Single Imide) Compound Synthesis, Modification And Nature Of The Research

Perylenediimides (PDIs) are key chromophores in dye stuff and pigmentchemistry. Due to their thermal, chemical, and photochemical stability as well as theirexcellent optical and electronic properties, they not only serve as industrial colorantsbut also find applications in organic field effect transistors, photovoltaic devices, andsingle molecule spectroscopy. Since the first member of the family was discovered in1913, PDIs have become one of the most important heterocyclic pigments. In recentyears, symmetrical perylene derivatives have been studyed deeply. But asymmetricperylene derivatives have been rarely discussed. In this paper, we have designed andsynthesized a series of asymmetric perylene monoimide derivatives, and discussedcharacterization of their structure, and their photophysical properties.Chapter1: The research and applications of perylene derivatives have beenreviewed. In addition, the research and applications of asymmetric perylenederivatives have been specially reviewed.Chapter2: A series of asymmetric perylene monoanhydride/monoimide diesterhave been designed and synthetized, and the photophysical properties have beendiscussed. The potassium salt of3,4,9,10-perylene tetracarboxylic acid wassynthetized by basic hydrolysis of3,4,9,10-perylene tetracarboxylic acid bisanhydride.The salt was treated with n-bromobutane in presence of K2CO3to obtain tetrabutylperylene tetracarbonate. In a mixed solvents of n-heptane and toluene, the ester wasacidic hydrolyzed by p-toluenesulfonic acid at one side to yield compounddibutyl-perylene-3,4-anhydride-9,10-dicarbonylate in80%yield.N-cyclohexyl-dibutyl-perylene-3,4-dicarboximide-9,10-dicarbonylate anddibutyl-perylene-3,4-dicarboximide-9,10-dicarbonylatewere synthesized by the imidization ofdibutyl-perylene-3,4-anhydride-9,10-dicarbonylate with cyclohexylamine andammonium acetate respectively. The bromination reaction of the3compounds werestudyed particularly. The1-Br-and7-Br-dibutyl-perylene-3,4-anhydride-9,10-dicarbonylate can be synthetized bybromination reaction, which can not be separated by column chromatography on silicagel. But1,7-diBr-dibutyl-perylene-3,4-anhydride-9,10-dicarbonylate only was thedibromo product. Only1-Br-N-cyclohexyl-dibutyl-perylene-3,4-dicarboximide-9,10-dicarbonylate was themono-bromo product.1,7-diBr-and1,6-diBr-N-cyclohexyl-dibutyl-perylene-3,4-dicarboximide-9,10-dicarbonylate were thedibromo product, which can not be separated by column chromatography on silica gel.The mono-bromo product of dibutyl-perylene-3,4-dicarboximide-9,10-dicarbonylatecontains indivisible1-Br-and7-Br-compound.1,7-diBr-and1,6-diBr-dibutyl-perylene-3,4-dicarboximide-9,10-dicarbonylate were the dibromo product,which can not be separated by column chromatography on silica gel. Chapter3: We can synthesize perylene monoimide in high yield by a method,which can be controlled. And the nitrification and substitution reaction of perylenemonoimide were studyed deeply. The synthesis started from tetrabutyl perylenetetracarbonate, which was acidic hydrolyzed by p-toluenesulfonic acid at one side toyield dibutyl-perylene-3,4-anhydride-9,10-dicarbonylate in a mixed solvents ofn-heptane and toluene.N-cyclohexyl-dibutyl-perylene-3,4-dicarboximide-9,10-dicarbonylate wassynthesized by the imidization of dibutyl-perylene-3,4-anhydride-9,10-dicarbonylatewith cyclohexylamine, which was acidic hydrolyzed by p-toluenesulfonic acid toyield perylene monoimide monoanhydride. Perylene monoimide was synthesized byadding Cu2O and perylene monoimide monoanhydride in toluene at refluxtemperatures. The nitration of perylene monoimide and the reaction of nitrationproduct of perylene monoimide with4-tert-butylphenol was studyed deeply. Wediscussed characterization of their structure, and their photophysical properties. Themono-nitrated perylene monoimide were synthesized, which contains1-nitro-and9-nitro-perylene monoimide.1,6-dinitro-,1,9-dinitro-and9,10-dinitro-perylenemonoimide were the three di-nitrated pruducts. The tri-nitrated perylene monoimidecontains1,6,9-trinitro-and1,9,10-trinitro-perylene monoimide. The di-nitrated andtri-nitrated perylene monoimide can be reacted whih4-tert-butylphenol step by step,but9,10-dinitro-perylene monoimide.Chapter4: Four asymmetric perylene derivatives were designed and synthesizedby brominated N-cyclohexyl-dibutyl-perylene-3,4-dicarboximide-9,10-dicarbonylatereacted with3-hydroxypyridine or8-hydroxyquinoline, which contained identifyinggroups. The interaction between four asymmetric perylene derivatives with ions insolution was analysised using UV-Vis and fluorescence spectra.