1. Effect Of End-capping Functional Groups On The Optoelec Prohertles Of Olrgothiophene Perivatires2. New Nydrido Iron Lomplenes Swproreed By Pcmels;Sythnesis,Reactivity And Gatalytic Appliantion In Hydrasilyla Of Aryl Latenes And Aldehydes

In the past decade, linear oligothiophene derivatives were widely used in electrochromics, organic thin film field-effect transistors (OFETS), organic light-emitting diodes (OLEDS), liquid crystal materials, and solar cells, due to their excellent optical and electrical properties. In these applications, it was crucial that these materials possess sufficient stability in ambient air condition to maintain functional performance characteristics. It is clear that there is a direct relationship between the structure and the optoelectronic property of oligothiophene derivatives. It was already reported that, different functional groups could be introduced in the molecular backbone to tailor the optoelectronic property and stability of the materials. But some key factors in molecular design which lead to optimal optoelectronic properties and high stabilities have been not known. Until now, it is very difficult to figure out what kind of the molecular structure brings optimum performance. The varieties of oligothiophene derivatives with good performance are few. In the past, symmetrically end-capping oligothiophenes (including donor-oligothiophene-donor, acceptor-oligothiophene-acceptor and donor-oligothiophene-acceptor systems) have been investigated amply, while there are still fewer examples of asymmetrically end-capping oligothiophene derivatives. Recently, it has been reported that some asymmetrically end-capping oligothiophene derivatives with highly ordered arrange could lead to better charge transport compared to corresponding symmetrically end-capping systems.So. in this paper, five novel oligothiophene derivatives asymmetrically end-capped by different functional groups (R=ethoxyl (EtOP3T), methylsulfanyl (MSP3T), acetyl (AcP3T), methylsulfonyl (MSO2P3T) and biphenyl (BP3T) groups) were synthesized using P3T as precursor, and they were characterized by by H nuclear magnetic resonance (1H NMR), mass spectrometry (MS) and Fourier transform Infra-red spectra (IR). The relationship between end-capping functional groups and optoelectronic properties of them was investigated. Thermal gravity analysis (TGA) and Cyclic Voltammetry (CV) demonstrate that MSO2P3T shows the highest thermal stability and oxidation stability among the five compounds. The results of scanning electron microscope (SEM) interpret that MSO2P3T displays excellent ability of self-film forming. In addition, the liquid crystal property of MSO2P3T was observed by polarized optical microscopy analysis (POM), and MSO2P3T was characterized by X-ray diffraction(XRD) before and after annealing process. The results reveal that the powder of MSO2P3T mainly exist in the structure of three-dimensional crystalline phase. After annealing process via liquid crystalline state, the molecule of MSO2P3T arrange in laminar states (20=4.36°, the interlamellar spacing is20.22A) evidently. Finally, the optimal structures and frontier molecular orbitals (HOMO and LUMO) of five compounds were obtained by theoretical calculation, and the highest oxidation stability and the best charge-transfer performance of MSO2P3T were explained theoretically. The results of experiments and theoretical calculations demonstrate that MSO2P3T is a potential candidate for thin film material. Currently, transition metal (Fe, Co and Ni) complexes in place of precious metal complex, have been widely used in the area of organic chemistry, drug synthesis and industrial catalysis, due to its advantages of low cost, environmental friendly and low toxicity. Iron complexes in low valence draw more and more attentions of researchers for its high reactivity and high selectivity. Trimethylphosphine, as a strong ligand, can form stable complex with transition metals, and its complexes was widely used in the areas of the inert bonds activation, cyclical catalysis and mechanism research.In this paper, iron complexes supported by trimethylphosphine was used as starting materials to carry out our research. Main contents were classified into three parts:1The sp-C-H bond in4-methoxybenzophenone imine was activated to obtain two new hydrido iron complexes1and2, using Fe(PMe3)4and FeMe2(PMe3)4as starting materials. The complexes1and2were characterized by IR,’H NMR,’’P NMR and X-ray single crystal diffraction. The new reactions of hydride complexes with methyl iodide (CH4I), ethyl bromide (C2H5Br), carbon monoxide (CO), carbon dioxide (CO2), carbon disulfide(CS2) and trimethyl silyl acetylene(TMSA) were studied. The products were isolated and also characterized by IR,1H NMR and31P NMR. Furthermore, four products were obtained in single crystals, and their molecular structures were characterized by X-ray single crystal diffraction. In addition, the possible mechanism of some reactions were proposed.2The hydrido iron complexes(containing the structure of benzophenone imine)1.2,3and4were used in catalytic application for hydrosilylation of aryl ketones and aldehydes. The effects of catalysts,solvents, temperature, time and different silanes on catalytic reactions were discussed. The optimal condition for hydrosilylation of aryl aldehydes is:complex3as catalyst(0.6%), triethoxysilane as hydrogen source. THF as solvent, temperature55C and time3hours. The optimal condition for hydrosilylation of aryl ketones is:complex3as catalyst(0.6%). triethoxysilane as hydrogen source, THF as solvent, temperature55℃and time4hours. In addition, the possible mechanism of catalytic hydrosilylation was proposed. Finally, the products of hydrosilylation were hydrolyzed to get the reduction products(alcohols) which was purified by column chromatography(to obtain the isolated yields) and characterized by1HNMR.3As a nickel complex also supported by trimethylphosphine, NiMe2(PMe3)3reacts with benzophenone imine to realized N-H activation which give birth to a dinuclear nickel(II) complex.