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

作者：Tang, Chunying; Shen, Yali; Sun, Peipei; Liu, ShuZhen; Han, Jingyu; Liu, Yun; Sun, Hui; Jia, Dingxian^*

来源：European Journal of Inorganic Chemistry, 2016, 2016(24): 3921-3926.

DOI：10.1002/ejic.201600580

• Manganese
• Cluster compounds
• Solvothermal synthesis
• Coordination modes
• Thioarsenates

New Mn thioarsenates [Mn(dien)(2)][Mn-6(mu(6)-S)(mu-N2H4)(3)(mu(3)-AsS3)(4)]mu H2O (1) and [Mn(1,2-dap)(3)][Mn-6(mu(6)-S)(N2H4)(2)(mu-N2H4)(2)(mu(3)-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 {[Mn-6(mu(6)-S)(mu-N2H4)(3)(mu(3)-AsS3)(4)](2-)}(infinity) network and a 2D {[Mn-6(mu(6)-S)(N2H4)(2)(mu-N2H4)(2)(mu(3)-AsS3)(4)](2-)}(infinity) layer, respectively, which are constructed by cubic [Mn-6(mu(6)-S)(mu(3)-AsS3)(4)] clusters and mu-N2H4 covalent linkers. In the [Mn-6(mu(6)-S)(mu(3)-AsS3)(4)] cluster, four As3+ cations occupy the four opposite vertexes, and six Mn2+ cations are located at the face centers. An S2- anion at the heart of the cube coordinates to six Mn2+ cations at the face center in a mu(6)-S mode, generating an octahedral Mn-6(mu(6)-S) core. The Mn-6(mu(6)-S) core and mu(6)-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 {[Mn-6(mu(6)-S)(mu-N2H4)(3)(mu(3)-AsS3)(4)](2-)}(infinity) anions through three mu-N2H4 bridging ligands. In 2, the [Mn6As4S13] cluster is joined by two mu-N2H4 bridging ligands and coordinated by two terminal N2H4 molecules, with formation of a 2D layer {[Mn-6(mu(6)-S)(N2H4)2(mu-N2H4)(2)(mu(3)-AsS3)(4)](2-)}(infinity). The room-temperature band gaps of 1 and 2 are 2.21 and 2.34 eV, respectively.

• 出版日期2016-8
• 单位苏州大学