溶液中杯[4]芳烃双冠-6与Cs^+配位化学研究

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

研究了溶液中杯 [4]芳烃双冠 -6(Bis C6)与 Cs+ 配位行为 .常温下 ,Bis C6/NPME(邻硝基苯甲醚 )体系单级萃铯百分率达 99.3 6% ,模拟料液中 ,Cs+ /Na+ 和 Cs+ /K+ 分离系数分别为 3 .92× 1 0 4 和 2 .2 1× 1 0 4 .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 Bis C6同时形成 1∶ 1 (单核 )和 2∶ 1 (双核 )的配合物 ,并且存在 [Bis C6·H2 O],[Bis C6· Cs+ ]+ ,[Bis C6·2 Cs+ · H2 O]2 + 和 [Bis C6· 2 Cs+ · NO- 3]+ 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 .

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+/K+ is 3.92×104 and 2.21×104 respectively. The local structure model of the complex showed that HNO_3 or H_2O 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·H_2O], [BisC6·Cs+]+, [BisC6·2Cs+·H_2O] 2+, [BisC6·2Cs+·NO-_3]+ etc. might exist in BisC6/NPME/HNO_3 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.