溶液中杯[4]芳烃双冠-6与Cs~+配位化学研究

高等学校化学学报 ›› 2005, Vol. 26 ›› Issue (3): 471.

溶液中杯[4]芳烃双冠-6与Cs~+配位化学研究

高建勋^1,3, 王炳武², 张琳³, 王建晨³, 宋崇立³, 刘涛⁴, 胡天斗⁴, 谢亚宁⁴, 张静⁴

1. 北京科技大学材料学院功能高分子材料研究室,北京 100083;
2. 北京大学化学与分子工程学院,北京 100871;
3. 清华大学核能与新能源研究院,北京 100084;
4. 中国科学院高能物理研究所,北京 100039

收稿日期:2004-09-13 出版日期:2005-03-10 发布日期:2005-03-10
通讯作者: 高建勋(1975年出生),男,博士,讲师,主要从事有机合成与有机配合物结构研究.E-mail:gaojianxun99@mails.tsinghua.edu.cn E-mail:gaojianxun99@mails.tsinghua.edu.cn
基金资助:
国家自然科学基金(批准号:96-A₁8-01)资助.

Coordination Chemistry of Calix[4]arene-biscrown-6 with Cs~+ in Solution

GAO Jian-Xun^1,3, WANG Bing-Wu², ZHANG Lin³, WANG Jian-Chen³, SONG Chong-Li LIU Tao³, HU Tian-Dou⁴, XIE Ya-Ning⁴, ZHANG Jing⁴

1. Institute of Polymer Material, Beijing University of Science and Technology, Beijing 100083, China;
2. College of Chemistry and Molecular Engineering, Peiking University, Beijing 100871, China;
3. Institute of Nuclear Energy and Technology, Tsinghua University, Beijing 100084, China;
4. Institute of High Energy Physics, Academy of Chinese Sciences, Beijing 100039, China

Received:2004-09-13 Online:2005-03-10 Published:2005-03-10

摘要/Abstract

摘要： 研究了溶液中杯[4]芳烃双冠-6(BisC₆)与Cs⁺配位行为.常温下,BisC₆/NPME(邻硝基苯甲醚)体系单级萃铯百分率达99.36%,模拟料液中,Cs⁺/Na⁺和Cs⁺/K²⁺分离系数分别为3.92×10⁴和2.21×10⁴.局域结构模型实验表明,配合物分子中可能存在水或(和)硝酸(根).ESI-MS谱表明,NPME体系中,铯离子与BisC₆同时形成1:1(单核)和2:1(双核)的配合物,并且存在[BisC₆·H₂O],[BisC₆·Cs⁺]⁺,[BisC₆·2Cs⁺·H₂O]₂+和[BisC₆·2Cs₁₀⁺·No₁₀^-3]10⁺等多种配合物分子.EXAFS实验表明,溶液中铯离子的配位数为7,形成7个氧配位的稳定结构,ADF计算验证了EXAFS实验结果.

关键词: 杯[4]芳烃双冠-6, 配位化学, 铯离子

Abstract: The coordination chemistry of Calix[4]arene-biscrown-6(BisC₆) with Cs⁺ was studied in solution. The extraction experiments demonstrated that Cs⁺ extracting percentage at the single stage was 99.36% in o-nitrophenyl methyl ether(NPME) at room temperature. In simulated HLLW, the separation factor of Cs⁺/Na⁺ and Cs⁺/K²⁺ is 3.92×10⁴ and 2.21×10⁴ respectively. The local structure model of the complex showed that HNO₃ or H₂O might be located in the complexes. ESI-MS showed that the cesium ion complex with BisC₆ might form both 1:1 (mononuclear) and 2:1 (bisnuclear) Cs⁺: ligand species and [BisC₆·H₂O], [BisC₆·Cs⁺]⁺, [BisC₆·2Cs⁺·H₂O]²⁺, [BisC₆·2Cs⁺·NO-₃]⁺ etc. might exist in BisC₆/NPME/HNO₃ system. The EXAFS results indicated that the coordination number of cesium in BisC₆ was seven and the complex structure with seven-oxygen coordination was stable. ADF computation verified the EXAFS results.

Key words: Calix[4]arene-biscrown-6, Coordination chemistry, Cs⁺

中图分类号:

O641.4

TrendMD:

高建勋, 王炳武, 张琳, 王建晨, 宋崇立, 刘涛, 胡天斗, 谢亚宁, 张静. 溶液中杯[4]芳烃双冠-6与Cs~+配位化学研究. 高等学校化学学报, 2005, 26(3): 471.

GAO Jian-Xun, WANG Bing-Wu, ZHANG Lin, WANG Jian-Chen, SONG Chong-Li LIU Tao, HU Tian-Dou, XIE Ya-Ning, ZHANG Jing . Coordination Chemistry of Calix[4]arene-biscrown-6 with Cs~+ in Solution. Chem. J. Chinese Universities, 2005, 26(3): 471.

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