Novel Fundamental Building Blocks and Site Dependent Isomorphism in the First Actinide Borophosphates

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• 作者：Shijun Wu ; Matthew J. Polinski ; Thomas Malcherek ; Ulrich Bismayer ; Martina Klinkenberg ; Giuseppe Modolo ; Dirk Bosbach ; Wulf Depmeier ; Thomas E. Albrecht-Schmitt ; Evgeny V. Alekseev
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：July 15, 2013
• 年：2013
• 卷：52
• 期：14
• 页码：7881-7888
• 全文大小：476K
• 年卷期：v.52,no.14(July 15, 2013)
• ISSN：1520-510X

文摘

Three novel uranyl borophosphates, Ag₂(NH₄)₃[(UO₂)₂{B₃O(PO₄)₄(PO₄H)₂}]H₂O (AgNBPU-1), Ag_(2-x)(NH₄)₃[(UO₂)₂{B₂P₅O_(20-x)(OH)_x}] (x = 1.26) (AgNBPU-2), and Ag_(2-x)(NH₄)₃[(UO₂)₂{B₂P_(5-y)As_yO_(20-x)(OH)_x}] (x = 1.43, y = 2.24) (AgNBPU-3), have been prepared by the H₃BO₃鈥揘H₄H₂PO₄/NH₄H₂AsO₄ flux method. The structure of AgNBPU-1 has an unprecedented fundamental building block (FBB), composed of three BO₄ and six PO₄ tetrahedra which can be written as 9鈻?[桅] 鈻?img src="/entityImage/?code=27E8&eTag=1d4sc6y" alt="" class="entityD" />3鈻?img src="/entityImage/?code=27E9&eTag=1d4sc6y" alt="" class="entityD" />鈻鈻?img src="/entityImage/?code=27E8&eTag=1d4sc6y" alt="" class="entityD" />3鈻?img src="/entityImage/?code=27E9&eTag=1d4sc6y" alt="" class="entityD" />鈻鈻?img src="/entityImage/?code=27E8&eTag=1d4sc6y" alt="" class="entityD" />3鈻?img src="/entityImage/?code=27E9&eTag=1d4sc6y" alt="" class="entityD" />鈻. Two Ag atoms are linearly coordinated; the coordination of a third one is T-shaped. AgNBPU-2 and AgNBPU-3 are isostructural and possess a FBB of two BO₄ and five TO₄ (T = P, As) tetrahedra (7鈻?鈻?img src="/entityImage/?code=27E8&eTag=1d4sc6y" alt="" class="entityD" />4鈻?img src="/entityImage/?code=27E9&eTag=1d4sc6y" alt="" class="entityD" />鈻鈻?. AgNBPU-3 is a solid solution with some PO₄ tetrahedra of the AgNBPU-2 end-member being substituted by AsO₄. Only two out of the three independent P positions are partially occupied by As, resulting in site dependent isomorphism. The three compounds represent the first actinide borophosphates.