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Study on the Synthesis and Property of Optoelectronic Materials Based on the BF3 ·Et2O Catalysed Friedel-Crafts Reaction

Author: ChangYongZheng
Tutor: LiuBin;JieLingHai
School: Nanjing University of Posts and Telecommunications
Course: Information materials
Keywords: Friedel-Crafts reaction Boron trifluoride etherate Dendrimers Steric Optical Properties
CLC: TN304.5
Type: Master's thesis
Year: 2011
Downloads: 92
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Abstract


Based on Boron trifluoride etherate (BF 3 · Et 2 O) catalyzed Friedel-Crafts reaction with mild reaction conditions, post-processing is simple, green non-toxic, etc., in order to the constructed \In today's organic photoelectric field, such as: an organic solar cell (OSC), an organic electroluminescence (OLED), organic field-effect transistor (OFET), electroluminescent organic materials storage and sensing the unique construction of the base. First, we have developed based on BF 3 · Et 2 O tertiary alcohols catalyzed Friedel-Crafts reaction, synthesis of a series such as linear, dumbbell-shaped, a branch type and other configuration of the 9,9 - diaryl fluorene compounds. By the fluorene group, xanthene and other steric hindrance group into the electron rich thiophene, bithiophene, carbazole and other aromatic groups on, T1 set of spectra that we thiophene after oxidation, red shift of the near 130 nm, spectral description oxidation is an effective way to regulate. Series T2, T3 series of emission spectrum, we can see, a fluorenyl group phenyl steric hindrance resulting in a blue shift of about 70 nm, indicating that steric hindrance into the phenyl group fluorene effectively regulate the molecular chains are in the way the π stacking configuration of the molecule, thereby adjusting the energy band structure of the material. For us to optimize the device structure to provide a reference. In this process we BF3? Et2O catalyzed Friedel-Crafts reaction with the new level of awareness of the reaction to explore a variety of factors (such as the feed ratio of the reaction, the order of addition, the reaction temperature, reaction time, the reaction substrate, etc. ) on the reaction products, the yield of the reaction. This gives us the design, optimized reaction provides a reference. It was found that by controlling the different feed ratio can be controlled fluorenyl phenyl group (PFMs) the number of substitution, further affecting its optical properties and thermal stability. The results show that by differential scanning calorimetry DSC (PFMs) capping the hole transporting material can improve the precursor glass transition temperature, showing the diversity of molecular conformation and strong steric effect. In addition, we also explored the hetero ring atom introduction of multi-reactivity and spectroscopic properties and found that the introduction of heterocyclic largely reduces the Friedel-Crafts reaction activity and cause spectral redshift. We will fluorene phenyl group into the steric hindrance carbazole 3 -, 6 - position, and then the carbazole 1 - position into pyrene, biphenyl, fluorenone, carbazole substituted alkyl group, to explore and steric substituents on the material band structure and molecular intra / inter-π stacking effects, and through theoretical simulation and experimental methods to combine each other evidence. The emission spectra of a dilute solution, 3,6-position of the carbazole groups introduced steric hindrance of its spectrum peak and the peak shape little effect, will cause a slight red shift spectrum, indicating orbitals HOMO and LUMO energy concentrated in the center of the carbazolyl group; carbazole By contrast in the introduction of different N-electron, electron donating group, found that the peak position of its emission spectrum is relatively large, with the ability to enhance the electron emission spectrum occurs redshift, the electrochemical results show that its HOMO level increases, the energy gap decreases, indicating substituent effect on its orbital HOMO and LUMO energy change is relatively large. Dendrimers (Dendrimer) is in addition to small organic molecules and polymers other than the third category of optical materials, which combines the clear structure of small molecules and polymers dual advantages of good stability, is a broad application prospects of a class of optoelectronic materials. But the complexity of synthetic steps, the reaction leading to the development of low yield subject to certain limitations. We use BF 3 · Et 2 O-catalyzed Friedel-Crafts reaction to achieve a high yield class of dendrimers green synthesis, constructed branched dendrimers G5 fluorenone structure can effectively suppress the green emission. In the solar cell material of the organic electroluminescence materials and made application of the organic optical materials to provide new synthetic methods and materials. In short, we help BF 3 · Et 2 O-catalyzed Friedel-Crafts reaction to build a series of multi-function and topology diarylfluorene compounds; the space steric hindrance group into the carbazole molecule which to explore three-dimensional effect on the molecular intra / inter-π stacking effects and regulation of the energy band structure, molecular structure and material properties to explore the relationship; and utilize such Friedel-Crafts reaction yield synthesize a series of dendrimer-like compound molecules, through its spectral characterization and electrochemical characterization, exploring such materials in the organic semiconductor device applications.

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