CIESC Journal

• 材料科学与工程 • 上一篇    下一篇

具有分子内荷移跃迁配合物的合成与应用

傅铁祥;李丹   

  1. 长沙理工大学化学与环境工程系,湖南 长沙 410076

  • 出版日期:2006-11-25 发布日期:2006-11-25

Synthesis and application of complex with charge-transfer transition in molecule

FU Tiexiang;LI Dan   

  • Online:2006-11-25 Published:2006-11-25

摘要: 以2,2′-联吡啶-1,1′-二氧化物(bipyO2)、cis-1,2-二氰基乙烯-1,2-二硫醇钠(Na2mnt)和MnCl2为原料,合成了一种配体间存在荷移跃迁的混配型配合物并经元素分析、热谱、摩尔电导、红外和紫外光谱表征.该配合物化学式为Mn(mnt)(bipyO2),属电中性物质,热分解温度高于310℃.不溶于水和常见有机溶剂,可溶于DMSO.在氨气浓度为(6.0×10-5)~(8.5×10-4)mol· L-1的范围,该配合物对氨气具有良好的敏感性和选择性;用它制作的传感器最佳工作电压为15 V,传感器的平均回收率为100.3%,响应时间为40 s,恢复时间为45 s.可用于微量氨的监测.

Abstract: A mixed-ligands complex Mn(mnt)(bipyO2)with charge-transfer transition from one ligand to the other was synthesized by the reaction of bipyO2(2,2′-bipyridine-1,1′-dioxide),Na2 mnt(maleonitriledithiolate)and MnCl2.The determinations by means of elemental analysis,infrared spectra,UV-Vis spectra,molar conductivity and TG-DTA showed that the complex was electrically neutral.It was thermostable brown solid below 310℃.The electronic spectra of the complexe in DMSO solvate exhibited intensive absorption bands at 250—290 nm(π-π* in bipyO2 and mnt),360—390 nm(π-π* in mnt)and intensive absorption bands at 410—430 nm was assigned as a metal-mnt π to bipyO2π* charge-transfer transition.The study of sensitivity properties showed that the complex was a good sensitive material for ammonia.The sensor made from the complex has good sensitivity and selectivity to ammonia.at working voltage 15 V and NH3 concentration in the range of (6.0×10-5)—(8.5×10-4)mol·L-1.The value rate of recovery of the sensor was 100.3% in average.The response time of the sensor was about 40 s,and the return time was about 45 s.The sensor could be used for detecting trace ammonia.