Study On The Synthesis And Third-order Nonlinear Optical Properties Of Ferrocene Organometallic Functional Dyes

The organic third-order nonlinearoptical materials is a research focus in organic functional material fields. These materials can be successfully applied in the area of optical fiber communication , optical communication, optical data storage, laser medical, laser weapon and so on.Based on the evaluation of the bibliographer and the analysis of the principle of nonlinear optical,the relationship between molecular design, structures and optical properties of third-order nonlinear optical organic materials were reviewed. The parameters and measure techniques of third-order nonlinear optical materials were described. According to the principle of molecular design,a series of 21 ferrocenyl organometallic functional dyes were designed and synthesized , among which 11 structures were no found. The main synthetic mechanisms and processes were studied. All the compounds were characterized by 1H NMR,MS and UV.A series of 16 schiff-base ferrocene organometallic functional dyes which had largeÏ€-conjugated systems were designed and synthesized starting from ferrocenecarboxaldehyde and substitutional amine. Ferrocenecarboxaldehyde was prepared starting from Ferrocene,AlCl3 and ethyl ortho-formate via fomylation.The process of reactions were discussed and the parameters of the reactions were selected. The results showed that the optimal parameters were as follows: catalyst alkaline Al2O3, solvent xylene, reflux 10 h. The yield was 59.1% .The influence of different substituted amine on the reaction yields was compared. It concluded that the amine with more intense basicity give the higher yield. The reaction is also operated under solvent-free and HSVM comditions.High Speed Vibration Milling(HSVM) uses High-energy ball-milling to produce mechanical energy to induce chemical reactions, the collision between the reactant molecules more directly, efficiently and the efficiency of the reactions will be higher. Especially suitable for the reactions of fused ring amine and ferrocenecarboxaldehyde .The yields were 25.4⁹7.2%.The process of synthesis of 1-ferrocenyl-2 -(2'-formylthiophenyl) ethane was selected which was starting from thienyl vinylferrocene and n-butyllithium via formation. 4 third-order nonlinear optical organometallic materials were obtained via condensation reaction from substitutional amine and formylferrocene,1-ferrocenyl-2- (2'-formyl- thiophenyl) ethane or 1-ferrocenyl-2-(p-formylphenyl) ethane. Investigated the synthsis of 1,1'-diformyl ferrocene of substitution method and oxidation process.A new symmetrical ferrocene derivative was synthesized by condensation reaction.The third-order nonlinear optical properties of the materials were measured using femtosecond degenerate four-wave mixing. The third-order nonlinear optical susceptibilitiesχ(3) of six vinylferrocene organometallic functional dyes were 2.55^-3.78×10^-13 esu. The second-order hyperpolarizabilitiesγof the molecules were 2.42^-3.60×10^-31esu. The response times were 51-98 fs. The third-order nonlinear optical susceptibilitiesχ(3) of four schiff-base ferrocene organometallic functional dyes were 2.21³.32×10^-13esu. The second- order hyperpolarizabilitiesγof the molecules were 2.10³.15×10^-31esu. The response times were 42-63 fs.