The Preparation And Characterization Of Bay-Substituted Perylene Diimide Derivatives

Perylene diimide(PDI)derivatives are a kind of polycyclic aromatic hydrocarbons with strong ?-? conjugation and good molecular coplanarity.PDI derivatives exhibit excellent optical,thermal and chemical stabilities.Thus,they have a wide application prospect in the fields of organic field-effect transistors,light-emitting diodes,solar cells,et al.The optical properties of PDI derivatives are closely related to their chemical structures and self-assembly behaviors.So it has important scientific significance and application value to study the chemical modification and aggregation structure.In this dissertation,we use perylene diimides as the basic building block,and a series of novel perylene derivatives were obtained via bay-functionalized modification and its self-assembly behaviors and optical properties were studied.The main research contents are as follows:(1)The development process and research status of organic photoelectric materials were briefly described.The research background,derivatization reactions and applications in fluorescent chemosensor were introduced.Then the modification of molecular structure and function exploration as the research topics were proposed.(2)Perylene diimide and polyhedral oligosilsesquioxane(POSS)were used as the raw materials.The unilateral selenium-heterocyclic perylene diimide POSS-SePDI and bilateral selenium-heterocyclic perylene diimide POSS-2SePDI were prepared through nitrification and the continued incorporation of selenium at the bay area.TGA and DSC experiments show that selenium-heterocyclic PDI derivatives have a good thermal stability.The experimental results of UV-Vis absorption spectra and fluorescence emission spectra reveal that the selenium-heterocyclic PDI derivatives still manifest obvious aggregation behaviors in high concentration solution and solid film state despite the large volume of substituents.In addition,X-ray diffraction experiments show that the selenium-heterocyclic PDI derivatives have three-dimensionally ordered crystal structures.(3)A series of tetrachlorinated diperylene diimides(4CldiPDIs)with different substituents were synthesized through Ullmann reaction promoted by L-proline and CuI.TGA experiment results show that these 4CldiPDI derivatives have a good thermal stability,spectrum experiment results manifest that these 4CldiPDI derivatives have broad absorption spectra and narrow bandgaps due to the increase in conjugate length.Therefore,these materials have potential application value in photovoltaic devices et al.(4)Through imidization,nitration,reduction and acetylation steps,amidated perylene diimide derivative POSS-AMPDI containing POSS substituent was obtained.Due to the silicon-oxygen bond cleavage mechanism and the deprotonation effect of the amide bond,such derivatives can be used for the selective detection of fluoride ion,which have potential applications in the field of visual sensors.