New thallium iodates—Synthesis, characterization, and calculations of Tl(IO3)3 and Tl4(IO3)6, [Tl+3Tl3+(IO3)6]

Two new thallium iodates have been synthesized, Tl(IO3)3 and Tl4(IO3)6 [Tl+3Tl3+(IO3)6], and characterized by single-crystal X-ray diffraction. Both materials were synthesized as phase-pure compounds through hydrothermal techniques using Tl2CO3 and HIO3 as reagents. The materials crystallize in space groups R-3 (Tl(IO3)3) and P-1 (Tl4(IO3)6). Although lone-pairs are observed for both I5+ and Tl+, electronic structure calculations indicate the lone-pair on I5+ is stereo-active, whereas the lone-pair on Tl+ is inert.