Synthesize And Self-assembly Of Dendritic Functional Polymers Based On Perylene Bisimide/Triazine

Supramolecular chemistry is the chemistry which focuses on architecture and functionalization of molecular aggreagets associated with weak inter-actions. These weak interactions include vander Waals, hydrogen bonding,π-πinteraction, hydrophobic interaction and etc. Supramolecular self-assembly via molecular recognition has been one core branch of supramolecular chemistry. Dendrimers are a new class of macromolecules which are synthesized in a repetitive reaction sequence of nearly quantitative reactions by branch group. They have recently attracted much attention because of their unique property of controllable well-defined structure by hierarchically reaction and consequent novel physical and chemic properties. 1, 3, 5-Triazine dendritic derivatives can be used as donor and acceptor in hydrogen bonding at the same time, so that they have been widely applied in supramolecular self-assembly because of their special characters.In this dissertation, we have synthesized dendritic functional polymers by condensation reaction between three different triazine dendrons and Perylene-3,4,9,10-tetracarboxylic acid dianhydride based on summarization of literatures, then further studied their photoelectronic property and micro-structure of the self-assembly. Firstly, 2, 4-bis（laurylamino）-6-chloro-1, 3, 5- triazine were prepared used cyanuric chloride and Lauryl amine as raw materials, then the triazine-based dendrons have been synthesized separatelly used 1,6-hexamethylendiamine, 1,2-ethanediamine, N-Aminoethylpiperazine linking groups by the convergent method, which have been used in the chemic decorate of Perylene-3,4,9,10-tetracarboxylic acid dianhydride at last. So, three new dendritic polymers were synthesized: S1, S2, S3. Their chemic structures were confirmed by IR and ¹HNMR, and the conditions of synthesize were discussed.The hydrogen bonding and intenseπ-πinteraction in the self-assembly process of S1、S2、S3 have been investigated by ¹HNMR, Uv/Vis and fluorescence spectra. Due to the different structure of the three dendritic polymers, there are some difference between their UV/Vis and fluorescence spectra in the different solvents .The property in the UV/Vis and fluorescence spectra showed the formation of face-to-face H-type aggregates in all solvents.Considering the structure character, changing solvents, concentration of monomers, assembly time, the micro-structures of S1、S2、S3 under different conditions were emphatically investigated. SEM images indicated that honeycomb-film could be obtained under the specifically concentration of all three dendritic polymers in solvent. The effect of time and concentration on the micro-structure of S1、S2 and S3 was remarkable. The results also showed that well-defined sphere structure can only be obtained by self-assembly of S1 and S2 in CH₂Cl₂ solution but not found in S3 and that only the sphere structure in S1 could slowly growth into stick stucture along with the time. To our best knowledge, these outcomes were fist reported and supplied as a novel material for functional devices.It was founded in these systemically investigation that the morphology of the self-assembly were not only related to the structures of dendritic polymers, hydrogen bonding andπ-πinteraction, but also to the solvents, concentration of monomers and assembly time. These results provide an important scientific basis to the study on further develop new-style dendritic function polymers, the influences for the morphology control of supramolecular on different conditions and the mechanism of self-assembly. It is a great meaning to the dominate of functional supramolecular polymers in the application of function nano-photoelectronic devices.