轻稀土氯化物与2,3,11,12-四苯基-1,4,7,10,13,16-六氧-2,11-十八环二烯配合物的合成及XPS研究

Synthesis and XPS Satellite Phenomena of Complexes of the Light Rare Earth Chloride with 2, 3, 11, 12-Tetraphenyl-1, 4, 7, 10, 13, 16-hexaoxa-2, 11-coyclooctadecadiene

本工作合成了轻稀土氯化物与题目不饱和冠醚所形成的三种新的轻稀土配合物。元素分析数据说明稀土氯化物与配体的化学配比是1:1。我们着重对这些配合物进行了X射线光电子能谱研究,得到了组成原子芯能级电子(Ln 3d_(5/2),O 1s,C 1s,Cl 2p)的结合能变化信息。在LnCl_3·L和LnCl_3中观察到Ln 3d_(5/2)[Ln=Ce(Ⅲ),Pr(Ⅲ),Sm(Ⅲ)]的伴峰结构,其伴峰能前者分别为3.8和-4.2eV,后者为3.9,-4.5和-3.1eV。这是由于Cl 3p→Ln 4f电荷转移跃迁所引起的,铈属于“振起”(Shake-up)过程,镨和钐属于“振落”(Shake-down)过程。

Three new complexes of the light rare earth (Ⅲ) chloride with the titled unsaturated crown ether (L) have been synthesized in the mixed solvent. Elemental analysis indicated that the stoichometry of LnCl_3 with L is 1:1. The core-electron (Ln 3d_(5/2), O 1s, C 1s and Cl 2p) of LnCl_3 and its complexes has been studied by X-ray photoelectron spectra. Satellite phenomena have been observed for Ln 3d_(5/2) signals in the rare earth chloride and complexes. These satellites are discussed in terms of coexcitations of the charge-trasfer type, principally Cl 3p→Ln 4f transitions. The satellites of cerium are due to transition energy greater than zero, the satellites of prasodymium and samarium are due to transition energy smaller than zero. The former ones belong to 'shake-up' processes, the later are 'shake-down' processes.