稀土卟啉配合物电子结构和光谱的INDO/CI研究

利用ＩＮＤＯ／ＣＩ方法研究镧系金属卟啉配合物中稀土离子的络合高度及溶剂配位， 发现稀土卟啉配合物的优化分子构型和络合高度随稀土离子半径减小而降低。对系列稀土卟啉配合物的电子光谱主要吸收带进行了指认， 计算结果与实验值能较好地吻合。讨论了稀土卟啉化合物的电子结构及能级变化规律， 并分析了它们的特征电子光谱。

Zhang Keli, Yuan Jibing, Yuan Liangjie, Sun Jutang( Department of Chemistry, Wuhan University, Wuhan 430072, China ) The RE metal benzoates were synthesized by hydrothermal reaction. The complexes were characterized by elemental analysis, IR and X ray powder diffraction. They can be represented by general formula Ln(C 6H 5COO) 3(Ln=La, Nd, Sm, Eu, Gd, Dy and Er). All of them are monoclinic with layered structure. The mechanism of thermal decomposition of RE metal benzoates was studied by using TG, DTA, IR, and gas chromatography mass spectrometry. The thermal decomposition of the RE benzoates in nitrogen proceeds in two stages: firstly it decomposes to form RE 2O(CO 3) 2 and organic compounds, then RE 2O(CO 3) 2 decomposes further to form RE metal oxides and carbon dioxide. The organic compounds obtained from the first step of the reaction are mainly benzophenone, 9,10 anthraquinone, 1,3 Diphenylisobenzofuran and so on.