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化学进展 2013, Vol. 25 Issue (05): 809-820 DOI: 10.7536/PC121123 前一篇   后一篇

• 综述与评论 •

质谱在多金属氧簇化学中的应用

徐冲, 范艳璇, 范琳媛, 曹洁*, 胡长文*   

  1. 北京理工大学化学学院 原子分子簇科学教育部重点实验室 北京 100081
  • 收稿日期:2012-11-01 修回日期:2012-12-01 出版日期:2013-05-24 发布日期:2013-04-15
  • 通讯作者: 曹洁, 胡长文 E-mail:jcao@bit.edu.cn;cwhu@bit.edu.cn
  • 基金资助:

    北京理工大学基础科研基金项目(No. 20121942006)和111学科引智基地(B07012)资助

Application of Mass Spectrometry in Polyoxometalate Chemistry

Xu Chong, Fan Yanxuan, Fan Linyuan, Cao Jie*, Hu Changwen*   

  1. Key Laboratory of Cluster Science, Ministry of Education, School of Chemistry, Beijing Institute of Technology, Beijing 100081, China
  • Received:2012-11-01 Revised:2012-12-01 Online:2013-05-24 Published:2013-04-15

随着多金属氧簇化学的发展,迫切需要将多金属氧簇的液相反应过程和固相结构有机结合起来,以便更好地指导功能导向性多金属氧簇的设计与合成。传统的分析方法对一些特殊结构的多金属氧簇以及溶液自组装机理的研究具有局限性。随着软电离技术的发展,尤其是电喷雾电离(ESI)和基质辅助激光解吸电离(MALDI)的发明,质谱(MS)技术越来越多应用在简单无机化合物、配合物及金属有机化合物的研究中。多金属氧簇属无机高分子,是一类结构较特殊的无机配合物,多阴离子自身常带多个负电荷。钼、钨等具有较多同位素,可方便通过理论模拟与实际测量同位素分布的对比确定簇离子的准确组成。本文综述了质谱技术在多金属氧簇化学中的应用,如ESI-MS分析多阴离子在溶液中存在形式、监测反应过程、推断自组装机理,并对其在多金属氧簇化学中的应用前景进行了展望。

With the fast development of polyoxometalate (POM) chemistry,there is a need to bridge the gap between solid-state structure and solution properties of POM which is helpful to design and synthesize function-directed POMs. Conventional analytical techniques have signicant drawbacks especially for study of special structured POMs and investigation of the formation mechanism in solutions. With the development of soft ionization techniques——matrix assisted laser desorption ionization (MALDI) and especially electrospray ionization (ESI), mass spectrometry (MS) became one of most powerful analytical techniques applicable to simple inorganic, coordination and organometallic compounds. Polyoxometalates are a kind of inorganic polymers which are ideal candidates to be examined using high-resolution mass spectrometry since they are intrinsically charged and have characteristic isotopic envelopes, resulting from the stable isotopes of W and Mo, which can be precisely fitted to determine the exact formula. This paper reviews the research progress of the application of mass spectrometry in polyoxometalate chemistry. ESI-MS can provide vital information of the cluster composition in solution and be used to probe the self-assembly mechanism in solution. In addition, the potential applications of mass spectrometry in the field are stated. Contents
1 Introduction
2 The use of mass spectrometry in polyoxometalate chemistry
2.1 Investigation of cluster composition in solution
2.2 Identification of protonation state and the clusters with structural defects
2.3 Study of gas-phase fragmentations
2.4 Verification of self-assembly process
2.5 Differentiation of isomers
3 Conclusion and perspectives

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摘要

质谱在多金属氧簇化学中的应用