【摘要】 应用乙酸锰、高锰酸钾和丙酸(或氯乙酸)混酸体系合成,得到了2个基于Mn12O12核心的十二核锰配合物,分子式分别为[Mn12O12(O2CMe)8(O2CEt)8(H2O)4].2H2O(1)和[Mn12O12(O2CMe)12(O2CCl3)4(H2O)4].4MeCO2H.8H2O(2)。X射线单晶衍射分析表明配合物1结晶于四方晶系I4空间群,晶胞参数为:a=b=2.650 5(3)nm,c=1.349 7(3)nm,Z=4;配合物2结晶于四方晶系I41/acd空间群,晶胞参数为:a=b=2.7067(1)nm,c=2.5880(2)nm,Z=8。这2个配合物结构都具备Mn12O12核心,与其他经典Mn12明星分子的核心相似。中心的Mn4O4立方核通过μ3-氧桥被非共面的Mn8O8环聚集在一起,而16个η2-μ-混合羧酸以不同方向在外围充当连接桥,同时提供了酸性环境。文中还分析了混酸体系的pKa值对配合物结构形成的影响。更多还原

【Abstract】 Two new Mn12O12 cores based dodecanuclear manganese complexes formulated with [Mn12O12(O2CMe)8(O2CEt)8(H2O)4]·2H2O(1) and [Mn12O12(O2CMe)12(O2CCl3)4(H2O)4]·4MeCO2H·8H2O(2) have been synthesized by the reaction of Mn(O2CMe)2·4H2O,KMnO4 and mixed acid of RCO2H and MeCO2H(R=Et(1),Cl3CCO2H(2)) in acidic conditions.X-ray diffraction crystal structure analysis shows that the complex 1 crystallizes in the tetragonal space group I4 has a=b=2.650 5(3) nm,c=1.349 7(3) nm and Z=4.The complex 2 crystallizes in tetragonal space group I41/acd has a=b=2.706 7(1) nm,c=2.588 0(2) nm and Z=8.In the two complexes,the structure of the Mn12O12 core is similar to that found in all classic Mn12 derivatives and comprises a central Mn4O4 cubane core surrounded by a nonplanar Mn8O8 ring held together with μ3-oxo bridges,while the peripheric bridging is ensured by sixteen η2-μ-mixed carboxylate anions in different orientations which provide an acidic condition.The effect of pKa data in each mixed acid system for obtaining the two complexes are also investigated in this article.更多还原