Design,Synthesis,and Property Study Of Organic Semiconductors Based On Derivatives Of Perylene Diimides And Naphthalene Diimides

Organic semiconductors have been paying much attention in the past ten years due to their many varieties, diverse nature, and low cost. At present, high performance materials has restricted the development of organic semiconductors. Perylene diimides and naphthalene diimides have showed potential applications as traditional organic semiconductors, and they have drawn much attention in the field of organic electronic materials. In this dissertation, we designed and synthesized a series of derivatives of perylene diimides (PDIs) and naphthalene diimides (NDIs) under the guidance of the organic chemistry knowledge and the design principle of organic semiconductors.1. By a new strategy, we first introduced two kinds of strong electron-withdrawing groups-trifluoromethyl and perfluorooctyl groups-to the bay area of 3,4,9,10-Perylene tetracarboxylic bis(benzimidazole) (PTCBI), and obtained three regioisomerically pure PTCBI derivatives 5a-5c. Compounds 5a-5c display strong solid state absorptions in the range of 400-700 nm, and their LUMO energy is at 4.37-4.43 eV indicating strong electron-accepting ability. Isomers mixture of PTCBI, trifluoromethyl-substituted PTCBI, and perfluorooctyl-substituted PTCBI are all n-type organic semiconductors with mobility 0.0071,0.002,0.0014 cm2 V-1 s-1, respectively, which is concluded by OFETs.2. A versatile synthesis of core-perfluoroalkylated PDIs and NDIs was developed, and with above method by esterification, perfluoroalkylation, hydrolysis, and condensation with amine,21 compounds including 1-perfluorooctyl-PDIs, 1,7-bis(perfluorooctyl)-PDIs, 1,6-bis(perfluorooctyl)-PDIs, mixture of 1,7-bis(trifluoromethyl)-PDIs and 1,6-bis(trifluoromethyl)-PDIs,2-perfluorooctyl-NDIs, and 2,6-bis(perfluorooctyl)-NDIs were efficiently synthesized. Solubility, electrochemistry and optical properties of above compounds were investigated. Their solubility can be adjusted by the size of alkyl groups attached on N atoms, and core-perfluoroalkylated 12e,13e,13f,13'e, mixture of 14d and 14'd,23b, and 23d with excellent solubility in common organic solvents are competitive as candidates of solution processable semiconductor. Core-perfluoroalkylated PDIs and NDIs with experimental LUMO energy 4.04-4.34 eV demonstrate strong electron accepting ability. For core-perfluoroalkylated PDIs have high fluorescence quantum yields (higher than 0.67).3. An efficient method of synthesizing oligomeric perylene by regioselective photocyclization was developed, and with this method, ladder oligomeric PDIs 28,29 and ladder oligomeric perylene ester 37 and 40 were obtained. Meanwhile, the key intermediates oligomeric perylene dianhydride (32 and 34) were efficiently obtained, which provide versatile platforms to produce oligomeric ladder PDIs with various functional side chains on the imide sites.4. For the first time, photocyclization with the sunlight was employed as a highly efficient and easy accessible method to obtain soluble ladder conjugated polymer. With this method, soluble ladder conjugated polymer LCPT was obtained. LCPT exhibits strong electron accepting ability, broad absorption, strong fluorescence, and excellent thermal stability, which make it a potential photoelectric material.