在水-乙醇混合体系中,将浓硝酸硝化的Sm2O3与1,10-邻菲哕啉反应,用冰醋酸调节pH≈4,形成醋酸根桥联的双核钐配合物[Sm2(CH3COO)4(NO3)2(phen)2](phen=1,10-邻菲哕啉),用元素分析、红外光谱和核磁共振谱等进行了表征,并用X射线衍射测定了配合物的晶体结构,此外,对配合物进行了非等温热分解动力学研究.该晶体属于三斜晶系,P1空间群,晶胞参数a=0.9796(3)nm,b=0.9813(4)nm,c=1.1273(4)nm,α=106.666(5)。β=113.034(5)°,γ=102.656(5)°,V=0.8854(5)nm^3,Z=1,μ=3.361mm^-1,Dc=1.915g/ cm^3,F(000)=498,R1=0.0596,wR2=0.1448.该配合物是双核分子,2个Sm(111)离子通过4个醋酸根的羧基桥联,每个中心离子分别与周围5个来自羧基的桥氧原子、一个硝酸根的两个氧原子和一个邻菲哕啉分子中的两个氮原子配位,形成九配位扭曲多面体.非等温热分解动力学研究结果表明,配合物第一步热分解反应可能为二级反应,其动力学方程为dw/dT=A/[βe^-E/RT(1-α)^2],分解反应的表观活化能为344.84kJ/mol,指前因子lnA=66.52.
Reaction of nitrated Sm203 with 1,10-phenanthroline in the system of EtOH/H20 with pH ≈4 adjusted by HAc resulted in a novel acetate anions bridged dinuclear Sm ( Ⅲ ) complex Sm2 (CH3COO)4· (NO3)2 (phen)2, the complex was characterized by elemental analysis, IR, NMR spectroscopy and the crystal structure was determined by X-ray diffraction. Besides, the kinetics of thermal decomposition of the complex was studied by thermal analysis technique under non-isothermal condition. The crystal structure belongs to the triclinic system, space group P1 with a =0. 979 6(3) nm, b =0. 981 3(4) nm, c = 1. 127 3(4) nm, α=106.666(5)°,β=113.034(5)°, γ=102.656(5)°, V=0.885 4(5) nm^3 Z=1 μ=3.361 mm^-1 Dc = 1. 915 g/cm^3, F(000) =498, R1 =0. 059 6, wR2 =0. 144 8. The possible reaction mechanism was suggested to be a second order chemical reaction. The kinetic equation may be expressed as dα/dT = A/[βe^-E/Rr( 1 -α)2]. The apparent activation energy and pre-exponential factor of the reaction were 344.84 kJ/mol and lnA = 66. 52, respectively.