| 混合价双核锰配合物[(bipy)2Mn(μ-O)2Mn(bipy)2](ClO4)3的合成晶体结构及性能 |
Synthesis Crystal Structure and Properties of Mixed-Valent Binuclear Manganese Complex[(bipy)2Mn(μ-O)2Mn(bipy)2](ClO4)3 |
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| 摘要: [Mn3O(O2CCH2Cl)6(C5H5N)2(H2O)]·CH2ClCOO·H2O在pH=4.5的HOAcNaOAc的缓冲水溶液中和2,2′联吡啶(bipy)反应,制得了混合价双核锰配合物[(bipy)2Mn(μ-O)2Mn(bipy)2](ClO4)3·1.5H2O。该配位化合物的X射线单晶衍射表明,该晶体属单斜晶系,空间群P21/c,晶胞参数:a=1.3854(3),b=1.3943(3),c=2.4225(5)nm,β=103.30°,V=4.554(2)nm3,Z=4,Dc=1.448g·cm-3。其紫外可见光谱在640nm处有一个峰,可指派为桥配体O2-到Mn(Ⅲ)的电荷迁移光谱.循环伏安实验说明,此配合物在半波电位E1/2为1.25V处,有一个可逆的氧化还原峰,这相应于(Ⅲ,Ⅳ)态氧化为(Ⅳ,Ⅳ)态,另外在0.37V处有一阴极峰,相应于(Ⅲ,Ⅳ)态还原为(Ⅲ,Ⅲ)态,在0.81V处有一氧化峰,相应于(Ⅲ,Ⅲ)态氧化为(Ⅲ,Ⅳ)态,这两个峰是不可逆的。 |
| 关键词: 混合价 锰双核配位化合物 晶体结构 合成 |
| 基金项目: 国家自然科学基金(No.29831010);陕西省教委专项基金(No.HF982224) |
| Abstract: Binuclear mixed valent manganese complex [(bipy)2Mn(μ-O)2 Mn(bipy)2](ClO4)3 was synthesied by the reaction of [Mn3O(O2CCH2Cl)6(C5H5N)2(H2O)]·CH2ClCOO· H2O with bipy and NaClO4 in the HAc NaAc buffer(pH=4.0). X-Ray diffraction result for the single crystal shows that the crystal is monoclinic, space group P21/c with a=1.3854(3), b=1.3943(3), c=2.4225(5)nm,β =103.30°, V=4.554(2)nm3, Z=4. Apeak of 640 nm in UV Vis spectrum is designed to electronic transition of bridge legand O2- to Mn(Ⅲ). Cyclic voltammogram shows the complex in CH3CN underwent reversible one electron reduction and oxidation at E1/2=1.25V. |
| Keywords: mixed-valent binuclear manganese complex crystal structure synthesis |
| 投稿时间：1999-10-18 修订日期：2000-03-06 |
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| 李君,张逢星,唐宗薰,史启祯,周忠远.混合价双核锰配合物[(bipy)2Mn(μ-O)2Mn(bipy)2](ClO4)3的合成晶体结构及性能[J].无机化学学报,2000,16(4):585-590. |
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