【摘要】 在乙腈溶液中,由混合价三核锰配合物[Mn3O(ClCH2COO)6(py)2]?(H2O)(py为吡啶)与2,2′-联吡啶(bipy)反应合成了混合价(Mn3IIIMnII)四核锰配合物[Mn4O2(ClCH2COO)7(bipy)2]?H2O.采用元素分析、红外光谱、热分析和X射线单晶衍射法确定了其组成和结构.标题化合物晶体属于三斜晶系,空间群P-1,晶胞参数:a=0.89854(13)nm,b=1.4027(2)nm,c=1.9037(3)nm,α=93.518(3)°,β=96.736(3)°,γ=94.875(3)°,V=2.3680(6)nm3,Z=2,Dc=1.734g/cm3,F(000)=1238,GOF=1.036,R1=0.0592,wR2=0.1162[I>2σ(I)].在标题化合物中,配位结构单元中心为一蝶型[Mn4(μ3-O)2]7+多核簇,含有2个Mn3(μ3-O)单元,具有近似C2对称轴.4个Mn离子均为六配位,外围配体为7个氯乙酸根和2个2,2′-联吡啶,处于变形的八面体环境.变温磁化率研究表明标题化合物在整体上表现为反铁磁性耦合作用,但在低温下的磁相互作用较为复杂.更多还原

【Abstract】 The reaction of trinuclear manganese complex [Mn3O(ClCH2COO)6(py)2]?(H2O) with 2,2′-bipyridine in CH3CN led to the new mixed valence tetranuclear III II Mn 3Mn complex of formulation [Mn4O2(ClCH2COO)7(bipy)2]?H2O. The structure and chemical composition of title complex were deter- mined by elemental analysis, IR spectrum, thermal analysis and X-ray diffraction analysis. The crystal structure belongs to triclinic system with space group P-1 and a=0.89854(13) nm, b=1.4027(2) nm, c= 1.9037(3) nm, α=93.518(3)°, β=96.736(3)°, γ=94.875(3)°, V=2.3680(6) nm3, Z=2, Dc=1.734 g/cm3, F(000)=1238, GOF=1.036, R1=0.0592, wR2=0.1162 [I>2σ(I)]. The analysis of the crystal structure in- dicates that the title complex has a butterfly [Mn4(μ3-O)2]7+core, which consists of two Mn3(μ3-O) units, with approximate C2 symmetric axis. The four manganese atoms are all six-coordinated with seven chloro- acetate acid anions and two 2,2′-bipyridine molecules, forming distorted octahedron configuration. Variable temperature magnetic susceptibility of the title complex showed the existence of intramolecular antiferro- magnetic interaction, and it was intricate at relatively low temperature.更多还原