A Study On Designed Synthesis And Photoelectric Property Of Ferrocenylimidazole Derivatives

In recent years,many scholars have synthesized a variety of compounds with special photoelectric properties and coordination ability in order to construct an ideal ion recognition model.In the reported compounds,the favorable photoelectric response function of ferrocenylimidazole derivative is paid more attention.The chemical property of ferrocenyl group with aromaticity and modifiability is very stability,and ferrocenyl group with unique electrochemical redox activity is also an excellence telecommunication reporting unit.Imidazolyl group with aromaticity is amphoteric compound,which can be combined with anion and coordinated with cation,using as good anion and cation identification unit.Combining ferrocenyl electrochemical active with imidazolyl fluorescence active,ferrocenylimidazole derivatives will possess photoelectric dual response function.Therefore,the compounds with ferrocenyl and imidazolyl groups are favorable model molecule for ion recognition.In dissertation,ferrocenylimidazole derivatives introducing different substituents on imidazolyl ring were synthesized by carbonyl ammonia ring-forming condensation reaction of?-diketone with different substituent using ferrocenyl formaldehyde and ammonium acetate as raw material in the presence of catalyst acetic acid.The feature of ferrocenylimidazole derivative with two flexible recognition arms is a binding with anion and cation and flexible coordination ability,and possesses photoelectric dual response function.The ion recognition ability,rule and influence factor to different metal ions for ferrocenylimidazole derivatives were researched by electrochemistry fluorescence spectra and so on.Molecule structure and coordination model of ferrocenylimidazole derivatives have also studied.The main research contents in the dissertation are as follows:1.The reaction material ferrocenyl formaldehyde Fc-CHO?1a?was synthesized by substitution reaction using Fc-H and N,N-Dimethylformamide as starting materials,chloroform as solvent and phosphoryl chloride as catalyst.2.By carbonyl ammonia ring-forming condensation reaction,the designed synthesis of four ferrocenylimidazole derivatives 2a-5a including pyridinyl,thiophenyl,furanyl and phenyl groups on matrix ferrocenylimidazole has carried out,respectively.3.The compounds 1a-5a were characterized by detecting melting point,infrared absorption spectrum,nuclear magnetic resonance spectrum and mass spectrometry,and their composition and molecular structure have been confirmed.4.The photoelectric response function and the influencing factors of ion recognition to various metal ions for compounds 2a-5a as ion probe molecule were studied using the methods of square wave voltammetry?SWV?,cyclic voltammetry?CV?,UV-Vis spectrum and fluorescence spectrum,The complex ratio of compounds 2a-5a to Al³⁺and Cr³⁺ion all is 1:1 by equimolar ultraviolet spectrum experiment.Using quantification of the fluorescence titration according to Benesi-Hilderbrand?BH?equation calculation,the detection limits of compound 2a to Al³⁺and Cr³⁺ion are 7.89×10^-77 M and 1.5×10^-55 M,respectively;complexing constant of compound 2a to Al³⁺and Cr³⁺ion are 9.17×10⁴ M^-1and 1.9×10⁶ M^-1,respectively;the detection limit of compound 3a to Al³⁺and Cr³⁺ion are 2.21×10^-66 M and 4.54×10^-55 M,respectively;complexing constant of compound 3a to Al³⁺and Cr³⁺ion are 2.53×10³ M^-11 and 3.57×10³ M^-1,respectively;the detection limit of compound 4a to Al³⁺and Cr³⁺ion are 3.06×10^-55 M and 2.40×10^-55 M,respectively;complexing constant of compound 4a to Al³⁺and Cr³⁺ion are 2.26×10³ M^-11 and 3.29×10³M^-1,respectively;the detection limit of compound 5a to Al³⁺and Cr³⁺ion are 2.99×10^-5M and 2.11×10^-66 M,respectively;complexing constant of compound 5a to Al³⁺and Cr³⁺ion are 1.43×10³ M^-11 and 3.28×10³ M^-1,respectively.5.The crystal and molecule structure of the complex from the coordinated reaction of compound 2a with Ag⁺ions were determined by X-ray single crystal diffraction.The crystal structure of complex fromed by compound 2a with Ag+ion reveals their complexing ratio is 2:2 through the coordination of alkaline N atom of imidazole ring and N atoms of pyridyl groups with Ag+ion.To research the recognition mechanism of compound 2a and Ag+ions in solution,the titration experiment of ¹H NMR for compound2a with Ag⁺ion was conducted.The results show thier recognition sites are consistent with determining result of crystal structure.