Syntheses, structures, and vibrational spectroscopy of the two-dimensional iodates Ln(IO3)3 and Ln(IO3)3(H2O) (Ln =Yb, Lu)

The reaction of Lu3+ or Yb3+ and H5IO6 in aqueous media at 180 oC leads to the formation of Yb(IO3)3(H2O) or Lu(IO3)3(H2O), respectively, while the reaction of Yb metal with H5IO6 under similar reaction conditions gives rise to the anhydrous iodate, Yb(IO3)3. Under supercritical conditions Lu3+ reacts with HIO3 and KIO4 to yield the isostructural Lu(IO3)3. The structures have been determined by single-crystal X-ray diffraction. Crystallographic data are (MoKα, λ=0.71073 A): Yb(IO3)3, monoclinic, space group P21/n, a=8.6664(9) A, b=5.9904(6) A, c=14.8826(15) A, β=96.931(2)o, V=766.99(13), Z=4, R(F)=4.23% for 114 parameters with 1880 reflections with I>2σ(I); Lu(IO3)3, monoclinic, space group P21/n, a=8.6410(9), b=5.9961(6), c=14.8782(16) A, β=97.028(2)o, V=765.08(14), Z=4, R(F)=2.65% for 119 parameters with 1756 reflections with I>2σ(I); Yb(IO3)3(H2O), monoclinic, space group C2/c, a=27.2476(15), b=5.6296(3), c=12.0157(7) A, β=98.636(1)o, V=1822.2(2), Z=8, R(F)=1.51% for 128 parameters with 2250 reflections with I>2σ(I); Lu(IO3)3(H2O), monoclinic, space group C2/c, a=27.258(4), b=5.6251(7), c=12.0006(16) A, β=98.704(2)o, V=1818.8(4), Z=8, R(F)=1.98% for 128 parameters with 2242 reflections with I>2σ(I). The f elements in all of the compounds are found in seven-coordinate environments and bridged with monodentate, bidentate, or tridentate iodate anions. Both Lu(IO3)3(H2O) and Yb(IO3)3(H2O) display distinctively different vibrational profiles from their respective anhydrous analogs. Hence, the Raman profile can be used as a complementary diagnostic tool to discern the different structural motifs of the compounds. - Graphical abstract: Four new metal iodates, Yb(IO3)3, Lu(IO3)3, Yb(IO3)3(H2O), and Lu(IO3)3(H2O), have all been isolated as single crystals through the use of hydrothermal reactions. Structural determinations using single-crystal X-ray diffraction have shown that the materials are all alike in that they contain two-dimensional structures. Vibrational profiles for all of the materials have been collected, using Raman spectroscopy, and analyzed