Synthesis Of Cyclic Phenanthroline Trimer And Its Application For COF System

Because the potential applications in the fields of energy storage, catalysis, separation, optical device and chemical sensing, the study on the covalent organic framework (COF) materials with their porosity and large surface area have become a new research field. Compared with the materials consisted of hydrogen bond associated skeletons or metal organic frameworks from coordination bonds, directly covalently bonded COF materials are more structurally stable with excellent heat resistance and hydrolysis resistance.The properties of COF materials are directly related to the design of the rigid skeleton unit. To date, the rigid frames mainly focus on a few compounds, such as porphyrin, phthalocyanine, triphenylene and pyrene etc., which greatly limits the development of COF materials. As an important class of nitrogen-containing organic conjugated molecules, phenanthroline possesses not only high stability but also excellent photoelectric activity and coordination feature and so on. Therefore, COF materials with phenanthroline as basic skeleton are expected to display new properties.This thesis mainly includes the following contents:(1) The synthesis of the monomer derivatives of halogen substituted phenanthroline.To synthesze the cyclic trimer,2,9-halogenated phenanthroline was chose as precursor. At first, the bromo-substitued compound7with high reactivty was prepared, which was proposed to be the precursor to syhthesize the rigid skeleton10. However, due to the polarity, it was difficult to separete out.Then chloro-substitued compound9with less reactivity was selected as the monomer, and the pure compound9was successfully obtained.(2) The synthesis of cyclic phenanthroline trimer of COF rigid unit.At first, with chloro-substitued compound9and bis(pinacolato)diboron as starting materials, rigid skeleton10was prepared through Suzuki-Miyaura coupling reaction with Pd-catalyst. By adjusting the reaction temperature and solvent, linear diphenanthroline11and dechlorinated by-product12were obtained respectively. Using compound9as starting materials through Ullmann reaction with Ni-catalyst, cyclic phenanthroline trimer10was successfully synthesized, which was verified by MALDI-TOF-Mass. On the other hand, to study the solubility of cyclic phenanthroline trimer, compound14with dodecyl chain was synthesized through Ullmann reaction. Although rigid skeleton14showed better solubility, no pure one was obtained due to the limitation of separation methods.(3) Application of cyclic phenanthroline frame for COF materials.With cyclic phenanthroline trimer10as rigid skeleton, the preliminary study to construct COF system was discussed.