Synthesis And Properties Of Dehydroabietic Acid-based Arvlamines Fluorescent Derivatives

Organic electroluminescent materials have attracted much attention in the research ofoptoelectronic information materials for the various advantages of lower turn-on voltage、fastresponse and high resolution, and so on. In additional, with the rapid development ofsupramolecular chemistry, the application of fluorescent molecular probe in life sciences hasattracted much attention. To design and synthesize some novel fluorescent derivatives havegradually become the focus of the organic synthesis field. In this dissertation, synthesis andfluorescent properties of dehydroabietic-based arylamines were investigated, and theirapplications as hole transporting materials in OLEDs and as fluorescent molecular probes intumor cells were performed, and some important results were obtained as follows:Firstly, two series of novel compounds comprising arylamine and dehydroabietic acidgroups were synthesized via C-N cross-coupling. For the first time, the diarylamines weresynthesized through C-N coulpling using palladium catalysts, instead of N-arylation reactionusing copper catalysts. The compounds were characterized by elemental analysis, FT-IR,NMR,mass spectrometry and X-ray diffraction. Their absorption、fluorescent spectra, quantum yield,lifetime, and fluorescent emission in solvents of different polority were studied.They haveabsorption maximum wavelength ranging from275-345nm，fluorescence emission rangingfrom348-448nm. The introduction of nathaphene and biphenyl moieties and electron-donorgroup causes a large red-shift of fluorescence emission spectra and increase of intensity. Anincrease of the solvent polarity causes a significant red-shift of the emission spectra of alldiarylamine compounds(5a~5g) and several triarylamine compounds with naphthalene(6f) andbisphenyl(6b,6h) moiety. However, the other triarylamine compounds only show minorresponses to solvent polarity. All compounds exsit different fluorescent intensity in differentpolarity solvents. Secondly, molecular configuration and HOMO、LUMO levels of compounds wereoptimized by DFT/B3LYP using Gaussian03. The relation bettween molecular structures andfluorescent properties was analysed. The results show the compounds with big conjugatedlength or substituents of electron-donor group exhibit narrower energy gap, which could havebetter fluorescent properties.The predicted results are in agreement with the experimentalvalues.Thirdly, the thermal properties and electrochemical of6a~6h were investigated bythermogravimetric analysis (TGA), differential scanning calorimetry(DSC), and cyclicvoltammetry (CV), respectively. The compounds present suitable HOMO levels (in a range of-4.63to-5.11eV) for hole injection, which is confirmed by theoretical calculations. Allcompounds are thermally stable. Organic light-emitting diode devices having6a、6d-6h as ahole transporting layer show better performance of maximum brightness, lower turn-on voltage,and maximum luminous efficiency than a comparable device NPB. These compounds could beexcellent candidates for applications in OLED devices.Finally, the fluorescence properties, photostability, cell toxicity and in vitro fluoresceneimaging of all compounds have been investigated. The percentage of cell survival aftertreatment of compounds5a~5g and6a~6h (2.0μM) to HeLa, SMMC-7721, SGC-7901andA549cells are above90%using the untreated cells as control, showing it has very lowcytotoxicity at this concentration. Fluorescence intensity of compounds5a、5b、5e、5g、6a、6b、6d、6e and6g have not obviously decrease as increase in irradiation duration, showing theirgood photostability. As seen from fluorescent imaging, compounds5a、5b、5e、5g、6a、6b、6d、6e and6g are all successfully taken up by all of the cells and strong blue fluorescencesignals are detected in these cells, suggesting it can be used as an effective fluorescent probe invitro. However, the cells treated with compounds5f、6c、6f and6h have no observedfluorescence sigal, which could be due to their lower photostability under the irradiation ofmicroscopy. In additional, after entrapping inside the tumor cells, the fluorescence intensity arenot uniform, the fluorescence intensity in cytoplasm is much stronger than in nuclear which indicating that the compounds accumulated in cytoplasm. Above properties indicate that thesecompoumds have potential to be used as cytoplasm fluorescent probes in biological diagnose.