高等学校化学学报 ›› 1981, Vol. 2 ›› Issue (1): 97.

• 论文 • 上一篇    下一篇

稀土乙酰丙酮络合物的激光拉曼和红外光谱(Ⅰ)

梁映秋, 刘举正, 刘国发, 赵永年, 王宇天   

  1. 吉林大学理论化学研究所
  • 收稿日期:1980-03-17 出版日期:1981-01-24 发布日期:1981-01-24

RAMAN AND INFRARED SPECTRA OF RARE EARTH ACETYLACETONATE COMPLEXES——I

Liang Yingqiu, Liu Juzheng, Liu Guofa, Zhao Yongnian, Wang Yutian   

  1. Institute of Theoretical Chemistry, Jilin University, Changchun
  • Received:1980-03-17 Online:1981-01-24 Published:1981-01-24

摘要: 本文测定了15个一水稀土乙酰丙酮络合物的激光拉曼和红外光谱,在401、415cm~(-1)附近的拉曼谱带对不同稀土离子表现敏感,它们随原子序数变化呈现“四分组”效应,这是第一次在振动光谱中观察到的镧系递变规律。该系列络合物的振动频率变化亦符合镧系“斜W”效应的规律,这些特征规律为确认401、415cm-1附近谱带为M—O拉伸振动提供了最好的证据。实验结果同时可用于讨论M—O键的性质。

Abstract: In this work, the Laser Raman and infrared spectra of 15 rare earth acetylacetonate complexes in the region 300-3300cm-1 are studied.The bands near 401 and 415 cm-1 are sensitive to a change in rare earth ion.The frequencies of these two bands change periodically with atomic number, showing the "tetrad effect" and ihe "inclined Weffect" characteristic of lanthanides, and the former was first observed in spectra of rare earth complexes.These effects provide strong evidence for assigning the band near 401cm-1 to the MO2 symmetric stretch and that near 415cm-1 to the MO2 antisymmetric stretch.Adiatomic molecule approximation may be used to estimate the M-Ostretching force constants from the M-Ovibrational frequencies.If the force constant is plotted against the atomic number, the curve shows also the "tetrad effect" .If the force constant is plotted against the logarithm of the stability constants of these complexes, two straight lines having different slope were obtained for light and heavy rare earth ions which cross at Eu.Since the force constants vary appreciably compared to the variation in stability constants for heavy rare earth acetylacetonate complexes, the force constant is a more precise structure parameter for describing these complexes.The C-Ostretching frequency in the infrared spectrum of acetylacetone decreases upon coordination with rare earth metal ions, which indicates that the charge transfer occurs.The negative charge in the acetylacetonate ring tends to be delocalized.Rare earth acetylacetonate complexes are usually considered to be ionic, but the present result indicates that a certain amount of covalency is present.

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