Iodide-Iodates M3[IO3]12·Ag4I, M = Bi, Tb, with a Framework Structure and High Second-Harmonic Generation Optical Response

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• 作者：Elena L. BelokonevaSergey Yu. Stefanovich ; Olga V. Dimitrova ; Alina S. Karamysheva ; Anatoly S. Volkov
• 刊名：Inorganic Chemistry
• 出版年：2017
• 出版时间：February 6, 2017
• 年：2017
• 卷：56
• 期：3
• 页码：1186-1192
• 全文大小：431K
• ISSN：1520-510X

文摘

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.