The Synthesis And Catalytic Properties Of Novel Porous Organic Polymers

Along with the continuous development of the industrial society,energy shortage and environmental pollution caused by human activities have become increasingly prominent.To alleviate this situation,development of environmentally friendly ener-gy resource and new materials is urgent.Porous materials have undergone evolution from the inorganic skeleton to pure organic networks,which plays an important role in many modern fields of science and technology.And there has been an explosion in research of novel porous organic functional materials over the last 20 years.According to the structural characteristics,porous organic polymers are mainly divided into four categories.Among them,cova-lent organic frameworks（COFs）has become a hot topic in current research because of its advantages of high crystallinity,large specific surface area,excellent stability and ease of functionalization.More and more researches have attempted to increase the synthetic possibility in different ways.However,the reaction system usually consists of two or more monomers,one of the main problems is the complicated screening of synthetic conditions.On the other hand,the sp²-carbon fully conjugated polymers have attracted widespread attention since its emergence,due to its extremely high stability and unique optoelectronic properties.However,the synthesis methods mainly focus on Knoevenagel and aldol condensation currently.The less-reversible carbon-carbon double bond formation makes it still challenging to spatially construct a well-defined organic framework withπ-extended two-dimensional structure through solution pro-cess.Therefore,from the perspective of synthetic strategies,two different types of functionalized porous organic polymers were designed and prepared.Part one,we take porphyrin as the core unit and introduce both amino and formyl functional groups,subsequently,A₂B₂-Por-COF was obtained in a variety of solvents by self-polycondensation.The porphyrin-based covalent organic frameworks possess high specific surface area,stability,and show excellent catalytic performance in both selective oxidation of sulfides and Knoevenagel condensation reactions.This“two-in-one”strategy greatly simplifies the screening process of synthetic conditions and provides a new method for facile constructing of covalent organic frameworks.Part two,a series of sp²-carbon fully conjugated microporous polymers were success-fully synthesized by Horner-Wittig reaction,which stands as the first exploration to prepare unsubstituted olefin-linked porous organic polymers by this reaction.Moreo-ver,these polymers show extremely high stability and excellent luminescence per-formance,which would give rise to potential applications in the fields of photocataly-sis and photosensing.