Studies On The Syntheses And Fluorescent Properties Of Triaryl Pyridine Derivatives And Metal Complexes Based On Coumarin

This dissertation consisted of the following two parts.Firstly,coumarins with excellent optical properties were introduced into the 2-and 6-positions of the pyridine ring,and the functional groups were also modified on the 4-position.It was used as a ligand for the cultivation and testing of metal complexes.Secondly,7-diethylaminocoumarin fragment was introduced into the 4-position of terpyridine.It was also used as a ligand for the cultivation and testing of metal complexes.The dissertation was divided into four chapters:The first chapter was the introduction part.It included the preparation and application of coumarin derivatives,triarylpyridine derivatives and terpyridine derivatives.The relevant induction,summary and outlook were generalized by utilizing the recent domestic and foreign research progress.The second chapter was the preparation of coumarin derivatives.Firstly,a series of 3-acetylcoumarin derivatives were successfully synthesis by grinding with piperidine as the catalyst using salicylaldehyde derivatives and ethyl acetoacetate as raw materials.The 3-acetylcoumarin derivatives were characterized by nuclear magnetic resonance spectroscopy.Secondly,the 3-aldehyde-7-diethylamine was successfully synthesis through the preparation of Wittig reagent and 7-diethylamino coumarin,and finally reacted with phosphorus oxychloride.The third chapter was the synthesis and fluorescence properties of triarylpyridine derivatives and metal complexes based on coumarin.It is divided into the following five parts: In the first part,three systems(7a-7e,8a-8e,9a-9e)were successfully synthesis by reacting with 3-acetylcoumarin derivatives and aromatic aldehyde,and using tetrabutylammonium hydrogen sulfate as a catalyst.The triarylpyridine derivatives were also tested for their solubility in different solvents,the test results showed that the solubility of system 7a-7e was better.The products 7a-7e were characterized by nuclear magnetic resonance spectroscopy and infrared spectroscopy.In the second part,7a-7e were tested by the UV absorption and fluorescence emission spectra.In the third part,the synthesis mechanism of 4-aryl-2,6-bis(7-diethylaminocoumarin-3-yl)pyridine was investigated by using related literatures.In the fourth part,the possible structural formula of 4-(4-chlorophenyl)-2,6-bis(7-diethylaminocoumarin-3-yl)pyridine was simulated by Gaussian calculations.In the fifth part,4-aryl-2,6-Bis(7-diethylaminocoumarin-3-yl)pyridine were used as a ligand and coordinated with copper acetate and zinc acetate respectively.The two needle-shaped single crystals were successfully obtained,which were tested by X-ray single crystal to be the crystals of ligands.The carbonyl oxygen on the coumarin ring in the 2-and 6-positions were outward,which was consistent with the structure simulated by the Gaussian calculation.Therefore,it was difficult to achieve coordination with the metal by the N atom on the pyridine ring,which was contrary to the initial experimental design.However,it was further proved that the coordination ability of triarylpyridine derivatives were poor.The fourth chapter was the synthesis and fluorescence properties of the terpyridine derivatives and metal complexes based on coumarin.It was mainly divided into the following three parts: In the first part,the(E)-3-(4-(2,2':6',2''-triadipyridyl)-4'-styryl)-7-diethylaminocoumarin(14)and(Z)-3-(4-(2,2':6',2''-tripyridyl)-4'-styryl)-7-diethylaminocoumarin(15)were successfully synthesis,which were characterized by nuclear magnetic resonance spectroscopy and infrared spectroscopy.In the second part,the UV absorption and fluorescence emission spectra of the compounds 14 and 15 were tested.In the third part,the coordination effects of compounds 14 and 15 with copper acetate were studied,and spectroscopic analysis of ligands and complexes were also tested by infrared spectra,UV absorption and fluorescence emission spectra.The results showed the infrared spectra of the complexes had a certain degree of violet shift compared to the ligands,and UV absorption and fluorescence emission spectra had a large degree of red shift.By the spectroscopic analysis of ligands and complexes,it can be determined that coordination occured between the pyridine N atom and copper acetate,which further illustrated the synthesis of the target complexes.