Dimensional Reduction From 2D Layer to 1D Band for Germanophosphates Induced by the 鈥淭ailor Effect鈥?of Fluoride

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• 作者：Chun-Zuo Huang ; Biao Liu ; Lei Wen ; Rong-Chuan Zhuang ; Jing-Tai Zhao ; Yuanming Pan ; Jin-Xiao Mi ; Ya-Xi Huang
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：July 20, 2015
• 年：2015
• 卷：54
• 期：14
• 页码：6978-6985
• 全文大小：649K
• ISSN：1520-510X

文摘

The 鈥渢ailor effect鈥?of fluoride, exclusively as a terminal rather than a bridge, was applied successfully to design low-dimensional structures in the system of transition metal germanophosphates for the first time. Two series of new compounds with low-dimensional structures are reported herein. K[M^IIGe(OH)₂(H_0.5PO₄)₂] (M = Fe, Co) possess flat layered structures built from single chains of edge-sharing M^IIO₆ and GeO₆ octahedra interconnected by HPO₄ tetrahedra. Their fluorinated derivatives, K₄[M^IIGe₂F₂(OH)₂(PO₄)₂(HPO₄)₂]路2H₂O (M = Fe, Co), exhibit band structures of two four-membered ring germanium phosphate single chains sandwiched by M^IIO₆ octahedra via corner-sharing. Both of these structures contain anionic chains of the condensation of four-membered rings built from alternating GeO₄桅₂ (桅 = F, OH) octahedra and PO₄ tetrahedra via sharing common GeO₄桅₂ (桅 = F, OH) octahedra, the topology of which is the same as that of the mineral kr枚hnkite [Na₂Cu(SO₄)₂路2H₂O]. Note that the switch from the two-dimensional layered structure to the one-dimensional band structure was performed simply by the addition of a small amount of KF路2H₂O to the reaction mixture. This structural alteration arises from the incorporation of one terminal F atom to the coordination sphere of Ge, which breaks the linkage between the transition metal and germanium octahedra in the layer to form the band structure.