Construction And Application Of Crystalline Porous Organic Structures Via The Schiff Base Formation

Crystalline, porous, organic structures are widely used in gas storage, heterogeneous catalysis, and photoelectricity due to their regular arrangements, large surface area, and easy functionalization. It is one of the research topics to design and synthesize functional crystalline porous organic structures.This thesis is focusing on the designed synthesis of functional organic porous crystalline structures and their applications. Utilizing the "bottom-up" strategy, we made the following progress:1. Using a double hydroxyl functionalized2,3-dihydroxyterephthalaldehyde and a planar1,3,5-tris(4-aminophenyl)benzene as the building blocks, a crystalline covalent organic framework (COF-OH) was successfully synthesized via the Schiff base formation in solvothermal conditions. COF-OH material has a2-D hexagonal crystalline structure and a large BET surface area of864m2/g. By utilization of the double hydroxyl functional groups, Cu(OAc)2-H2O was loaded into COF-OH material via the coordination bonds. The Cu incorporated material could be used as herterogeneous catalyst, and showed high activity in the Henry reaction.2. Using a azobenzene molecules as the functional building block, a crystalline covalent organic framework (COF-Azo) was successfully synthesized via the Schiff base formation. COF-Azo material possesses highly regular structure and a BET surface area of47m2/g. By utilization of the azobenzene functional groups, the dynamic response of COF-Azo material was tested by the irritation by UV light.3. Using the chiral norbornadiene diamine molecule as the functional building block, a crystalline0-D chiral macrocyclic structure was successfully synthesized via the Schiff base formation. The formation mechanism of the macrocyclic structure and their application in the detection of small molecules were investigated. Moreover, the macrocyclic structure could be easily reduced to the stable C-N crystalline structure.