Design And Synthesis Of Perylene Diimide Conjugated Oligomers And Polymers

Pryene imide compounds not only has unique fluorescent properties,electrochemical properties,but its strong ultraviolet visible region of the absorption and red light can also meet the requirements of red electroluminescent materials. Pyrene imide polycyclic aromatic hydrocarbons and their derivatives as a typical kind of conjugated polymers,has aroused peoples’ attenion increasingly on polymeroptoelectronic devices including polymer electroluminescent diode(OLED),organic field-effect transistors(OFET) and polymer solar cells(OPVC). Conjugate ladder polymer is a kind of important conjugated polymer,because of the larger π-conjugate system,pyrene imide and it’s derivatives has great application value in new photoelectric materials,pyrene imide compounds because of its large molar extinction coefficient,strong absorption ability,rigid plane, the appropriate level,high fluorescence quantum yield,good light stability and thermal stability,make it have a great application value in the field of organic semiconductor.The main contents of this thesis are as follows:1. 4-borate-2,7-di(t-butyl)pyrene(B1) and 4,9-diborate-2,7-di(t-butyl)pyrene(B2) were synthesized using 2,7-di(t-butyl)pyrene and bis(pinacolato)diboron. 1-bromo- N, N- diamyl-3,4,9,10- perylene tetracarboxylic diimide(B3) and 1,7- dibromo- N,N- diamyl-3,4,9,10-perylene tetracarboxylic diimide(B4) were synthesized using N,N-diamyl-3,4,9,10-perylene tetracarboxylic diimide obtained by perylene anhydride. Ladder conjugated oligomers W1,W2,W3 and W4 were prepared by a series of Suzuki coupling and cyclization reactions using the monomers B1,B2,B3 and B4.We characterized the molecular structure of the four oligomers by NMR and mass spectrometer.2. The ladder conjugated oligomer W was obtained by the Suzuki coupling reaction using 1,7- dibromo-N,N-diamyl-3,4,9,10- perylene tetracarboxylic diimide(B4) and the boronic esrerification product of B2.3. The four kinds of ladder conjugated oligomer can dissolved in the common organic solvents such as CH2Cl2,CHCl3, toluene and THF.But we found that the oligomers could show increase rigidity, lower solubility with the increase of plane. All the oligomers exhibited strong red fluorescence emission both in solution and thin film and there were significant redshifts both in the UV absorption peak and fluorescence emission peak(520-660 nm). The thermal properties of oligomers were investigated by thermogravimetric analysis(TGA) and different scanning calorimeter.The thermal-decomposition temperature of the oligomers were all above 350℃, which proved that all the oligomers had good thermal stability other than W4. The quantum yield of all the oligomers was high and effective and it could be better with the increasing of plane.4. We got the LOMO energy level and HOME energy level of W1 were-2.963 eV and 5.302 eV and that of W2 were-3.434 eV and-5.874 eV using B3LYP/6-31+G*.The two kinds of oligomer had higher obsorptivity, fluorescence quantum yield and lower LOMO energy compared to commonly used electronic transfer material.the oligomers will become the excellent electronic efficient injecton and thetransmission type of organic electroluminescent materials.