Synthesis, Characterization Of Meso-Position Sulfur Embedded Quinoidal Bisanthene

Polycyclic aromatic hydrocarbons(PAHs) with large, extended ? conjugation and small band gaps have promising applications as functional materials. In recent year, design, synthesis, properties and application of novel polycyclic aromatic compounds draw much attention. As a family member, bisanthene could be described as being composed of two anthracene rings conjoined by three single bonds. Bisanthene has good characters such as small band gap and planar diene structure, it can serve as a good building block to construct new PAHs by appropriate design and chemical modifications. Besides, bisanthene has far-red absorption at 662 nm, indicating great potential as a building block for near infrared(NIR) dyes.Quinoidal ?-conjugation usually possess long-wavelength absorption and multistage redox properties which make it as promising organic electronic materials. In addition, incorporating hetero-atoms into conjugated skeleton is an intriguing target because the introduction of hetero-atoms would induce a variety of intermolecular interactions, such as van der Waals interactions and heteroatom-heteroatom interactions(S ? ? ?S or Se? ? ? Se interactions), which is essential to achieve highly ordered supramolecular self-assembled structure and eventually excellent device performance. In this dissertation, synthesis, characterization of meso-position Sulfur embedded Quinoidal bisanthene-based PAHs have been investigated in details which is divided into three parts as summarized below.In the first part, On the basis of the relevant literature, research background and the development of PAHs are briefly introduced. Then, the synthesis, properties and development of bisanthene are reviewed, and some typical quinoidal structure are also presented. The purpose, significance and content of the paper are introduced at last.In the second part, it describes the raw materials used in the experiments and chemical reagents, purification reagents, detection method. Thione were prepared from corresponding thioxanthen-9-one via reaction with Lawesson's reagent followed by the Barton-Kellogg reaction with 9-diazothioxanthene derived from corresponding hydrazine to afford the thioepoxides. The resulting compound were then treated with copper powder to give the desired olefin precursor. Katz-modified Mallory photocyclization was carried out on olefin precursor for the purpose to obtain the target molecule. The reaction was conducted by irradiation of the benzene solution of olefin precursor with a 450 W medium-pressure mercury vapor lamp in the presence of I2 and propylene oxide. Unfortunately, only the partially cyclized product were obtained in 77% yield because there is no more stilbene structure in compound. The spectroscopic properties, electrochemical properties of intermediates and products were studied.In the last part, all intermediate products and products were characterized by NMR, MS. The optical properties were studied by UV-vis and fluorescence spectroscopy, the electrochemical properties were recorded by Cyclic voltammetry, and the band gap and orbital energy were calculated.