Preparation Supramolecular Assembly And Properties Of Perylene Diimide Derivatives

As an n-type organical semiconducting material, perylenetetracarboxylic dianhydride （PDIs）, havebeen widely applied in fluorescence probe, organic field-effect transistors, gas sensor and medicinebiological field. For the moment, the study of perylene imide derivatives is still very limited, however,much studies on the preparation of its one-dimensional nanostructures are very important in improvementof their devices property. In this dissertation, perylene imide possess important influence in thephotoelectric material derivatives, Herein, some perylenetetracarboxylic dianhydride derivaties aredesigned and synthesized, and their supramolecular self-assembly and propenties were investigated indetail. The main contents include:1. Compounds1,7-dibromoperylene-3,4:9,10-tetracarboxydianhydride、 N, N’-bis（n-dodecylamine）-perylene-3,4:9,10-bis（dicarboximide）(PTCDI-C₁₂), N,N’-bis（1H,1H-dodecy-lamine）-1,7-dibromoperylene-3,4:9,10–bis（dicerboximide）(PTCDI-Br₂C₁₂), N,N’-bis（n-dode-cylamine）-1,7-dicyano-perylene-3,4:9,10-bis-（dicerboximide）(PTCDI-CN₂C₁₂)are synthesized. Their super molecular self-assembly in thechloroform/methanol binary mixed solvent was studied and the micro/nano structures were obtained.Ammonia sensory properties based on conductometric gas sensors composed of single-crystallinemicro-/nanostructures of PTCDI-C₁₂, PTCDI-Br₂C₁₂and PTCDI-CN₂C₁₂were investigated and it foundthat core-cyanated PTCDI-CN₂C₁₂sensor was response to NH3gas. The initial sensitivity ofPTCDI-CN₂C₁₂sensor had a value of40%, then slight decreasing to37%in24h and could still keep astable value of37%after its exposure to air for14days.2. Compounds N,N’-bis（n-dodecylamine）-perylene-3,4:9,10-bis（dicarboximide）(PTCDI-C₁₂),N,N’-bis(n-dodecyla-3,4:9,10-bis-（dicarboximide）(PTCDI-ClC₁₂),N,N’-bis（1H,1H-heptafluorobutyl）-1,6,7,12-tetrachloroperylene-3,4:9,10-bis（dicerboximide）（PTCDI-ClC₄F₇） are synthesized. The determination ofsensing properties based on their conductometric gas sensors revealed that both PTCDI-ClC₁₂andPTCDI-ClC₄F₇devices had same sensitivity to hydrazine vapor and approximately4orders of magnitude inresistance decreased upon exposure to the hydrazine vapor （10ppm）. Whereas approximately2orders ofmagnitude in resistance decreased for another core-unsubstituted PTCDI-C₁₂gas sensor that was also prepared for comparison purpose. The reason for the differential response to the hydrazine vapor for thecore-tetrachlorinated PTCDI-ClC₁₂and core-unsubstituted PTCDI-C₁₂was independent of their surfacearea and morphologies and was ascribed to the difference in their reduction potentials that originated fromdifferent bay-substituted group and the twisted skeleton of the PTCDI-ClC₁₂molecule. The similar LUMOenergies level of PTCDI-ClC₁₂and PTCDI-ClC₄F₇leaded to both of them possessing similar sensingperformance, which in turn indicated the substituents at the imide positions have little effect on theimprovement of performance of perylenediimide derivatives gas sensors.3. Two perylenediimide derivatives N,N’-Bis（1H,1H-trifluoroethyl）-1,7-dibromoperylene-3,4:9,10-bis（dicarboximide）（PTCDI-3F） and N,N’-Bis（1H,1H-heptafluorobutyl）-1,7-dibromo-perylene-3,4:9,10-bis（dicarboximide）（PTCDI-7F） that bearing trifluoro ethyl and hepta-fluorine butyl at the imidepositions, respectively, were prepared. The determination of sensing properties based on theirconductometric gas sensors revealed that both devices were similarly sensitive to hydrazine vapor andapproximately4orders of magnitude in resistance decreased upon exposure to the hydrazine vapor （10ppm）. While the similar LUMO energies level of PTCDI-3F and PTCDI-7F leaded to both of thempossessing similar sensing performance, which in turn indicated the substituents at the imide positions havelittle effect on the improvement of performance of perylenediimide derivative gas sensors.