| In recent years,many research papers were written on the application of Ferrocene derivatives in electrochemistry,such as electrocatalysis and electroanalysis,but only a few studied the effects of different groups on the electrochemical parameters and kinetic parameters of Ferrocene and its derivatives systematically.In this paper,five types of Ferrocene derivatives were synthesized:FcE,FcA,FcDA,FcD and Fc BM.And the effects of different groups on the electronic properties of Ferrocene were studied from the electron effect and steric hindrance.Besides,on the basis of the above studies,four kinds of ferrocene benzimidazole derivatives with good electrochemical properties have been designed and synthesized:Fc B1,FcB2,FcB3 and Fc B4.The structures and properties of these compounds were studied through methods like IR,UV-Vis,1H NMR,13C NMR and CV.?1?In this paper,five Ferrocene derivatives:Fc E,FcA,FcDA,FcD and FcBM were synthesized with Ferrocene as raw material.Their electrochemical properties were characterized by methods like cyclic voltammetry,chronoamperometry and conductivity meter.The result shows that the peak potential of the Ferrocene and its derivatives basically has not changed??E?65 mV?with the increase of the scanning rates.And the peak current ip has a linear relationship with the scanning rate v1/2,which indicates that they have a reversible redox reaction on the surface of the electrode and the diffusion was controlled.The diffusion coefficients of FcE,FcA,FcDA,FcD and FcBM are 12.4×10-66 cm2·s-1,0.871×10-6cm2·s-1,0.713×10-6 cm2·s-1,0.625×10-6 cm2·s-11 and 0.184×10-6 cm2·s-11 respectively.When the Cp ring connects with the electrondrawing group,the density of the electron cloud on the Cp ring is reduced and it is hard to be oxidized.In the meantime,it will be difficult to contact electrodes due to steric hindrance effect if the substituents on the Cp ring become larger.Both of the two effects will lead to positive shift of oxidation-reduction potential,otherwise,the oxidation-reduction potential shifts negatively.In addition,the conductivity of Fc E,FcA,FcDA,FcD and FcBM acetonitrile solutions at room temperature were 16.8×10-6 S/cm,16.00×10-6 S/cm,16.64×10-6 S/cm,16.36×10-6 S/cm and 36.4×10-6 S/cm separately,which are higher than that in the acetonitrile solution 5.89×10-6 S/cm at room temperature.Besides,their electrical conductivity increases with the increase of temperature within a certain temperature range.?2?Four kinds of Ferrocene benzimidazole derivatives?FcB1FcB4?were synthesized through a series of reactions with Ferrocenecarboxaldehyde and parachloroaniline as raw material.The electrochemical properties and ion recognition properties of FcB1FcB4 were studied by cyclic voltammetry,chronoamperometry and UV Vis spectroscopy.The results showed that FcB1FcB4 all have a single electron reversible redox reaction on the surface of the electrode,and the reaction on the surface of the electrode is controlled by the diffusion.The diffusion coefficients are 2.201×10-7 cm2·s-1,3.522×10-7 cm2·s-1,4.197×10-77 cm2·s-11 and1.65×10-77 cm2·s-1 separately.In common anions,FcB1FcB4 can recognize F-in multichannel.The addition of F-makes the UV spectrum of the 448 nm near the 448 nm redshift,the absorbance increases,and the oxidation potential moves to the negative electrode193 mV,154 mV,120 mV and 208 mV respectively.In addition,FcB4 also showed recognition effect on AcO-and H2PO4-,and the oxidation potential shifted to the negative electrode 112 mV and 134 mV respectively.The results of NMR titration showed that the N-H protons on the benzimidazole ring in FcB1Fc B4 can form hydrogen bonds with F-to achieve recognition.After combining with F-,the chemical shifts of the four N-H protons move to low field 0.17 ppm,0.14 ppm,0.12 ppm,and 0.18 ppm separately. |
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