Investigation of New Alkali Bismuth Oxosulfates and Oxophosphates with Original Topologies of Oxo-Centered Units

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• 作者：Minfeng L眉 ; Marie Colmont ; Marielle Huv茅 ; Isabelle De Waele ; Christine Terryn ; Almaz Aliev ; Olivier Mentr茅
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：November 17, 2014
• 年：2014
• 卷：53
• 期：22
• 页码：12058-12065
• 全文大小：625K
• ISSN：1520-510X

文摘

Two new alkali bismuth oxosulfates, [Bi₁₂O₁₅]Li₂(SO₄)₄ (I) and [Bi₇K₂O₈]K(SO₄)₄ (II), have been synthesized by heating a mixture of Bi₂O₃, CuSO₄5H₂O, and A₂CO₃ (A = Li, K), and characterized by single crystal XRD, transmission electron microscopy, and multiphoton SHG and IR spectroscopy. In the above formula the [Bi_xO_y] subunits denote the 3D-porous (I) or 1D-columnar (II) polycationic host-lattice formed of edge-sharing OBi₄ or O(Bi,K)₄ oxocenterd tetrahedra. The SO₄^{2鈥?/sup> groups and alkali ions are arranged into channels in the interstices leading to original opened crystal structures for these two first reported alkali oxo-bismuth sulfates. The strong adaptability of the oxocentered framework is demonstrated by the possibility of preparing single crystals of [Bi_8.73K_0.27O₈]K_1.54(PO₄)₄ (III) whose crystal structure is similar to those of II with disorder between OBi₄ and O(Bi₃,K) tetrahedra and different channel occupancy due to the aliovalent replacement of SO₄2鈥?/sup> for PO₄3鈥?/sup>.}