高等学校化学学报

高等学校化学学报 ›› 1996, Vol. 17 ›› Issue (4): 509.

• 论文 • 上一篇    下一篇

[Mn2(bzacen)2(MeOH)2(μ-4,4′-bipy)](ClO4)2的合成、结构和谱学性质

刘世雄, 冯云龙   

  1. 福州大学化学系, 福州 350002
  • 收稿日期:1995-06-03 出版日期:1996-04-24 发布日期:1996-04-24
  • 通讯作者: 刘世雄,男,52岁,教授,博士生导师.
  • 作者简介:刘世雄,男,52岁,教授,博士生导师.

Synthesis, Crystal Structure and Spectral Properties of [Mn2(bzacen)2(MeOH)2(μ-4,4′-bipy)](ClO4)2

LIU Shi-Xiong, FENG Yun-Long   

  1. Department of Chemistry, Fuzhou University, Fuzhou 350002
  • Received:1995-06-03 Online:1996-04-24 Published:1996-04-24

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摘要： 合成了[Mn2(bzacen)2(MeOH)2(μ-4,4′-bipy)](ClO4)2化合物,并测定其晶体结构。该晶体属单斜晶系,空间群P21/n,晶胞参数:a=1.3082(3)nm,b=1.2713(3)nm,c=1.8006(5)nm,β=110.91(2)°,Z=2,μ=5.97cm-1,R=0.0580,GOF=1.66.在配合物阳离子中,4,4′-联吡啶桥联2个[Mn(bzacen)(MeOH)]+,而锰原子具有3个N原子和3个O原子形成的扭曲八面体配位构型。红外光谱和拉曼光谱均表明,形成配合物后,vC=N、vC=O、和vC=C移向低频。红外光谱的1110cm-1谱带表明ClO4-未与Mn(Ⅲ)配位,812cm-1振动说明4,4′-bipy充当桥联二齿配体。拉曼光谱中的463cm-1和401cm-1别为Mn-O和Mn-N的振动带。电子光谱证明存在d-d*、d-π*和π-π*跃迁。电极电位测定显示该配合物Mn(Ⅲ)的价态是稳定的。

关键词: Schiff碱, Mn(Ⅲ)配合物, 晶体结构, 光谱性质

Abstract: The title complex[Mn2(bzacen)2(MeOH)2(μ-4,4′-bipy)](ClO4)2 crystallizes themonoclinic system, space group P21/n, with parameters: a=1.3082(3)nm,b=1.2713(3)nm,c=1.8006(5) nm,β=110.91(2)°,V=2.798(2)nm3,Dc=1.45g/cm3,Z=2,F(000)=1268,μ=5.97 cm-1.The final Rvalue is 0.0580 for 2961 observed reflectionswith I≥3σ(I).The complex cation has a bimeric structure with a 4,4′-bipyridine bridgingthe two[Mn(bzacen)(MeOH)]+ moieties.Mn(Ⅲ)ion shows a distorted octahedral coordination with four bonds to N2O2 donor atoms of Schiff base ligand bzacen2- in the basic plane,one Oatom of the MeOHand one Natom of the bridging 4,4′-bipyridine being in the twoopposite sites.The shifts of vC=N,vC=O and vC=C to lower frequencies in IRand Raman spectraindicate that the ligand bzacen2-is coordinated to Mn atom through its nitrogen and oxygenatoms, The lines observed at 463 cm-1 and 401 cm-1 in Raman spectrum are assigned toMn-Oand Mn-Nvibrations, respectively.The obsorption at about 1110 cm-1 shows that ClO4- is not coordinated with Mn atom.There are π-π* transiti On,d-π* chrge-transfer transitlons and d-d* transition in electronic spectrum.The current potential curve in acetonitrileexhbits that Mn(Ⅲ)is in a stable valence state.

Key words: Schiff base, Manganese complex, Crystal structure, Spectrum properties

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