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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.

Different ions include , , , and .

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

Properties

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

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 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.

List

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
(NH4)3(IO2F2)3·H2O orthorhombic Pnma a=15.102 b=12.685 c=7.369 Z=4 1411.8 4.55 no
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
(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
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;
CoIO3F monoclinic P21/n a=4.9954 b=5.2110 c=12.5179 β=95.347°
NiIO3F monoclinic P21/n
ZnIO3F monoclinic P21/m 4.2 0.00 birefringence 0.219 at 546 nm
orthorhombic Pca21 a=13.954 b=6.9261 c=4.7629 4.34 10 laser damage threshold 298.40 MW cm; decompose 300 °C; dipole moment density: 0.0908 D Å
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 ∞ layers sandwiching Na; birefringence Δnexp ~ 0.203 at 1064 nm
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
Sr4O(IO3)3(I3O7F3)BF4 R3c a=9.7216 c=38.759 absorption band at 250 nm; decompose 380 °C
CdIO3F P212121 4.22 6.2
Rb2MoO2F3(IO2F2) orthorhombic Cmc21 a 11.806 b 10.128 c 7.6661 3.77 5
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
Cs2MoO2F3(IO2F2) orthorhombic Cmc21 a =12.2153 b =10.4656 c =7.8560 3.43 4.5
BaIO3F monoclinic P21/c 4.32 0
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
BaIO2F3 orthorhombic Cmca a=6.334 b=6.343 c=23.300 4.27 0 birefringence Δn=0.133 at 1064 nm
Ba2 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
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
Rb2WO2F3(IO2F2) orthorhombic Cmc21 a=11.726 b=10.188 c=7.666 4.42
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
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

References

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Iodates
HIO3 He
LiIO3 Be +BO3 C (NH4)IO3
+NO3 		O +F
-F 		Ne
NaIO3 Mg(IO3)2 Al(IO3)3 Si P +SO4 Cl Ar
KIO3 Ca(IO3)2 Sc(IO3)3 Ti(IO3)4 V Cr Mn(IO3)2 Fe(IO3)2
Fe(IO3)3 		Co(IO3)2 Ni(IO3)2 Cu(IO3)2 Zn(IO3)2 Ga(IO3)3 Ge As Se Br Kr
RbIO3 Sr(IO3)2 Y(IO3)3 Zr(IO3)4 Nb Mo Tc Ru Rh Pd AgIO3 Cd(IO3)2 In(IO3)3 Sn(IO3)4 Sb Te I Xe
CsIO3 Ba(IO3)2 * Lu(IO3)3 Hf(IO3)4 Ta W Re Os Ir Pt Au(IO3)3 Hg2(IO3)2
Hg(IO3)2 		TlIO3 Pb(IO3)2 Bi(IO3)3 Po At Rn
Fr Ra(IO3)2 ** Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
 
* La(IO3)3 Ce(IO3)3 Pr(IO3)3 Nd(IO3)3 Pm(IO3)3 Sm(IO3)3 Eu(IO3)3 Gd(IO3)3 Tb(IO3)3 Dy(IO3)3 Ho(IO3)3 Er(IO3)3 Tm(IO3)3 Yb(IO3)3
** Ac Th(IO3)4 Pa U(IO3)2 Np(IO3)4 Pu(IO3)4 Am Cm Bk Cf Es Fm Md No
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