Magnetism and Raman spectroscopy of the dimeric lanthanide iodates Ln(IO3)3 (Ln=Gd, Er) and magnetism of Yb(IO3)3

Colorless single crystals of Gd(IO3)3 or pale pink single crystals of Er(IO3)3 have been formed from the reaction of Gd metal with H5IO6 or Er metal with H5IO6 under hydrothermal reaction conditions at 180 °C. The structures of both materials adopt the Bi(IO3)3 structure type. Crystallographic data are (MoKα, λ=0.71073 Å): Gd(IO3)3, monoclinic, space group P21/n, a=8.7615(3) Å, b=5.9081(2) Å, c=15.1232(6) Å, β=96.980(1)°, V=777.03(5) Z=4, R(F)=1.68% for 119 parameters with 1930 reflections with I>2σ(I); Er(IO3)3, monoclinic, space group P21/n, a=8.6885(7) Å, b=5.9538(5) Å, c=14.9664(12) Å, β=97.054(1)°, V=768.4(1) Z=4, R(F)=2.26% for 119 parameters with 1894 reflections with I>2σ(I). In addition to structural studies, Gd(IO3)3, Er(IO3)3, and the isostructural Yb(IO3)3 were also characterized by Raman spectroscopy and magnetic property measurements. The results of the Raman studies indicated that the vibrational profiles are adequately sensitive to distinguish between the structures of the iodates reported here and other lanthanide iodate systems. The magnetic measurements indicate that only in Gd(IO3)3 did the 3+ lanthanide ion exhibit its full 7.9 μB Hund's rule moment; Er3+ and Yb3+ exhibited ground state moments and gap energy scales of 8.3 μB/70 K and 3.8 μB/160 K, respectively. Er(IO3)3 exhibited extremely weak ferromagnetic correlations (+0.4 K), while the magnetic ions in Gd(IO3)3 and Yb(IO3)3 were fully non-interacting within the resolution of our measurements (∼0.2 K). © 2008 Elsevier Inc. All rights reserved.