Synthesis, Characterization And Properties Of Solution-processable And Porous Diarylfluorene-based Organic Optoelectronic Polymers

Diaryl fluorenes are not only excellent raw materials to the preparation of organic photoelectric semiconductors but also 3D molecules with strong distortion that lack the flexibility to pack efficiently resulting in creation of sufficient free volumes to facilitate increased porosity, therefore they are suitable building blocks for the synthesis of porous polymers. Based on our previous works, in this thesis we have designed a series of plans to prepare porous polymers and resolved some problems existing in the filed of porous materials. In the first plan, two conjugated porous polymers, typical blue-light emitting materials, were produced via Yamamoto reaction and they display high surface area and excellent stabilities of thermal behavior. However, these polymers, synthesized in metal-catalyzed regimes, are not insoluble and infusible materials that destroyed solution-processable realization. In the second plan, a series of hypercrosslinked polymers were produced via BF3·Et2Omediated Feridel-Crafts reaction of oligomeric tertiary alcohol with arene and they present excellent stabilities of fluorescent emission and thermal behavior. Although these hypercrosslinked polymers have a rigid structure without any alkyl chains, they can still stably disperse in common organic solvents and be processed by solvent-casting to form contiguous films. Not only have we successfully producted solution-processable porous polymers but also the used reactions avoided metal-catalyzed regimes. Nevertheless, because hypercrosslinked polymers can not dissolve into organic solvents in real significance, their films with high quality can not be obtained that hinders their potential applications in other fields. In the third plan, we artfully synthesize an annular molecule that looks like the shape of rectangle via BF3·Et2O-mediated intramolecular Feridel-Crafts reaction. Based on this annular monomer, one soluble porous polymer, PGCz, was preparaed through Yamamoto reaction. Although the data about porosity of PGCz are not enough good, PGCz can be easily prepared into thin films with high quality and porous stractures by spin-coating and they also present excellent stabilities of fluorescent emission and thermal behavior. This kind of porous polymer has totally broken the long deadlock that porous organic polymers are hard to be processed, especially, as a solution, therefore this project is significative for multiple aspects of science.