| 溶液中杯[4]芳烃双冠-6与Cs~+配位化学研究 |
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| 引用本文： | 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[J]. 高等学校化学学报, 2005, 26(3): 471-475 |
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| 作者姓名： | 高建勋 王炳武 张琳 王建晨 宋崇立 刘涛 胡天斗 谢亚宁 张静 |
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| 作者单位： | 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 |
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| 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.
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| 关 键 词： | 杯[4]芳烃双冠-6 配位化学 铯离子 |
| 文章编号： | 0251-0790(2005)03-0471-05 |
| 收稿时间： | 2004-09-13 |
Coordination Chemistry of Calix[4]arene-biscrown-6 with Cs+ in Solution |
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| 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[J]. Chemical Research In Chinese Universities, 2005, 26(3): 471-475 |
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| Authors: | GAO Jian-Xun WANG Bing-Wu ZHANG Lin WANG Jian-Chen SONG Chong-Li LIU Tao HU Tian-dou XIE Ya-Ning ZHANG Jing |
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| Affiliation: | 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 |
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| 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. |
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| Keywords: | Calix[4]arene-biscrown-6 Coordination chemistry Cs+ |
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