波谱学杂志 ›› 1987, Vol. 4 ›› Issue (4): 325-335.

• 研究论文 • 上一篇    下一篇

五种还原Keggin结构杂多阴离子的ESR谱

毛友钢1, 岳世泰1, 裘祖文1, 王恩波2   

  1. 1. 吉林大学理论化学研究所;
    2. 东北师范大学化学系
  • 收稿日期:1987-03-16 出版日期:1987-12-05 发布日期:2018-01-22
  • 基金资助:
    国家自然科学基金委员会资助项目

THE ESR SPECTRA OF FIVE REDUCED KEGGIN'S HETEROPOLYANIONS

Mao Yougang1, Yue Shitai1, Qiu Zuwen1, Wang Enbo2   

  1. 1. Institute of Theoretical Chemistry, Jilin University;
    2. Department of Chemistry, North East Normal University
  • Received:1987-03-16 Online:1987-12-05 Published:2018-01-22

摘要: 本文报道了五种具有Keggin结构的还原杂多阴离子的溶液和-150℃冷冻ESR谱,它们是SiV2Mo10O406-、bSiV2Mo9O407--、PV3Mo9O406-、PV3W9O406-和VV3W9O406-。在室温下pH≤3时,所有杂多酸阴离子均为8条锐线,pH=7-8时,均为8+15条线并且随着放置时间增长逐步变成8条线。在-150℃时均呈现出V4+8条线的复杂粉末谱,作者根据一种修正的Ble-aney方法成功地模拟了这些冷冻谱,得出g、g、A、A,按照DeArmond理论计算了近似的K、α值并讨论了它们的物理意义。最后从异构体的数目和简并度的观点初步解释了观察不到V3物种22条超精细线的原因。Back

关键词: ESR, 杂多兰, 杂多阴离子

Abstract: The ESR spectra of five reduced heteropolyanions belonging to the Keggin structure are reported in this paper. They are SiV2Mo10O406-, SiV3Mo9O407-, PV3MO9O406-, PV3W9O406- and VV3W9O406-. At room temperature and pH≤ 3, their spectra contained 8 hfs lines, while at pH=7-8, 8+15 hyperfine lines. Their shape change gradually and finally turned to 8-lines spectrum after a long period of time. The frozen spectra at - 150℃ exhibited complicated 8 line spectra which were successfully simulated based on slightly modified Bleaney's theory.The ESR parameters g g A A were determined and the approximate K, α values were calculated based on DeArmond's theory. The physical meaning of the results are discussed and the failure of observing the 22 hfs lines of Vs species are primarily explained according to the number and degeneracy of the isomers present in the V3 species.

Key words: ESR, heteropolyanions, heteropoly-blue