混配型配合物Ni(mnt)(bipyO2)的合成与气敏性能

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10 V时,在氨气浓度小于2.6 mmol?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20 s,恢复时间为45 s.可用于微量氨的定量分析.

Synthesis and Gas Sensitive Properties of Mixed-Ligand Complex Ni(mnt)(bipyO2) with Big Conjugate System

A mixed-ligand complex Ni(mnt)(bipyO2) with large conjugate system was synthesized by reaction of bipyO2(2,2′-bipyridine-1,1′-dioxide),mnt2－(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 ℃. The ultraviolet absorption spectra of the complex in DMSO solution exhibited intensive absorption bands at 255～290 nm(π-π* in bipyO2 and mnt), 310～340 nm(n-π*, metel cation to ligands), 370～420 nm(π-π* in mnt) and 440～520 nm, and the latter was assigned as a large conjugate system interlocking metal ion and ligands π to π* 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 voltage 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.