3,4-二甲氧基苯乙酸邻菲咯啉轻稀土配合物的合成、晶体结构、荧光光谱及热行为(英文)

Synthesis,Crystal Structure,Luminescence Spectrum and Thermal Analysis of Light Rare Earth Complexes from 3,4-Dimethoxyphenylacetic Acid and 1,10-Phenanthroline

合成了3,4-二甲氧基苯乙酸邻菲咯啉轻稀土配合物:[RE2(DMPA)6(phen)2](RE=Ce(1),Pr(2),Nd(3),Eu(4);HDMPA=3,4-二甲氧基苯乙酸,C12H12O4;phen=1,10-邻菲咯啉),用元素分析、红外光谱、热重分析对产物进行表征,用单晶X-射线衍射方法测定了配合物3的晶体结构。配合物C84H82Nd2N4O24(3)属于三斜晶系,P1空间群,晶胞参数:a=1.24206(9)nm,b=1.24456(9)nm,c=1.477 88(11)nm,α=90.617(4)°,β=103.486(4)°,γ=116.870(3)°,晶胞体积:V=1.963 8(2)nm3,晶胞内结构基元数Z=1,分子量Mr=1 820.02,电子数F(000)=926,密度Dc=1.539 g.cm-3,吸收系数μ(Mo Kα)=1.389 mm-1。测定了铕配合物的荧光光谱,荧光光谱表明,配合物显示了铕髥离子的特征发射,这表明配体将吸收的能量有效地转移给了中心离子,配体起到了很好的敏化作用。同时也测定了铕配合物的热分解情况,并利用TG-DTG曲线采用非等温积分法和微分法研究了热分解动力学机理。

Four light rare earth coordination polymers [RE2（DMPA）6（phen）2]（RE=Ce（1）,Pr（2）,Nd（3）,Eu（4）;HDMPA=3,4-dimethoxyphenylacetic acid,C12H12O4;phen=1,10-phenanthroline） were synthesized and characterized by elemental analysis,IR,TG-DTG and X-ray crystallographically.The single-crystal X-ray diffraction studies demonstrated that complex 3 is crystallize in triclinic space group P1 with a=1.242 06（9） nm,b=1.244 56（9） nm,c=1.477 88（11） nm,α=90.617（4）°,β=103.486（4）°,γ=116.870（3）°,V=1.963 8（2） nm3,Z=1,Mr=1 820.02,F（000）=926,Dc=1.539 g·cm-3,μ（Mo Kα）=1.389 mm-1 and formed 3D supramolecular architectures by hydrogen bonds and π-π stacking interactions.In all these complexes,the coordination number around RE（III） center is nine.The fluorescence spectrum of complex 4 is investigated.It is indicated that the luminescence behavior of complex results from metal-centered emission,ligand can transfer the energy to the central metal efficiently and can sensitize the central metal.The thermal decomposition of complex 4 and its kinetic mechanisms and equations are studied under the non-isothermal integral and differential methods in air by TG-DTG curves.CCDC： 732322,3.