混配型配合物Ni(mnt)(bipyO_2)的合成与气敏性能

Synthesis and Gas Sensitive Properties of Mixed-Ligand Complex Ni(mnt)(bipyO_2) with Big Conjugate System

以cis-1,2-二氰基乙烯-1,2-二硫醇钠(Na2(mnt))、2,2'-联吡啶-1,1'-二氧化物(bipyO2)和NiCl2为原料,合成了一种具有大共轭体系的混配型配合物.用元素分析、差热-热重分析、摩尔电导、红外和紫外光谱对配合物进行表征.该配合物化学式为Ni(mnt)(bipyO2),平面正方形结构,属电中性物质,热分解温度高于335℃.不溶于水和常规有机溶剂,可溶于DMSO.该配合物是一种氨敏材料,用它制作的传感器对氨气具有良好的敏感性和选择性;当工作电压为10V时,在氨气浓度小于2.6mmol·L-1的范围,传感器的输出信号对氨气呈线性响应.传感器的平均回收率为100.2%,响应时间为20s,恢复时间为45s.可用于微量氨的定量分析.

A mixed-ligand complex Ni (mnt) (bipyO(2)) with large conjugate system was synthesized by reaction of bipyO(2) (2, 2'-bipyridine-1, 1'-dioxide), nmt(2-) (maleonitriledithiolate) and NiCl2. The determinations of elemental analysis, IR, UV, molar conductivity and TG-DTA showed the complex to have electroneutrality and a square planar structure. It is a thermostable brown solid under temperature 335 degreesC. The ultraviolet absorption spectra of the complex in DMSO solution exhibited intensive absorption bands at 255 similar to 290 nm( pi-pi(*) in biPYO(2) and mnt), 310 similar to 340 nm (n-pi(*), metel cation to ligands), 370 similar to 420 nm(pi-pi(*) in mnt) and 440 similar to 520 nm, and the latter Was assigned as a large conjugate system interlocking metal ion and ligands pi to pi(*) transition. The study of sensitive properties showed the complex to be a good sensitive material of ammonia. The sensor manufactured using the complex has a good sensitivity and selectivity to ammonia. When working voltage is 10 V and NH3 concentration is less than 2.6 mmol . L-1. The output votage of the sensor varied linearly in response to the change of NH3 concentration (Fig. 3). The average recovery rate of the sensor is 100.2% (Table 4). The responsive time is about 20 s, and the return time is about 45 s. The sensor could be used in quantitative Analysis of trace ammonia.