Unprecedented 3D and 2D Frameworks of Manganese Thioarsenates Based on Heterometallic Cubic Cluster [Mn₆(µ₆-S)(AsS₃)₄] and Covalent Linker N₂H₄

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• 作者：Chunying Tang ; Yali Shen ; Peipei Sun ; ShuZhen Liu ; Jingyu Han ; Yun Liu ; Hui Sun and Dingxian Jia
• 刊名：European Journal of Inorganic Chemistry
• 出版年：2016
• 出版时间：August 2016
• 年：2016
• 卷：2016
• 期：24
• 页码：3921-3926
• 全文大小：1401K
• ISSN：1099-0682c

文摘

New Mn thioarsenates [Mn(dien)₂][Mn₆(µ₆-S)(µ-N₂H₄)₃(µ₃-AsS₃)₄]·H₂O (1) and [Mn(1,2-dap)₃][Mn₆(µ₆-S)(N₂H₄)₂(µ-N₂H₄)₂(µ₃-AsS₃)₄] (2) (dien = diethylenetriamine; 1,2-dap = 1,2-diaminopropane) were solvothermally synthesized with the synergistic assistance of coordinative polyamines and hydrazine. Compounds 1 and 2 contain a 3D {[Mn₆(µ₆-S)(µ-N₂H₄)₃(µ₃-AsS₃)₄]^2–}_⋡ network and a 2D {[Mn₆(µ₆-S)(N₂H₄)₂(µ-N₂H₄)₂(µ₃-AsS₃)₄]^2–}_⋡ layer, respectively, which are constructed by cubic [Mn₆(µ₆-S)(µ₃-AsS₃)₄] clusters and µ-N₂H₄ covalent linkers. In the [Mn₆(µ₆-S)(µ₃-AsS₃)₄] cluster, four As³⁺ cations occupy the four opposite vertexes, and six Mn²⁺ cations are located at the face centers. An S^2– anion at the heart of the cube coordinates to six Mn²⁺ cations at the face center in a µ₆-S mode, generating an octahedral Mn₆(µ₆-S) core. The Mn₆(µ₆-S) core and µ₆-S coordination mode are observed for the first time in the Mn/As/S system. In 1, the cubic [Mn₆As₄S₁₃] clusters are connected into a 3D framework of {[Mn₆(µ₆-S)(µ-N₂H₄)₃(µ₃-AsS₃)₄]^2–}_⋡ anions through three µ-N₂H₄ bridging ligands. In 2, the [Mn₆As₄S₁₃] cluster is joined by two µ-N₂H₄ bridging ligands and coordinated by two terminal N₂H₄ molecules, with formation of a 2D layer {[Mn₆(µ₆-S)(N₂H₄)₂(µ-N₂H₄)₂(µ₃-AsS₃)₄]^2–}_⋡. The room-temperature band gaps of 1 and 2 are 2.21 and 2.34 eV, respectively.