cmc21 | a 11.806 b 10.128 c 7.6661 | 3.77 | 5 | [1][13] | |||
| CsIO2F2 | orthorhombic | Pca21 | a=8.781 b=6.377 c=8.868 Z=4 | 496.58 | 4.5 | 3 | [5] | ||
| Cs3(IO2F2)3•H2O | Pnma | 3.37 | 0 | [1] | |||||
| Cs(IO2F2)2•H2O•H3O | monoclinic | P21/c | 2.77 | 0 | [1] | ||||
| CsIO4 | Pnma | 0 | [1] | ||||||
| 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 | [1][13] | |||
| 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 | [11] | |
| 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 | [16] | ||
| Ba2[GaF5(IO3F)] | 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 | [19] | ||||
| Pb4O(IO3)3(I3O7F3)BF4 | R3c | a =9.8184 c =38.867 | absorption band at 283 nm; decompose 300 °C | [12] | |||||
| 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 | [20] | ||
| CsBi2(IO3)2F5 | monoclinic | P21 | a=5.750 b = 5.864 c = 15.640 β=100.509º Z = 2 | 523.8 | 6.313 | colourless | [20] |
References
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