Structural Diversity, Optical and Magnetic Properties of a Series of Manganese Thioarsenates with 1,10-Phenanthroline or 2,2鈥?Bipyridine Ligands: Using Monodentate Methylamine as an Alkalinity Regulat

详细信息    查看全文

• 作者：Guang-Ning Liu ; Guo-Cong Guo ; Feng Chen ; Shuai-Hua Wang ; Jing Sun ; Jin-Shun Huang
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：January 2, 2012
• 年：2012
• 卷：51
• 期：1
• 页码：472-482
• 全文大小：557K
• 年卷期：v.51,no.1(January 2, 2012)
• ISSN：1520-510X

文摘

The exploration in two hydro(solvo)thermal reaction systems As/S/Mn²⁺/phen/methylamine aqueous solution and As/S/Mn²⁺/2,2鈥?bipy/H₂O affords five new manganese thioarsenates with diverse structures, namely, (CH₃NH₃){[Mn(phen)₂](As^VS₄)}路phen (1 and 1鈥?/b>), (CH₃NH₃)₂{[Mn(phen)]₂(As^VS₄)₂} (2), {[Mn(phen)₂](As^III₂S₄)}_n (3), {[Mn(phen)]₃(As^IIIS₃)₂}路H₂O (4), and {[Mn(2,2鈥?bipy)₂]₂(As^VS₄)}[As^IIIS(S₅)] (5). Compound 1 comprises a {[Mn(phen)₂](As^VS₄)}^{鈭?/sup> complex anion, a monoprotonated methylamine cation and a phen molecule. Compound 2 contains a butterfly like {[Mn(phen)]₂(AsVS₄)₂}2鈥?/sup> anion charge compensated by two monoprotonated methylamine cations. Compound 3 is a neutral chain formed by a helical 1_{鈭?/sub>(AsIIIS2鈥?/sup>) vierer chain covalently bonds to [MnII(phen)]2+ complexes via all its terminal S atoms. Compound 4 features a neutral chain showing the stabilization of noncondensed (AsIIIS3)3鈥?/sup> anions in the coordination of [MnII(phen)]2+ complex cations. Compound 5 features a mixed-valent AsIII/AsV character and an interesting chalcogenidometalates structure, where a polycation formed by the connection of two [Mn(2,2鈥?bipy)2]2+ complex cation and a (AsVS4)3鈥?/sup> anion acts as a countercation for a polythioarsenate anion, [AsIIIS(S5)]鈭?/sup>. The title compounds exhibit optical gaps in the range 1.58鈥?.48 eV and blue photoluminescence. Interestingly, compound 1 displays a weak second harmonic generation (SHG) response being about 1/21 times of KTP (KTiOPO4). Magnetic measurements show paramagnetic behavior for 1 and dominant antiferromagnetic behavior for 2鈥?b>5}}. Of particular interest is 4, which is the first manganese chalcogenide showing spin-canting characteristic.