具有分子内荷移跃迁配合物的合成与应用  

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

作　　者：傅铁祥[1] 李丹[1] 

机构地区：[1]长沙理工大学化学与环境工程系,湖南长沙410076

出　　处：《化工学报》2006年第11期2772-2777,共6页CIESC Journal

基　　金：湖南省自然科学基金项目(01JJY3010).~~

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15V,传感器的平均回收率为100·3%,响应时间为40s,恢复时间为45s.可用于微量氨的监测.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^＊ 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 Vand 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 about 40 s, and the return time was about 45 100.3% in average. The response time s. The sensor could be used for detecting of the sensor was trace ammonia.

关 键 词：锰 传感器 配合物 cis-1 2-二氰基乙烯-1 2-二硫醇钠 2 2-联吡啶-1 1'-二氧化物 

分 类 号：O614.71[理学—无机化学]