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Published on: May 29, 2018
Iodide-Iodates M3[IO3]12·Ag4I, M = Bi, Tb, with a Framework Structure and High Second-Harmonic Generation Optical
Elena L Belokoneva1, Sergey Yu Stefanovich2, Olga V Dimitrova1
1Geological Faculty, Department of Crystallography, Lomonosov Moscow State University , Leninskije Gory 1, Moscow, 119992 GSP2, Russia.
Abstract:
Single crystals of two new iodide-iodates, Bi3[IO3]12·Ag4I and Tb3[IO3]12·Ag4I, are synthesized in hydrothermal systems. The anionic parts in both iodide-iodates are characterized as a complex charged framework of isolated IO3 umbrella-like groups and large Bi(Tb)-O polyhedra similar to those previously found in La3[IO3]12[IO3](Pb3O). Broad channels along the c-axis contain compensators: (Ag3I)2+ umbrella-like groups and additional Ag+ ions which form Ag44+ tetrahedral clusters augmented with I- halogen. New iodates possess significantly higher second-order nonlinear optical characteristics compared to the previously known lead-containing compounds REE3[IO3]12[IO3](Pb3O), REE = La, Pr, Nd. The difference is related to the polar ordering of umbrella-like (Ag3I)2+ groups in the channels in the new iodide-iodate. Additionally, planar-coordinated Ag atoms add three Ag atoms in umbrellas forming [Ag4I]3+ polar clusters in the channels.
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