Synthesis,Structure And High-efficiency Luminescence Property Of Triphenylamine-based Complexes And Polymers

The research of efficient stimulus-responsive metal organic framework materials and polymers has become a hot research topic.Stimulus-responsive organic compounds will have obvious differences in color and performance(quantum efficiency,fluorescence intensity)before and after the material under the stimulus of external conditions(such as pressure,temperature,light,p H,etc.).These differences change in temperature sensing and pressure transmission.There are certain application prospects in the fields of sensing,anti-counterfeiting,memory storage,and optical switches.Based on the investigation of triphenylamine complexes and polymers,we can find that the color luminescence and high quantum efficiency(QY)of triphenylamine complexes and polymers can be found in this article.Two complementary color luminescent dyes can produce high-efficiency white light emitting materials through reasonable adjustments,which have potential applications in lighting equipment,LEDs,and display media.Next,we will be divided into three sections to describe separately:the stimulus responsiveness and high quantum efficiency of triphenylamine complex under external conditions,the complementary color luminescent material of the complex film emits white light,and the high quantum efficiency of polymers.The research content is as follows:(1)According to the synthesis method in the reference,the tris(4-(pyridin-4-yl)phenyl)amine(TPPA),5-phenylisophthalic acid(H₂L)ligand was synthesized,and the metal salt zinc acetate was hydrothermally Synthesis method to form metal complex[Zn(TPPA)(H₂L)]·2DMF·H₂O.The crystal structure was measured by X-ray single crystal diffraction,and then the quantum efficiency,variable temperature fluorescence,different pressure and grinding,solvent effects and other related fluorescent properties of metal Zn complex 1 were studied using the FS5 fluorometer.1 It has a certain response under temperature changes,external pressure,and solvent.Among them,Zn complex 1 exhibits reversible mechanical fluorescence properties under conditions of varying temperature and external pressure.In addition,in the case of grinding,the wavelength of Zn complex 1 has a red shift of 50nm,the quantum efficiency has changed from 60.2%before grinding to81.5%after grinding,and the quantum efficiency has increased by 21.3%.This may be due to the fact that during the grinding process,the Zn complex from the crystalline state to the amorphous state.Using tris(4-(pyridin-4-yl)phenyl)amine(TPPA)and Cu₄I₄(PPh₃)₄ as raw materials,the metal Cu I complex 2 was synthesized by hydrothermal synthesis method.By studying its temperature-changing fluorescence properties,it can be found that as the temperature increases,the complex changes from dual emission to single emission,and a certain red shift can be seen through normalization.This may be due to phosphorescence exhibiting dual emission at low temperatures.As the temperature increases,phosphorescence the disappearance becomes a broad singlet emission peak.Using 9,10-bis(imidazole-1-methylene)anthracene,4,4-diphenyl ether dicarboxylic acid and zinc acetate as raw materials,a Zn(??)complex[Zn(H₂L)(tib)]n·3n H₂O(complex 3,H₂L=4,4-diphenyl ether dicarboxylic acid,tib=9,10-bis(imidazole-1-methylene)anthracene.The structure of complex 3 was characterized by IR,elemental analysis,and X-ray single crystal diffraction.The temperature-variable fluorescence test of complex 3 was carried out under the excitation state of 365 nm.The result of fluorescence test showed that complex 3 had a certain response to temperature.The fluorescence spectrum of complex 3was investigated under different excitation wavelengths,and it was found that with the increase of excitation wavelength,the CIE chromatogram of complex 3 showed a span from green light to yellow light to red light,which can be applied for excellent adjustable and colorful luminescent materials.(2)Through the synthesis of the first part of the synthesis of metal Zn complex 1 and the fluorescence properties,it can be found that the complex 1 is blue-green light under ultraviolet light irradiation,and the ground complex is yellow light under ultraviolet light irradiation,and the quantum efficiency is increased by 21.3%,reaching 81.5%.By dissolving complex 1 and polymethyl methacrylate in CH₂Cl₂ solvent,making two kinds of films before and after grinding,it is found that complex 1 fluorescent(yellow)light film material has high quantum efficiency and can be applied to blue LEDs to realize white light material emission.At the same time,the quantum efficiency of the film before and after grinding is consistent with the quantum efficiency of the complex before and after grinding.The quartet emission peak appears after the film is made,which may be caused by the intermolecular charge transfer(CT).The quartet is the doublet of 5-phenylisophthalic acid,the singlet of the ligand TPPA and the complex peak.After comparison,it is found that the polished film can emit better white light effect under excitation at 460nm,and has a higher quantum efficiency.Since the emission peak of the ligand TPPA is located in the blue region and the emission peak of the complex is located in the yellow region,we tried to adjust the ratio of the ligand TPPA and the complex to make their emission peak intensity basically the same,emitting white light,and the quantum efficiency reached 80%the above.(3)The TPPA polymer was synthesized by crosslinking the ligand tris(4-(pyridin-4-yl)phenyl)amine(TPPA)synthesized in the first part with 1%chloromethyl polystyrene resin and reacting with ammonium hexafluorophosphate.The TIPA polymer was synthesized by cross-linking tris(4-(imidazol-4-yl)phenyl)amine(TIPA)with 1%chloromethyl polystyrene resin and reacting with ammonium hexafluorophosphate.The fluorescence properties of the above two polymers were measured,and it was found that the TPPA polymer emits red light and the TIPA polymer emits blue light.The quantum efficiencies of both are above 90%.Among them,TPPA polymer can have great application prospects in biological imaging and white light materials due to its extremely high quantum efficiency.