Study On The Synthesis Of Phenanthroline Organometallic Third-Order Nonlinear Optical Materials

In the rapidly growing field of the organic functional materials, organic third-order optical materials are the forefront of research activities. These materials have numerous applications,such as optical fiber communication,optical communication,optical data storage,laser medical, laser weapon and so on.Based on the inspecting of reference,the analysis of nonlinear optical effect and its mechanism,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 properties of materials were described. According to the principle of molecular design,two series of five phenanthroline organometallic third-order nonlinear optical materials were designed and synthesized,among which 3 are new compounds.The main synthetic mechanisms and processes are studied.The symmetrical organometallic third-order nonlinear optical compounds tris（1,10-phenanthroline-κN1,κN10）-Nickel（2+）,tris（1,10-phe-nanthroline-κN1,κN10）-ruthenium（2+） are prepared from Phenanthroline by the reaction with Nickel,ruthenium ion in methanol.The novel unsymmetrical organometallic third-order nonlinear optical compounds[2-（1H-imidazo[4,5-f][1,10]phenanthroline-2-yl-κN7,κN8）phenol] bis（1,10-phenanthroline-κN1,κN10）Nickel（2+）,[2-（1H-imidazo[4,5-f] [1,10]phenanthroline-4-yl-κN7,κN8）methoxylbenzene]bis（1,10-phenanthro -line-κN1,κN10）Nickel（2+）,[2-（1H-imidazo[4,5-f][1,10]phenanthroline-4 -yl-κN7,κN8）nitrylbenzene]bis（1,10-phenanthroline-κN1,κN10）Nickel（2+） are prepared from Phenanthroline by the reaction of oxidation, condensation and complexation.The process parameters of oxidation,condensation and complexation were optimized.The optimum reation conditions for oxidation are as followed:n（phenanthroline）:n（sodium bromide）=1:4,reaction temperature 110℃,refluxing reaction time 4h.The optimum reation conditions for condensation are as followed:one pot reation,reaction temperature 80℃, n（1,10-Phenanthroline-5,6-dione）:n（o-Hydroxybenzal-dehyde）= 1:1.2, reaction time 2h,n（1,10-Phenan-throline-5,6-dione）:n（ammonium acetate）= 1:20.The optimum reation conditions for complexation are as followed:n（NiCl₂·6H₂O）:n（phenanthroline）:n（2-（2’-hydroxyphenyl） -imidazo[4,5-f][1,10]phenanthro-line）= 1:2.2:1.2,former reaction time 2h,latter reaction time 3h,reaction temperature 65℃.The yields of the oxidation and condensation reactions increased to 92%and 93.1%from 40%and 70%respectively.